Sodium alginate fiber biological material fiber with hollow structure and preparation method thereof

Abstract

The invention discloses a preparation method of a sodium alginate fiber biological material fiber with a hollow structure and a sodium alginate fiber.The preparation method comprises the following steps that 101, CaCl2 particles are dissolved in deionized water and fully stirred, and a CaCl2 / H2O core layer spinning solution is prepared; step 102, dissolving sodium alginate in deionized water, heating to improve the solubility of the sodium alginate in the deionized water, and fully stirring to obtain an SA / H2O cortex spinning solution; and step 103, respectively extruding the SA / H2O skin layer spinning solution and the CaCl2 / H2O core layer spinning solution into a CaCl2-removed coagulating bath through a coaxial needle at the speeds of 200 [mu] L.min <-1 > and 200 [mu] L.min <-1 >, and aging to obtain the hollow fiber. According to the preparation method, a coaxial spinning process is adopted, and the problems of fluid fracture and the like caused by drafting instability can be effectively avoided. Hollow fibers are used for replacing solid rod-shaped fibers, the process is efficient, convenient, energy-saving and environment-friendly, the experiment repeatability is high, a high-voltage electric field and toxic substances are not involved in the preparation process, and damage to biological tissues is avoided.

Description

Technical Field

[0001] The invention relates to the technical field of sodium alginate fiber biomaterials, in particular to a method for preparing sodium alginate fiber biomaterial fibers with a hollow structure and the sodium alginate fibers. Background Art

[0002] Sodium alginate is a multifunctional natural polysaccharide with good stability, solubility and viscosity. It has a wide range of application potentials and plays an important role in many fields such as food, pharmaceuticals, and water treatment. With the increasing demand for natural materials and the pursuit of environmentally friendly products, the application prospects of sodium alginate are even broader. Sodium alginate fiber is a biopolymer fiber obtained by wet spinning or electrospinning technology using polyanionic polymers extracted from algae as raw materials. It has hygroscopicity and high biocompatibility and is widely used in biomedical fields such as tissue engineering, cell culture, and drug delivery. The traditional wet spinning technology is to dissolve sodium alginate into a solution and then inject the spinning solution into a coagulation bath through the spinning nozzle. The silk flow solidifies into silk in a very short time. However, the silk spun in this way is a solid round rod with a low specific surface area, adsorption energy, and poor loading effect. At the same time, the mechanical properties of the round rod-shaped fiber are poor. Such a structure limits the application field of sodium alginate fiber.

[0003] Therefore, how to produce a functional sodium alginate fiber with high specific surface area, high mechanical properties, high adsorption and release capacity and capable of transporting drugs is a problem that needs to be urgently solved in the present invention. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a sodium alginate fiber biological material fiber with a hollow structure and the sodium alginate fiber to solve the problems in the prior art.

[0005] In a first aspect, the present invention provides a method for preparing a sodium alginate fiber biomaterial fiber having a hollow structure, comprising the following steps:

[0006] Step 101, dissolving CaCl2 particles in deionized water, stirring fully, to obtain a CaCl2 / H2O core layer spinning solution;

[0007] Step 102, dissolving sodium alginate in deionized water, heating to increase the solubility of sodium alginate in the deionized water, and stirring sufficiently to obtain a SA / H2O skin spinning solution;

[0008] Step 103: The SA / H2O skin spinning solution and the CaCl2 / H2O core spinning solution were respectively passed through a coaxial needle at a rate of 200 μL·min －1 and 200 μL·min －1The hollow fibers were extruded into a CaCl2 coagulation bath and aged at a speed of .

[0009] As described above, the method for preparing the sodium alginate fiber biomaterial fiber with a hollow structure, wherein, preferably, in step 101, the amount of CaCl2 used is 5g, the amount of deionized water used is 95g, and the mass fraction of the CaCl2 / H2O solution is 5wt%.

[0010] As described above, the method for preparing the sodium alginate fiber biomaterial fiber with a hollow structure, wherein, preferably, in step 102, the amount of sodium alginate used is 1.0004 g, the amount of deionized water used is 19.0002 g, and the mass fraction of the SA / H2O solution is 5 wt%.

