阅读说明：本技术 一种表面具有二氧化钛刺结构的聚丙烯腈纤维制备方法 (Preparation method of polyacrylonitrile fiber with titanium dioxide thorn structure on surface ) 是由 王晟 王騊 孙国峰 于 2021-03-19 设计创作，主要内容包括：本发明公开了一种将二氧化钛负载在聚丙烯腈纤维上的制备方法,包括以下步骤：1)将1-5份(重量比)的PAN粉末加入5-20份(重量比)的DMF中,得到溶液1；2)将0.1-0.4份(重量比)的聚乙烯-聚丙二醇和0.2-0.8份(重量比)十六烷基三甲基溴化铵加入15-35ml的水混合搅拌获得溶液,将该溶液和溶液1相混合得到溶液2；3)将上述溶液2进行静电纺丝,得到聚丙烯腈纤维；4)将上述聚丙烯腈纤维加入5％-25％的硫酸钛水溶液中,进行水热处理；5)水热处理后将步骤4)中获得的混合物离心分离。本发明制备的复合聚丙烯腈纤维表面长满了二氧化钛刺结构,可以良好的结合光催化粉体材料和纤维柔性载体。(The invention discloses a preparation method for loading titanium dioxide on polyacrylonitrile fiber, which comprises the following steps: 1) adding 1-5 parts by weight of PAN powder into 5-20 parts by weight of DMF to obtain a solution 1; 2) adding 0.1-0.4 part (by weight) of polyethylene-polypropylene glycol and 0.2-0.8 part (by weight) of hexadecyl trimethyl ammonium bromide into 15-35ml of water, mixing and stirring to obtain a solution, and mixing the solution and the solution 1 to obtain a solution 2; 3) carrying out electrostatic spinning on the solution 2 to obtain polyacrylonitrile fibers; 4) adding the polyacrylonitrile fiber into 5-25% titanium sulfate aqueous solution for hydrothermal treatment; 5) centrifuging the mixture obtained in step 4) after the hydrothermal treatment. The surface of the composite polyacrylonitrile fiber prepared by the invention is full of titanium dioxide thorn structures, and the photocatalytic powder material and the fiber flexible carrier can be well combined.)

1. A preparation method for loading titanium dioxide on polyacrylonitrile fibers is characterized by comprising the following steps:

1) adding 1-5 parts by weight of PAN powder into 5-20 parts by weight of DMF to obtain a solution 1;

2) adding 0.1-0.4 part (by weight) of polyethylene-polypropylene glycol and 0.2-0.8 part (by weight) of hexadecyl trimethyl ammonium bromide into 15-35ml of water, mixing and stirring to obtain a solution, and mixing the solution and the solution 1 to obtain a solution 2;

3) carrying out electrostatic spinning on the solution 2 to obtain polyacrylonitrile fibers;

4) adding the polyacrylonitrile fiber into 5-25% titanium sulfate aqueous solution for hydrothermal treatment;

5) centrifuging the mixture obtained in step 4) after the hydrothermal treatment.

2. The polyacrylonitrile fiber obtained by the preparation method according to claim 1, wherein the surface of the polyacrylonitrile fiber has a titanium dioxide spine structure.

3. The method for preparing titanium dioxide supported on polyacrylonitrile fiber according to claim 1, wherein the PAN powder has a purity of 99%; mw was 15 ten thousand.

4. The method for preparing titania-supported polyacrylonitrile fiber according to claim 3, wherein the stirring and mixing in step 1) are carried out for 12 to 36 hours.

5. The preparation method for supporting titanium dioxide on polyacrylonitrile fiber according to claim 4, wherein the step 2) is mixing and stirring for 3-6 hours.

6. The method for preparing supported titania on polyacrylonitrile fiber according to claim 5, wherein the conditions of step 3) electrospinning are as follows: the voltage is 10-13 kV; spinning speed: 0.1-0.3 mL/h; the spinning distance is 15-20 cm; the rotating speed of the roller is 45-80 r/min; the temperature is controlled at 25-30 ℃ and the humidity is controlled at 30-60%.

7. The method for preparing titanium dioxide supported on polyacrylonitrile fiber according to claim 6, wherein the hydrothermal treatment in step 4) is performed in an autoclave.

8. The method for preparing titanium dioxide supported on polyacrylonitrile fiber according to claim 7, wherein the step 4) is carried out under hydrothermal treatment, specifically 150-180 degree hydrothermal condition for 12-36 hours.

