CN102776706A - Method for preparing polyetherimide amphipathic composite nano-scale fiber membrane - Google Patents

Abstract

The invention relates to a method for preparing a polyetherimide amphipathic composite nano-scale fiber membrane, comprising the following steps: (1) mixing dichloromethane with N,N-dimethylacetamide to prepare a mixed solvent; adding polyetherimide and polyvinylpyrrolidone (PVP) into the mixed solvent; and oscillating for 8 to 24h till complete dissolution to obtain a spinning solution; and (2) adopting the spinning solution for electrostatic spinning, and finally drying to obtain the composite nano-scale fiber membrane. The preparation method is simple; the condition is mild; the evenly-mixed composite nano fiber membrane can be prepared in a single step; the prepared fiber has a smooth surface and is even in fineness; and in addition, the diameter distribution of the fiber is in a range of 400 nm to 1500nm.

Description

A kind of preparation method of polyetherimide amphiphilic composite nanoscale fiber membrane

technical field

The invention belongs to the field of preparation of composite nanofiber membranes, in particular to a preparation method of polyetherimide amphiphilic composite nanoscale fiber membranes.

Background technique

Nanocomposite materials are new materials developed in recent years. Since the size of nanocomposite materials is between molecules and bulk phases and belongs to mesoscopic system, it shows special properties different from molecules and bulk phases, and has obvious surface effects, Quantum size effect, small size effect and macroscopic quantum tunneling effect present many excellent physical and chemical properties. There are many common methods for preparing nanocomposites, such as: intercalation composite method, sol-gel method, in-situ polymerization method, ultrasonic method, chemical dispersion additive method, blending method, direct insertion method of polymer solution, blending method Polymer melting direct insertion method, etc.

Due to the upsurge of nanotechnology in recent years, there have been more and more reports on the preparation of functional nanofibers using high-voltage electrospinning technology. Researchers have attempted to prepare nanofibrous membranes from a variety of polymer materials (including natural and synthetic polymers, proteins, and even small molecules) through electrospinning to exert the functional performance of materials at the nanoscale. At the same time, these nanofibers are commonly used in many fields such as medicine, separation and purification, energy, environmental protection, and catalytic reactions.

High-voltage electrospinning technology is a top-down nano-manufacturing technology. The jet is formed by overcoming the liquid surface tension and viscoelastic force of the droplet at the capillary tip of the nozzle by an external electric field force. Under the joint action of electrostatic repulsion, Coulomb force and surface tension , the atomized liquid jet is bent, stretched, and split by high frequency, and is drawn tens of millions of times in tens of milliseconds, and nano-scale fibers are obtained at the receiving end through solvent volatilization or melt cooling. This technology has simple process, convenient operation, wide selection of materials, strong controllability, and can prepare nanofibers with microstructure characteristics through nozzle design. It is considered to be a method that may realize the industrial production of continuous nanofibers. The preparation of functional nanofibers by this technology has a good prospect. In the research of blending electrospinning to prepare composite nanofibers, some problems have arisen, which limit the co-solution/blending spinning of different substances. These problems include the difficulty of obtaining solvents that can simultaneously have good solubility for different functional substances, or these A good co-solvent does not guarantee that the polymer material can form nanofibers under the conditions of the electrospinning process. Therefore, the research on electrospinning technology still has a long way to go.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for preparing a polyetherimide amphiphilic composite nanoscale fiber membrane. The preparation method is simple and the preparation conditions are mild. Between 400-1000nm.

A kind of preparation method of polyetherimide amphiphilic composite nanoscale fiber membrane of the present invention comprises the following steps:

(1) Preparation of spinning solution: Mix dichloromethane (DCM) and N,N-dimethylacetamide (DMAC) to make a mixed solvent, add polyetherimide PEI and polyvinylpyrrolidone PVP to the above mixture In the solvent, shake for 8-24 hours until completely dissolved to obtain the spinning solution;

(2) Electrospinning: Electrospinning is carried out with the above spinning solution, and finally dried to obtain a composite nanofiber membrane.

The weight ratio of polyetherimide to polyvinylpyrrolidone in step (1) is 1.0:1.0-5.0.

The polyvinylpyrrolidone PVP described in step (1) is polyvinylpyrrolidone PVPK90.