[0011] As described above, in the method for preparing the sodium alginate fiber biomaterial fiber with a hollow structure, preferably, in step 102, the heating treatment time is 4 hours, the heating temperature is 60° C., and the speed of the magnetic stirrer is 600 r / min.

[0012] As described above, in the method for preparing the sodium alginate fiber biomaterial fiber with a hollow structure, preferably, in step 103, the specification of the coaxial needle is 17G / 21G.

[0013] In a second aspect, the present invention provides a sodium alginate fiber, which is prepared by the aforementioned method for preparing a sodium alginate fiber biological material fiber with a hollow structure.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] 1. The preparation method adopts coaxial spinning process, which can effectively avoid problems such as fluid rupture caused by drafting instability. Hollow fibers are used instead of solid rod-shaped fibers. The process is efficient, convenient, energy-saving and environmentally friendly, and the experimental repeatability is strong. The preparation process does not involve high-voltage electric fields and toxic substances, and will not cause harm to biological tissues.

[0016] 2. The sodium alginate fiber obtained by the preparation method of the present invention has a special internal structure, namely a hollow structure. The fiber with this structure has a high specific surface area, and the surface area per unit volume is much higher than that of solid fiber, which makes it have unique advantages in many occasions where specific surface area is required; the hollow fiber has high permeability, and the existence of the internal cavity makes it easier for liquid or gas to pass through the fiber, thereby improving the permeability; the structure of the hollow fiber has good mechanical properties and can withstand greater pressure and tension.

[0017] 3. The hollow sodium alginate fibers obtained by the preparation method of the present invention can obtain fibers with different morphologies by adjusting the type of needle or the concentration of the sodium alginate solution. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a simplified introduction diagram of the preparation method of the present invention;

[0019] Figure 2 is the appearance image of sodium alginate fibers with different contents prepared in Example 1;

[0020] Figure 3 The sodium alginate and Ca mentioned in Example 1 2+ Cross-linked structure;

[0021] Figure 4 is the tensile curve of sodium alginate fibers with different contents prepared in Example 1;

[0022] Figure 5 is an infrared image of sodium alginate fibers with different contents prepared in Example 1;

[0023] Figure 6 These are appearance images of sodium alginate fibers obtained in Example 2 under different treatment methods;

[0024] Figure 7 is the tensile curve of the sodium alginate fiber obtained in Example 2 under different treatment methods;

[0025] Figure 8 These are SEM images of the cross sections of the solid fibers and hollow fibers prepared in Example 2. DETAILED DESCRIPTION

[0026] The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, but should not be construed as limiting the present invention.

[0027] In a first aspect, the present invention provides a method for preparing a sodium alginate fiber biomaterial fiber having a hollow structure, comprising the following steps:

[0028] Step 101, dissolving CaCl2 particles in deionized water, stirring thoroughly, to obtain a CaCl2 / H2O core layer spinning solution.

[0029] Step 102: dissolving sodium alginate in deionized water, heating to increase the solubility of sodium alginate in the deionized water, and stirring sufficiently to obtain a SA / H2O skin spinning solution.

[0030] Step 103: The SA / H2O skin spinning solution and the CaCl2 / H2O core spinning solution were respectively passed through a coaxial needle at a rate of 200 μL·min －1 and 200 μL·min －1 The hollow fibers were extruded into a CaCl2 coagulation bath and aged at a speed of .

[0031] In the embodiment provided in the present application, in step 101, the amount of CaCl2 is 5g, the amount of deionized water is 95g, and the mass fraction of CaCl2 / H2O solution is 5wt%. In step 102, the amount of sodium alginate is 1.0004g, the amount of deionized water is 19.0002g, and the mass fraction of SA / H2O solution is 5wt%. In step 102, the heating time is 4h, the heating temperature is 60°C, and the speed of the magnetic stirrer is 600r / min. In step 103, the coaxial needle specification is 17G / 21G.

[0032] The preferred preparation method comprises the following steps:

[0033] First, the cortical solution is prepared. In a container, sodium alginate is dissolved in deionized water to prepare a sodium alginate solution with a mass fraction of 5wt%. Because it takes a certain amount of time for sodium alginate to dissolve in water, the temperature can be appropriately increased to speed up the dissolution of sodium alginate in deionized water. Usually, we use a water bath to heat the sodium alginate solution at a temperature of 40-60°C. At the same time, in order to increase the dissolution rate of sodium alginate particles, sodium alginate is added to deionized water at room temperature in multiple times.