9. The method for preparing titania-supported polyacrylonitrile fiber according to claim 8, wherein the polyacrylonitrile fiber with titania is obtained by washing the product of the centrifugal separation in step 5) with ethanol and deionized water.

Technical Field

The invention relates to a preparation method for loading titanium dioxide on polyacrylonitrile fibers.

Background

Anatase phase TiO2 is the most widely used semiconductor photocatalyst at present due to its chemical stability, strong oxidation-reduction properties, corrosion resistance, non-toxicity and low cost. TiO2 has several advantages as a photocatalyst: 1. the solar energy is converted into chemical energy for utilization. 2. The degradation speed is high, OH generated by photoexcited holes is a strong oxidation free radical, and most organic matters including refractory organic matters can be successfully decomposed in a short time. 3. The degradation is not selective, and almost any organic pollutant can be degraded. 4. The method has the characteristics of high stability, light corrosion resistance, no toxicity and the like, and does not generate secondary pollution in the treatment process; the organic pollutants can be oxidatively degraded into CO2 and H2O, and are non-toxic to humans. TiO2 photocatalyst has been attracting attention because it has antibacterial, deodorizing, oil stain decomposing, mildew and algae preventing, and air purifying effects under irradiation of sunlight or an indoor fluorescent lamp.

On the other hand, since the photocatalytic material is generally a powder material, it is necessary to consider that the photocatalytic material is supported on a carrier when the photocatalytic material is put into practical use, thereby solving the problem of convenience in recycling and use. Fibrous materials, which have softness and large loading areas, are ideal carrier materials. How to better combine the photocatalytic powder material with the organic flexible carrier is one of the targets pursued in the field of practicality.

The present invention has been made to solve the above problems.

Disclosure of Invention

The invention aims to provide a preparation method for loading titanium dioxide on polyacrylonitrile fibers.

The purpose of the invention is realized by the following technical scheme:

a preparation method for loading titanium dioxide on polyacrylonitrile fibers comprises the following steps:

1) adding 1-5 parts by weight of PAN powder into 5-20 parts by weight of DMF to obtain a solution 1;

2) adding 0.1-0.4 part (by weight) of polyethylene-polypropylene glycol and 0.2-0.8 part (by weight) of hexadecyl trimethyl ammonium bromide into 15-35ml of water, mixing and stirring to obtain a solution, and mixing the solution and the solution 1 to obtain a solution 2;

3) carrying out electrostatic spinning on the solution 2 to obtain polyacrylonitrile fibers;

4) adding the polyacrylonitrile fiber into 5-25% titanium sulfate aqueous solution for hydrothermal treatment;

5) centrifuging the mixture obtained in step 4) after the hydrothermal treatment.

Furthermore, the surface of the polyacrylonitrile fiber has a titanium dioxide thorn structure.

Preferably, the PAN powder has a purity of 99%; mw was 15 ten thousand.

Further, stirring and mixing for 12-36 hours in the step 1).

Preferably, step 2) is mixed and stirred for 3 to 6 hours.

Further, the electrostatic spinning conditions in step 3) are as follows: the voltage is 10-13 kV; spinning speed: 0.1-0.3 mL/h; the spinning distance is 15-20 cm; the rotating speed of the roller is 45-80 r/min; the temperature is controlled at 25-30 ℃ and the humidity is controlled at 30-60%.

Preferably, the hydrothermal treatment in step 4) is carried out in an autoclave.

Further, the step 4) is carried out for 12-36 hours under the hydrothermal condition of 150-180 degrees.

Further, washing the product obtained by centrifugal separation in the step 5) with ethanol and deionized water to obtain the polyacrylonitrile fiber loaded with titanium dioxide.

Has the advantages that:

the method comprises the steps of mixing a specific polyethylene-polypropylene glycol and hexadecyl trimethyl ammonium bromide induction system with a polyacrylonitrile fiber/N, N-dimethylformamide solution, and obtaining the polyacrylonitrile fiber containing the induction system through electrostatic spinning; then mixing the fiber with a titanium sulfate solution, and carrying out hydrothermal treatment to obtain the polyacrylonitrile fiber loaded with titanium dioxide; the surface of the composite polyacrylonitrile fiber is full of titanium dioxide thorn structures, so that the photocatalytic powder material and the fiber flexible carrier can be well combined; the preparation process of the product is relatively simple, the conditions are easy to control, and the product is easy for large-scale industrial production.

Drawings

FIG. 1 is a scanning electron microscope image of polyacrylonitrile fiber loaded with titanium dioxide, and the scale size in the image is 1 μm.

