HPC / CA nanofiber membrane and preparation method and application thereof

The HPC/CA nanofiber membrane was prepared by electrospinning, which solved the water solubility problem of hydroxypropyl cellulose, achieved the morphological stability of the nanofiber membrane, and expanded its application in the medical field.

CN120776512APending Publication Date: 2025-10-14MINJIANG UNIVERSITY
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Patent Information

Application Number
CN202410402346.8
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-04-03
Publication Date
2025-10-14

AI Technical Summary

Technical Problem

The high water solubility of hydroxypropyl cellulose limits its application in the medical field and makes it difficult to maintain the morphology of the nanofiber membrane.

Method used

HPC/CA nanofiber membrane was prepared by electrospinning. Hydroxypropyl cellulose and cellulose acetate were mixed, N,N-dimethylformamide was used as solvent, the stirring temperature and heating rate were controlled to form a stable HPC/CA mixed solution, and electrospinning was performed in a low humidity environment.

Benefits of technology

The water solubility problem of HPC is overcome, so that the nanofiber membrane still maintains its morphology after contacting water, broadening its application in the biomedical field.

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Abstract

The invention discloses an HPC / CA nanofiber membrane and a preparation method and application thereof, the preparation method comprises the following steps: mixing hydroxy propyl cellulose, cellulose acetate and N, N-dimethylformamide, stirring until the hydroxy propyl cellulose and the cellulose acetate are dissolved, and cooling at room temperature to obtain an HPC / CA mixed solution; the HPC / CA mixed solution is subjected to electrostatic spinning, and the HPC / CA nanofiber membrane is obtained. HPC and CA are mixed through heating and stirring to prepare an HPC / CA mixed solution, then HPC and CA are fully combined under the action of high voltage through electrostatic spinning so as to achieve modification of CA on HPC, the obtained HPC / CA nanofiber membrane still keeps the morphology of the nanofiber membrane after being dried in water, the high water solubility of hydroxy propyl cellulose is overcome, the problem that HPC is melted in water is solved, and the HPC / CA nanofiber membrane has good application prospects. Therefore, the polymer material can be widely applied in the future life, and the application range of the polymer material in the field of biological medicines is widened.
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Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer medical materials, and particularly relates to a HPC / CA nanofiber membrane and a preparation method and application thereof. BACKGROUND

[0002] Hydroxypropyl cellulose (HPC) is a semi-synthetic organic compound, which is a non-ionic cellulose ether and is easily soluble in water, ethanol and other polar organic solvents. The hydroxypropyl cellulose has good biocompatibility, excellent film-forming property, no pharmacological effect and toxicity, no harm to physiology, strong antibacterial property and biodegradability. The superior conditions of the hydroxypropyl cellulose make it a new type of pharmaceutical excipient, which has great potential in the medical application prospect. In addition to the medical field, the hydroxypropyl cellulose is also widely used in injection devices, coatings, cosmetics, food and papermaking fields. However, due to the characteristic that the hydroxypropyl cellulose is dissolved in water, the practical application of the hydroxypropyl cellulose is hindered, and therefore the application of the HPC nanofiber membrane in the medical field cannot be promoted. SUMMARY

[0003] In view of the defects in the prior art, the purpose of the present application is to provide a preparation method of a HPC / CA nanofiber membrane, which uses hydroxypropyl cellulose (HPC) as a base material, uses N,N-dimethylformamide (DMF) as a solvent and adds cellulose acetate (CA), and uses an electrospinning method to construct a nanofiber membrane.

[0004] Another purpose of the present application is to provide a HPC / CA nanofiber membrane.

[0005] Another purpose of the present application is to provide the application of the above-mentioned HPC / CA nanofiber membrane in high polymer medical dressings.

[0006] The purpose of the present application is achieved by the following technical solutions.