The volume ratio of dichloromethane to N,N-dimethylacetamide in the mixed solvent described in step (1) is 5.0-6.0:1.0.

公司）控制，采用铝箔平板接收纤维。In the electrospinning described in step (2), a 5mL syringe is used as the solution reservoir; a flattened needle is used as the capillary for spraying thin streams, and the needle is a No. 5 stainless steel injection needle with an inner diameter of 0.5mm. The generator is ZGF2000 type, Shanghai Suter Electric Co., Ltd., and the flow of spinning liquid is controlled by a micro-injection pump (USA

company) control, using an aluminum foil plate to receive the fiber.

The parameters of the electrospinning process described in step (2) are: the propulsion rate is 1.0-2.0mL/h, the distance between the receiving plate and the spinneret is 10-25cm, the voltage is 12-16kv, the ambient temperature is 20-25°C, and the ambient humidity is 67 ±4%.

The fiber diameter distribution in the composite nanoscale fiber membrane obtained in step (2) is 400-1000 nm.

Beneficial effect:

(1) The preparation method of the present invention is simple, the conditions are mild, and a uniformly mixed composite nanofiber membrane can be prepared in a single step;

(2) The surface of the fiber obtained in the present invention is smooth, the thickness is uniform, and the fiber diameter is distributed between 400-1500nm.

Description of drawings

Figure 1 is a high-voltage electrospinning process diagram;

Fig. 2 is a scanning electron microscope picture of polyetherimide/polyvinylpyrrolidone composite nanofibers when electrospinning at a high voltage of 12kv;

Figure 3 is a scanning electron microscope picture of polyetherimide/polyvinylpyrrolidone composite nanofibers at a high voltage of 15kv for electrospinning;

Fig. 4 is a scanning electron microscope image of polyetherimide/polyvinylpyrrolidone composite nanofibers when electrospinning at a high voltage of 16kv.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

The preparation of polyetherimide/polyvinylpyrrolidone composite nanofibers, the specific steps are as follows:

(1) Preparation of spinning solution

Put 6mL of dichloromethane (DCM) and 1mL of N,N-dimethylacetamide (DMAC) into a conical flask with a stopper, place it in a constant temperature shaking shaker (25°C) and vibrate for 10min, and polymerize Add 0.2000 g of ether imide (PEI) and 0.4000 g of polyvinylpyrrolidone (PVP) into the solvent, and shake at constant temperature for 24 hours.

(2) Electrospinning

公司）控制，采用铝箔平板接受纤维。电纺工艺参数：推进速率1.0mL/h，接收板离喷丝口距离15cm，电压12kv。其他条件：环境温度为25℃，环境湿度67±4%。Put the above spinning solution into the solution reservoir, use a flattened needle (No. 5 stainless steel injection needle, inner diameter 0.5 mm) as the capillary for jetting fine flow, connect it to a high-voltage generator (ZGF2000 type, Shanghai Sute Electric Co., Ltd.), and spin The flow of silk liquid was controlled by a micro-syringe pump (USA

company) control, using an aluminum foil plate to receive the fibers. Electrospinning process parameters: the propulsion rate is 1.0mL/h, the distance between the receiving plate and the spinneret is 15cm, and the voltage is 12kv. Other conditions: the ambient temperature is 25°C, and the ambient humidity is 67±4%.

(3) Collect the fibers and put them in a vacuum drying oven (at a constant temperature of 37°C) to dry for 2 days, and then test them with a scanning electron microscope, as shown in Figure 2.

Example 2

The preparation of polyetherimide/polyvinylpyrrolidone composite nanofibers, the specific steps are as follows:

(1) Preparation of spinning solution: Put 5mL of dichloromethane (DCM) and 1mL of N,N-dimethylacetamide (DMAC) into a conical flask with a stopper and place it on a constant temperature shaking shaker (25°C ) for 10 minutes, add 0.2000 g of polymer polyetherimide (PEI) and 0.4000 g of polyvinylpyrrolidone (PVP) into the solvent, and shake at constant temperature for 24 hours. .

公司）控制，采用铝箔平板接受纤维。(2) Electrospinning: Put the above spinning solution into the solution reservoir, use a flattened needle (No. 5 stainless steel injection needle, inner diameter 0.5mm) as the capillary for jetting fine flow, and connect it to a high-voltage generator (ZGF2000, Shanghai Suter Electric Co., Ltd.), the flow of spinning solution is controlled by a micro-syringe pump (USA

company) control, using an aluminum foil plate to receive the fibers.