Detailed Description

The present invention will be further described with reference to the following specific examples and accompanying drawings so that those skilled in the art can better understand the technical solutions of the present invention.

Example 1

A preparation method for loading titanium dioxide on polyacrylonitrile fibers comprises the following steps:

1) 1 part (weight ratio) of PAN powder (purity 99%, Mw: 15 ten thousand) are added into 5 parts by weight of DMF (N, N-dimethylformamide), stirred and mixed for 12 to 36 hours until the solution is completely dissolved to obtain a solution 1;

2) adding 0.1 part by weight of polyethylene-polypropylene glycol (F-127) and 0.2 part by weight of cetyltrimethylammonium bromide (CTAB) to 15ml of water, mixing and stirring for 3 hours to obtain a solution, and mixing the solution and the solution 1 to obtain a solution 2;

3) the solution 2 was electrospun under the following conditions: the voltage is 10 kV; spinning speed: 0.1 mL/h; the spinning distance is 15 cm; the rotating speed of the roller is 45 r/min; controlling the temperature at 25 ℃ and the humidity at 30%; obtaining polyacrylonitrile fiber;

4) adding the polyacrylonitrile fiber into a 5% titanium sulfate aqueous solution, stirring for 3 minutes, transferring into a high-pressure kettle, and treating for 12 hours under the hydrothermal condition of 150 ℃;

5) and after hydrothermal treatment, centrifugally separating the mixture obtained in the step 4), and washing for 3 times by using ethanol and deionized water to obtain the polyacrylonitrile fiber loaded with titanium dioxide.

Fig. 1 is a scanning electron microscope image of polyacrylonitrile fiber loaded with titanium dioxide prepared in this example.

According to observation, the surface of the polyacrylonitrile fiber is loaded with a titanium dioxide thorn structure, and the method mixes a specific polyethylene-polypropylene glycol and hexadecyl trimethyl ammonium bromide induction system with the polyacrylonitrile fiber/N, N-dimethyl formamide solution and obtains the polyacrylonitrile fiber containing the induction system through electrostatic spinning; then mixing the fiber with a titanium sulfate solution, and carrying out hydrothermal treatment to obtain the polyacrylonitrile fiber loaded with titanium dioxide spines; the surface of the composite polyacrylonitrile fiber is full of titanium dioxide thorn structures, and the photocatalytic powder material and the fiber flexible carrier can be well combined.

Example 2

A preparation method for loading titanium dioxide on polyacrylonitrile fibers comprises the following steps:

1) adding 5 parts by weight of polyacrylonitrile fiber powder into 20 parts by weight of DMF, and stirring and mixing for 36 hours until the polyacrylonitrile fiber powder is completely dissolved to obtain a solution 1;

2) adding 0.4 part (by weight) of polyethylene-polypropylene glycol and 0.8 part (by weight) of cetyltrimethylammonium bromide into 35ml of water, mixing and stirring for 6 hours to obtain a solution, and mixing the solution and the solution 1 to obtain a solution 2;

3) the solution 2 was electrospun under the following conditions: the voltage is 13 kV; the spinning speed is 0.3 mL/h; the spinning distance is 20 cm; the rotating speed of the roller is 80 r/min; controlling the temperature at 30 ℃ and the humidity at 60%; obtaining polyacrylonitrile fiber;

4) adding the polyacrylonitrile fiber into 25% titanium sulfate aqueous solution, stirring for 5 minutes, moving into a high-pressure kettle, and treating for 36 hours under the hydrothermal condition of 180 ℃;

5) and after hydrothermal treatment, centrifugally separating the mixture obtained in the step 4), and washing for 3 times by using ethanol and deionized water to obtain the polyacrylonitrile fiber loaded with titanium dioxide.

Example 3

A preparation method for loading titanium dioxide on polyacrylonitrile fibers comprises the following steps:

1) adding 1 part (weight ratio) of PAN powder into 20 parts (weight ratio) of DMF, and stirring and mixing for 36 hours until complete dissolution to obtain a solution 1;

2) adding 0.1 part by weight of polyethylene-polypropylene glycol and 0.8 part by weight of cetyltrimethylammonium bromide to 15ml of water, mixing and stirring for 6 hours to obtain a solution, and mixing the solution and the solution 1 to obtain a solution 2;

3) the solution 2 was electrospun under the following conditions: the voltage is 10-13 kV; spinning speed: 0.1-0.3 mL/h; the spinning distance is 15-20 cm; the rotating speed of the roller is 45-80 r/min; controlling the temperature at 25-30 ℃ and the humidity at 30-60%; obtaining polyacrylonitrile fiber;

4) adding the polyacrylonitrile fiber into a 5% titanium sulfate aqueous solution, stirring for 5 minutes, transferring into a high-pressure kettle, and treating for 12 hours under the hydrothermal condition of 150 ℃;

5) and after hydrothermal treatment, centrifugally separating the mixture obtained in the step 4), and washing for 3 times by using ethanol and deionized water to obtain the polyacrylonitrile fiber loaded with titanium dioxide.