[0007] A preparation method of a HPC / CA nanofiber membrane, comprising the following steps:

[0008] Step 1, mixing hydroxypropyl cellulose (HPC), cellulose acetate (CA) and N,N-dimethylformamide (DMF), stirring until the hydroxypropyl cellulose (HPC) and the cellulose acetate (CA) are dissolved, cooling at room temperature to obtain a HPC / CA mixed solution, wherein the mass ratio of the hydroxypropyl cellulose (HPC) to the cellulose acetate (CA) is (0.6-1):(0.2-0.5);

[0009] In step 1, the ratio of the mass fraction of the hydroxypropyl cellulose (HPC) to the volume fraction of the N,N-dimethylformamide (DMF) is (6-10):100, the unit of the mass fraction is g, and the unit of the volume fraction is mL.

[0010] In step 1, the stirring speed is 300-800 rpm.

[0011] In step 1, after mixing the hydroxypropyl cellulose (HPC), the cellulose acetate (CA) and the N,N-dimethylformamide (DMF), the mixture is first stirred at room temperature 15-30℃ for 4-7 h, then stirred at 30-40℃ for 2-4 h, and finally stirred at 50-60℃ for 1-4 h.

[0012] In the above technical solution, the temperature rising rate from room temperature 15-30℃ to 30-40℃ is 5-15℃ / h, and the temperature rising rate from 30-40℃ to 50-60℃ is 5-15℃ / h.

[0013] In step 2, the HPC / CA mixed solution is subjected to electrospinning to obtain an HPC / CA nanofiber membrane.

[0014] In step 2, the electrospinning is performed in an environment with air relative humidity ≤30% RH.

[0015] In step 2, the feeding flow rate of the electrospinning is 0.5-1.0 mL / h, the horizontal distance between the nozzle and the center of the collection spool is 15-20 cm, and the vertical distance is 10-15 cm; the rotation speed of the collection roller is 250-300 rpm, the outer diameter of the needle tip is 1.28 mm, and the inner diameter of the needle tip is 0.86 mm.

[0016] In step 2, the voltage of the electrospinning is 22-30 V.

[0017] An HPC / CA nanofiber membrane, comprising: hydroxypropyl cellulose (HPC) and cellulose acetate (CA), wherein the ratio of the hydroxypropyl cellulose (HPC) to the cellulose acetate (CA) is (6-10):(2-5) in terms of mass fraction.

[0018] Application of the above HPC / CA nanofiber membrane in high polymer medical dressings.

[0019] Compared with the prior art, the present application has the beneficial effects that: the present application mixes HPC and CA by heating and stirring to prepare an HPC / CA mixed solution, and then fully combines HPC and CA under the action of high voltage electricity by electrospinning to realize the modification of HPC by CA, so that the obtained HPC / CA nanofiber membrane still maintains the morphology of the nanofiber membrane after drying in water, overcomes the high water solubility of hydroxypropyl cellulose (HPC), solves the problem that HPC is dissolved in water, and enables the HPC to be more widely used in future life, thereby widening the use of such high polymer materials in the field of biological medicine. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 is a photo of the HPC / CA nanofiber membrane in the first control group;

[0021] Figure 2 is a photo of the HPC / CA nanofiber membrane after being soaked in water at 25℃ for 1h;

[0022] Figure 3 is a morphology diagram of the HPC / CA nanofiber membrane in the first experimental group under a scanning electron microscope after being soaked in water and dried;

[0023] Figure 4 is a morphology diagram of the HPC / CA nanofiber membrane in the first control group under a scanning electron microscope;

[0024] Figure 5 is a biological atomic force microscope observation diagram of the HPC / CA nanofiber membrane in the second control group;

[0025] Figure 6 is a biological atomic force microscope observation diagram of the HPC / CA nanofiber membrane in the second experimental group in a wet state after being soaked in water. DETAILED DESCRIPTION

[0026] The technical solutions of the present application are further described below in combination with specific embodiments.

[0027] The raw materials involved in the following examples are as follows:

[0028] Hydroxypropyl cellulose (HPC) is purchased from Nanjing Yujian Pharmaceutical Technology Co., Ltd.;

[0029] Cellulose acetate (CA) is purchased from Shanghai Maikelin Biochemical Technology Co., Ltd.;

[0030] N,N-dimethylformamide (DMF) is purchased from Shanghai Wakai Biotechnology Co., Ltd.