Electrospinning process parameters: the propulsion rate is 1.0mL/h, the distance between the receiving plate and the spinneret is 20cm, and the voltage is 15kv. Other conditions: the ambient temperature is 25°C, and the ambient humidity is 67±4%.

(3) Collect the fibers and put them in a vacuum drying oven (at a constant temperature of 37°C) to dry for 2 days, and then test them with a scanning electron microscope, as shown in Figure 3.

Example 3

The preparation of polyetherimide/polyvinylpyrrolidone composite nanofibers, the specific steps are as follows:

(1) Preparation of spinning solution

Put 6mL of dichloromethane (DCM) and 1mL of N,N-dimethylacetamide (DMAC) into a conical flask with a stopper, place it in a constant temperature shaking shaker (25°C) and vibrate for 10min, and polymerize Add 0.2000 g of ether imide (PEI) and 0.4000 g of polyvinylpyrrolidone (PVP) into the solvent, and shake at constant temperature for 24 hours.

(2) Electrospinning

Put the above spinning solution into the solution reservoir, use a flattened needle (No. 5 stainless steel injection needle, inner diameter 0.5 mm) as the capillary for jetting fine flow, connect it to a high-voltage generator (ZGF2000 type, Shanghai Sute Electric Co., Ltd.), and spin The flow of silk liquid was controlled by a micro-syringe pump (USA company) control, using an aluminum foil plate to receive the fibers. Electrospinning process parameters: the propulsion rate is 1.0mL/h, the distance between the receiving plate and the spinneret is 15cm, and the voltage is 16kv. Other conditions: the ambient temperature is 25°C, and the ambient humidity is 67±4%.

(3) Collect the fibers and put them in a vacuum drying oven (at a constant temperature of 37°C) to dry for 2 days, and then test them with a scanning electron microscope, as shown in Figure 4.

Claims (7)

1. the preparation method of a PEI amphiphilic composite nanometer level tunica fibrosa comprises the following steps:

(1) with carrene and DMAC N,N mixed mixed solvent, PEI and polyvinylpyrrolidone PVP are joined in the above-mentioned mixed solvent, vibration 8-24h extremely dissolve fully spinning solution;

(2) adopt above-mentioned spinning solution to carry out electrostatic spinning, final drying promptly gets composite Nano level tunica fibrosa.

2. the preparation method of a kind of PEI amphiphilic composite nanometer level tunica fibrosa according to claim 1 is characterized in that: the weight ratio of PEI described in the step (1) and polyvinylpyrrolidone is 1.0:1.0-5.0.

3. the preparation method of a kind of PEI amphiphilic composite nanometer level tunica fibrosa according to claim 1 is characterized in that: the polyvinylpyrrolidone PVP described in the step (1) is polyvinylpyrrolidone PVPK90.

4. the preparation method of a kind of PEI amphiphilic composite nanometer level tunica fibrosa according to claim 1 is characterized in that: the volume ratio of carrene and DMAC N,N is 5.0-6.0:1.0 in the described mixed solvent of step (1).

5. the preparation method of a kind of PEI amphiphilic composite nanometer level tunica fibrosa according to claim 1 is characterized in that: adopt the 5mL syringe as the solution storage storage in the electrostatic spinning described in the step (2); The syringe needle that employing is scabbled is as the capillary that sprays thread, and described syringe needle is No. 5 stainless steel syringe needles, internal diameter 0.5mm; The spinning solution flow is controlled by micro-injection pump; Adopt the dull and stereotyped fiber that receives of aluminium foil.

6. the preparation method of a kind of PEI amphiphilic composite nanometer level tunica fibrosa according to claim 1; It is characterized in that: the electric spinning process parameter described in the step (2) is: advance speed 1.0-2.0mL/h; Dash receiver leaves spinning nozzle apart from 10-25cm; Voltage 12-16kv, environment temperature is 20-25 ℃, ambient humidity 67 ± 4%.

7. the preparation method of a kind of PEI amphiphilic composite nanometer level tunica fibrosa according to claim 1 is characterized in that: distribution of fiber diameters is at 400-1000nm in the composite Nano level tunica fibrosa that obtains in the step (2).

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