[0034] Next, the core layer solution is prepared by dissolving calcium chloride in deionized water in a container to prepare a calcium chloride solution with a mass fraction of 5 wt%. Solid calcium chloride particles have a strong solubility in deionized water, and can be fully dissolved in deionized water by stirring with a glass rod.

[0035] Then, prepare the sodium alginate gel fiber with hollow structure: inject the spinning solution into the coaxial needle respectively, wherein the injection speed of the cortex spinning solution and the core spinning solution is 200 μL / min, try to observe and control the stop and start of the syringe to make the cortex spinning solution and the core spinning solution enter the needle at the same time, and then inject it into a coagulation bath with a calcium chloride concentration of 5wt%, so as to form a gel by the cross-linking reaction of sodium alginate and divalent metal ions to prepare the gel fiber. The coagulation bath is configured by calcium chloride and deionized water. When the spinning solution enters the coagulation bath, it is coagulated into fibers instantly. The fiber formation mechanism is mainly that sodium alginate will quickly exchange ions when encountering calcium ions to form irreversible calcium alginate gel. The immersion time of the gel is also crucial, and it needs to be immersed in the coagulation bath for 0.5-1h. If the immersion time is too short, the gel reaction of sodium alginate is incomplete.

[0036] Finally, the fibers were washed with deionized water and dried at room temperature.

[0037] In a second aspect, the present invention provides a sodium alginate fiber, which is prepared by the aforementioned method for preparing a sodium alginate fiber biological material fiber with a hollow structure. The hollow sodium alginate fiber prepared by the method of the present invention has a good specific surface area and mechanical properties, and the formation of a hollow tube meets more field requirements, has special functionality, and changes the structure of sodium alginate that only has a cylindrical and oblate cylindrical shape, providing more possibilities for the use of sodium alginate fiber.

[0038] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0039] Example 1

[0040] This embodiment discloses a method for preparing a sodium alginate fiber with a hollow structure prepared from a solution with a mass concentration of 1wt%, 3wt%, 5wt%, or 7wt%, comprising the following steps:

[0041] 1) CaCl2 was added and dissolved in deionized water to prepare a CaCl2 / H2O core layer spinning solution.

[0042] 2) SA is added and dissolved in deionized water, and the mixture is heated, stirred and mixed to obtain a SA / H2O skin spinning solution.

[0043] 3) SA / H2O skin spinning solution and CaCl2 / H2O core spinning solution were respectively passed through the coaxial needle at 200 μL·min －1 and 200 μL·min －1 The fiber is extruded into a deionized water coagulation bath at a speed of 0.5-1h to obtain the fiber.

[0044] The fiber obtained in Example 1 was displayed in appearance, and the result is as follows: Figure 2 shown; Figure 2 A is 1wt% fiber; Figure 2 B is 3wt% of fiber, Figure 2 C is 5wt% fiber, Figure 2 D is 7 wt% of fibers. Figure 2 Although there is a fiber structure on the surface of A, its continuity is poor, the surface is not smooth, and the texture is soft. Figure 2 B and Figure 2 The fiber wall of C is smooth and has good fiber structure. Figure 2 D cannot form fibers, probably because the viscosity of 7 wt % sodium alginate solution is too high.

[0045] A single tensile test was performed on 1wt%, 3wt%, and 5wt% sodium alginate hollow fiber gels using a mechanical tensile machine. The results are as follows: Figure 3 As shown in the figure, it shows that with the increase of the mass concentration of sodium alginate, the mechanical properties of the fiber are strengthened to varying degrees. The reason may be that the increase of the content of sodium alginate provides more carboxyl groups and Ca 2+ Electrostatic interactions occur, and the increase in carboxyl content results in more oxygen atoms acting as sites for Ca 2+ Chelation occurs, making the alginate chains more tightly bound and more coordinated, forming a stable structure, such as Figure 4 shown.

[0046] Figure 5 The near infrared spectra of 1wt%, 3wt%, and 5wt% sodium alginate hollow fiber gels are shown in Figure 1. －1 Left and right and 3300cm －1 The stretching vibrations of the O-H bond and the C=O bond of the carboxyl group are on the left and right, and the peak intensity increases with the increase of sodium alginate concentration.