[0031] The instruments and models involved in the following examples are as follows:

[0032] Electrospinning machine, JDF05 (Changsha Nayi Instrument Technology Co., Ltd., Changsha, China).

[0033] The rotation speed of magnetic stirring in the following examples was 600 rpm.

[0034] Example 1

[0035] A preparation method of an HPC / CA nanofiber membrane, comprising the following steps:

[0036] Step 1, 0.7 g of hydroxypropyl cellulose (HPC), 0.3 g of cellulose acetate (CA) and 10 mL of N,N-dimethylformamide (DMF) were mixed in a beaker, and stirred at room temperature of 25 °C for 6 h, under stirring, heated in a water bath to 40 °C (the heating rate from room temperature to 40 °C was 10 °C / h), and then continuously stirred at 40 °C for 4 h, finally, under stirring, heated in a water bath to 60 °C (the heating rate from 40 °C to 60 °C was 10 °C / h), and stirred at 60 °C for 3 h until HPC and CA were completely dissolved, and cooled at room temperature of 25 °C for 1 h (under stirring), to obtain an HPC / CA mixed solution;

[0037] Step 2, electrospinning was performed after the HPC / CA mixed solution was taken by a syringe, to obtain an HPC / CA nanofiber membrane, wherein the air relative humidity of electrospinning was 30% RH, the feeding flow rate was 0.5 mL / h, the horizontal distance between the nozzle and the center of the collection spool was 20 cm, the vertical distance between the nozzle and the center of the collection spool was 15 cm; the rotation speed of the collection drum was 300 rpm, the nozzle was an international standard 18G type needle (the outer diameter of the needle tip was 1.28 mm, the inner diameter was 0.86 mm, and the voltage of electrospinning was 30 kV.

[0038] Example 2

[0039] A preparation method of an HPC / CA nanofiber membrane, which was basically the same as the “preparation method of an HPC / CA nanofiber membrane” in Example 1, and the only difference was that “0.7 g of hydroxypropyl cellulose (HPC), 0.3 g of cellulose acetate (CA) and 10 mL of N,N-dimethylformamide (DMF) were mixed in a beaker” was replaced by “1 g of hydroxypropyl cellulose (HPC), 0.5 g of cellulose acetate (CA) and 10 mL of N,N-dimethylformamide (DMF) were mixed in a beaker”.

[0040] The HPC / CA nanofiber membrane prepared in Example 1 was cut to obtain two pieces of HPC / CA nanofiber membranes with a length of 2 cm and a width of 1.5 cm. The morphology of one HPC / CA nanofiber membrane was observed after soaking in water at 25°C for 1 hour. Figure 2 The photo shown was taken and dried as the first experimental group; another HPC / CA nanofiber membrane was not soaked in water as the first control group, and the morphology was observed, as shown in FIG. Figure 1 Photos shown. Figure 2 It was observed that the HPC / CA nanofiber membrane was insoluble in water and became transparent.

[0041] The two HPC / CA nanofiber membranes in the first experimental group and the first control group were observed and photographed using a scanning electron microscope (Hitachi SEM TM4000, Hitachi Technology Co., Ltd., Japan). Figure 3 and Figure 4 shown. Figure 3 This is the morphology of the HPC / CA nanofiber membrane of the first experimental group after soaking in water and drying under a scanning electron microscope;

[0042] Figure 4 The morphology of the HPC / CA nanofiber membrane in the first control group under a scanning electron microscope. Figure 3 and Figure 4 It can be seen that after the HPC / CA nanofiber membrane is dried in water, it still maintains the nanofiber membrane morphology (the morphology of the HPC / CA nanofiber membrane has not changed), indicating that the addition of CA can overcome the characteristic of HPC that it dissolves in water and changes the water solubility of HPC.