Example 4

A preparation method for loading titanium dioxide on polyacrylonitrile fibers comprises the following steps:

1) adding 3 parts by weight of PAN powder into 10 parts by weight of DMF, and stirring and mixing for 20 hours until complete dissolution to obtain a solution 1;

2) adding 0.3 part (by weight) of polyethylene-polypropylene glycol and 0.5 part (by weight) of cetyltrimethylammonium bromide into 25ml of water, mixing and stirring for 4 hours to obtain a solution, and mixing the solution and the solution 1 to obtain a solution 2;

3) the solution 2 was electrospun under the following conditions: the voltage is 12 kV; spinning speed: 0.2 mL/h; the spinning distance is 18 cm; the rotating speed of the roller is 60 r/min; controlling the temperature at 28 ℃ and the humidity at 45%; obtaining polyacrylonitrile fiber;

4) adding the polyacrylonitrile fiber into a 15% titanium sulfate aqueous solution, stirring for 4 minutes, moving into a high-pressure kettle, and treating for 24 hours under a 165-degree hydrothermal condition;

5) and after hydrothermal treatment, centrifugally separating the mixture obtained in the step 4), and washing for 3 times by using ethanol and deionized water to obtain the polyacrylonitrile fiber loaded with titanium dioxide.

Example 5

A preparation method for loading titanium dioxide on polyacrylonitrile fibers comprises the following steps:

1) adding 5 parts by weight of PAN powder into 5 parts by weight of DMF, and stirring and mixing for 12 hours until complete dissolution to obtain a solution 1;

2) adding 0.4 part (by weight) of polyethylene-polypropylene glycol and 0.2 part (by weight) of cetyltrimethylammonium bromide into 35ml of water, mixing and stirring for 3 hours to obtain a solution, and mixing the solution and the solution 1 to obtain a solution 2;

3) the solution 2 was electrospun under the following conditions: the voltage is 10 kV; spinning speed: 0.1 mL/h; the spinning distance is 15 cm; the rotating speed of the roller is 45 r/min; controlling the temperature at 25 ℃ and the humidity at 30%; obtaining polyacrylonitrile fiber;

4) adding the polyacrylonitrile fiber into 25% titanium sulfate aqueous solution, stirring for 3 minutes, moving into a high-pressure kettle, and treating for 36 hours under the hydrothermal condition of 180 ℃;

5) and after hydrothermal treatment, centrifugally separating the mixture obtained in the step 4), and washing for 3 times by using ethanol and deionized water to obtain the polyacrylonitrile fiber loaded with titanium dioxide.

Example 6

A preparation method for loading titanium dioxide on polyacrylonitrile fibers comprises the following steps:

1) adding 5 parts by weight of PAN powder into 20 parts by weight of DMF, and stirring and mixing for 12 hours until complete dissolution to obtain a solution 1;

2) adding 0.4 part by weight of polyethylene-polypropylene glycol and 0.2 part by weight of cetyltrimethylammonium bromide to 35ml of ultrapure water, mixing and stirring for 3 hours to obtain a solution, and mixing the solution with the solution 1 to obtain a solution 2;

3) the solution 2 was electrospun under the following conditions: the voltage is 10 kV; spinning speed: 0.3 mL/h; the spinning distance is 20 cm; the rotating speed of the roller is 45 r/min; controlling the temperature at 30 ℃ and the humidity at 60%; obtaining polyacrylonitrile fiber;

4) adding the polyacrylonitrile fiber into 25% titanium sulfate aqueous solution, stirring for 3 minutes, transferring into a high-pressure kettle, and treating for 12 hours under the hydrothermal condition of 180 ℃;

5) and after hydrothermal treatment, centrifugally separating the mixture obtained in the step 4), and washing for 3 times by using ethanol and deionized water to obtain the polyacrylonitrile fiber loaded with titanium dioxide.