[0047] Example 2

[0048] This embodiment discloses various processing methods of sodium alginate fibers and comparison with solid rod-shaped sodium alginate fibers, including the following steps:

[0049] 1) The best sample, i.e. 5 wt% hollow sodium alginate fiber, was selected from Example 1 above;

[0050] 2) Taking out sections of 5wt% sodium alginate fiber and placing them in air for 12h-24h;

[0051] 3) taking a portion of the 5wt% sodium alginate fiber in sections and drying them in an oven at a temperature of 50°C for a drying time of 15 min to 20 min;

[0052] 4) taking a portion of the 5wt% sodium alginate fiber in sections and soaking it in a 75% ethanol-water solution for 12h-24h;

[0053] 5) A 5 wt % sodium alginate solution is placed in a syringe with a needle of 14G, and injected into a coagulation bath with a calcium chloride concentration of 5 wt % to obtain solid sodium alginate fibers.

[0054] The appearance of the above five types of fibers are shown in the figure below: Figure 6 shown. Figure 6 A is the fiber that has been oven dried for 15-20 minutes; Figure 6 B is the fiber air-dried for 12h-24h; Figure 6C is a solid rod-shaped fiber; Figure 6 D is the fiber treated with ethanol aqueous solution.

[0055] The mechanical properties of the above five fibers are compared. Figure 7 As shown, the following conclusions are drawn: the prepared gel fiber will lose water and its mechanical properties will decrease; the mechanical properties of hollow sodium alginate fiber are better than those of solid sodium alginate fiber, where the tensile stress and strain of hollow fiber are about 2MPa and 300% respectively, while the tensile stress and strain of solid fiber are about 0.6MPa and 130%; ethanol-water solution is not conducive to the preservation of fiber and will reduce the elongation of fiber.

[0056] The microstructure of 5wt% hollow sodium alginate fiber is compared with that of solid sodium alginate. The SEM image is shown in Figure 8 shown.

[0057] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0058] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0059] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

[0060] The above describes in detail the structure, features and effects of the present invention based on the embodiments shown in the drawings. The above is only a preferred embodiment of the present invention, but the present invention is not limited to the scope of implementation shown in the drawings. Any changes made according to the concept of the present invention, or modifications to equivalent embodiments with equivalent changes, which still do not exceed the spirit covered by the description and drawings, should be within the protection scope of the present invention.

Claims

1. A method for preparing a sodium alginate fiber biological material fiber with a hollow structure, characterized in that: The following steps are involved: Step 101, dissolving CaCl2 particles in deionized water, stirring fully, to obtain a CaCl2 / H2O core layer spinning solution; Step 102, dissolving sodium alginate in deionized water, heating to increase the solubility of sodium alginate in the deionized water, and fully stirring with a magnetic stirrer to obtain a SA / H2O skin spinning solution; Step 103: The SA / H2O skin spinning solution and the CaCl2 / H2O core spinning solution were respectively passed through a coaxial needle at a rate of 200 μL·min －1 and 200 μL·min －1 The hollow fibers were extruded into a CaCl2 coagulation bath and aged at a speed of .

2. The method for preparing a sodium alginate fiber biological material fiber with a hollow structure according to claim 1, characterized in that: In step 101, the amount of CaCl2 used is 5g, the amount of deionized water used is 95g, and the mass fraction of the CaCl2 / H2O solution is 5wt%.

3. The method for preparing a sodium alginate fiber biological material fiber with a hollow structure according to claim 1, characterized in that: In step 102, the amount of sodium alginate used is 1.0004 g, the amount of deionized water used is 19.0002 g, and the mass fraction of the SA / H2O solution is 5 wt%.

4. The method for preparing a sodium alginate fiber biological material fiber with a hollow structure according to claim 1, characterized in that: In step 102, the heating treatment time is 4 hours, the heating temperature is 60° C., and the speed of the magnetic stirrer is 600 r / min.

5. The method for preparing a sodium alginate fiber biological material fiber with a hollow structure according to claim 1, characterized in that: In step 103, the coaxial needle specification is 17G / 21G.

6. A sodium alginate fiber, characterized in that: The hollow-structured sodium alginate fiber is prepared by the method for preparing the biological material fiber according to any one of claims 1 to 5.

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