[0043] The HPC / CA nanofiber membrane prepared in Example 2 was cut to obtain two HPC / CA nanofiber membranes with a length of 2 cm and a width of 1.5 cm. Among them, one HPC / CA nanofiber membrane was soaked in water at 25°C for 1 hour as the second experimental group and observed in a wet state; the other HPC / CA nanofiber membrane was not soaked in water as the second control group. The two HPC / CA nanofiber membranes in the second experimental group and the second control group were observed and photographed using a biological atomic force microscope (Nanowizard 4XP, Bruker Technology Co., Ltd., USA).

[0044] Figure 5 This is the biological atomic force microscopy observation image of the HPC / CA nanofiber membrane of the second control group. Figure 6For the second experimental group, the HPC / CA nanofiber membrane was observed by atomic force microscopy in the wet state after soaking in water. It was observed that the HPC / CA nanofiber membrane was not soluble in water. Hydroxypropyl cellulose (HPC) is a water-soluble polymer material. After blending with cellulose acetate (CA), the HPC / CA nanofiber membrane does not dissolve in water in the wet state after soaking in water. Figure 5 and Figure 6 It can be seen that the surface roughness of the HPC / CA nanofiber membrane in the second experimental group increases. The increase in surface roughness indicates that the fiber swells but does not dissolve. Therefore, the HPC / CA nanofiber membrane has the characteristics of wet swelling and increased surface roughness, but does not dissolve in water.

[0045] The above has exemplarily described the present application. It should be noted that any simple modification, change or other equivalent replacement that does not deviate from the core of the present application and can be made by those skilled in the art without creative labor falls within the protection scope of the present application.

Claims

1. A method for preparing HPC / CA nanofiber membrane, characterized in that: The following steps are involved: Step 1: mixing hydroxypropyl cellulose, cellulose acetate, and N,N-dimethylformamide, stirring until the hydroxypropyl cellulose and cellulose acetate are dissolved, and cooling at room temperature to obtain an HPC / CA mixed solution, wherein the ratio of the hydroxypropyl cellulose to the cellulose acetate is (0.6-1): (0.2-0.5) by mass; Step 2: electrospinning the HPC / CA mixed solution to obtain an HPC / CA nanofiber membrane.

2. The preparation method according to claim 1, characterized in that In step 1, the ratio of the mass fraction of the hydroxypropyl cellulose to the volume fraction of the N,N-dimethylformamide is (6-10):100, the unit of the mass fraction is g, and the unit of the volume fraction is mL.

3. The preparation method according to claim 1, characterized in that In step 1, hydroxypropyl cellulose, cellulose acetate and N,N-dimethylformamide are mixed and stirred at room temperature (15-30° C.) for 4-7 hours, then at 30-40° C. for 2-4 hours, and finally at 50-60° C. for 1-4 hours.

4. The preparation method according to claim 1, characterized in that In step 2, the electrospinning is performed in an environment where the relative humidity of air is ≤30% RH.

5. The preparation method according to claim 1, characterized in that In step 2, the feed flow rate of the electrospinning is 0.5-1.0 mL / h, the horizontal distance between the nozzle and the center of the collecting reel is 15-20 cm, and the vertical distance is 10-15 cm; the rotation speed of the collecting roller is 250-300 rpm, the outer diameter of the needle tip is 1.28 mm, and the inner diameter of the needle tip is 0.86 mm.

6. The preparation method according to claim 1, characterized in that In step 2, the voltage of the electrospinning is 22-30V.

7. The preparation method according to claim 1, characterized in that In step 1, the stirring speed is 300-800 rpm.

8. The preparation method according to claim 3, characterized in that The heating rate from room temperature (15-30°C) to 30-40°C is 5-15°C / h, and the heating rate from 30-40°C to 50-60°C is 5-15°C / h.

9. A HPC / CA nanofiber membrane, characterized in that include: The ratio of hydroxypropyl cellulose and cellulose acetate is (6-10): (2-5) by mass.

10. Use of the HPC / CA nanofiber membrane according to claim 9 or the HPC / CA nanofiber membrane obtained by the preparation method of any one of claims 1 to 8 in polymer medical dressings.