阅读说明：本技术 一种二氧化钛/聚酰亚胺复合材料的制备方法 (Preparation method of titanium dioxide/polyimide composite material ) 是由 周雨薇 于 2021-09-01 设计创作，主要内容包括：本发明涉及一种二氧化钛/聚酰亚胺复合材料的制备方法,属于高分子复合材料领域。该二氧化钛/聚酰亚胺复合材料的制备方法为利用两亲性聚酰亚胺的特殊官能团所体现的亲疏水性与油溶性的特性,在水/N-甲基吡咯烷酮溶液中进行自组装,在自组装的同时,向溶液中加入二氧化钛的前驱体钛酸丁酯,在聚酰亚胺组装体表面进行原位生长具有光催化性能的纳米二氧化钛,过滤,干燥后最终得到了集吸附光催化于一体的二氧化钛/聚酰亚胺复合材料。本发明的制备方法简单快捷,成本低,性能高效稳定,易于分离回收等优点,易实现工业化。本发明所制备的二氧化钛/聚酰亚胺复合材料对亚甲基蓝的吸附性能大于150mg/g,在300W汞灯的照射60min后,吸附的亚甲基蓝全部分解。(The invention relates to a preparation method of a titanium dioxide/polyimide composite material, belonging to the field of polymer composite materials. The preparation method of the titanium dioxide/polyimide composite material comprises the steps of utilizing the characteristics of hydrophilicity and hydrophobicity and oil solubility embodied by special functional groups of amphiphilic polyimide, carrying out self-assembly in a water/N-methyl pyrrolidone solution, adding a titanium dioxide precursor butyl titanate into the solution during the self-assembly, carrying out in-situ growth of nano titanium dioxide with photocatalytic performance on the surface of a polyimide assembly, filtering, and drying to finally obtain the titanium dioxide/polyimide composite material integrating absorption and photocatalysis. The preparation method has the advantages of simplicity, rapidness, low cost, high-efficiency and stable performance, easiness in separation and recovery and the like, and is easy to realize industrialization. The adsorption performance of the titanium dioxide/polyimide composite material prepared by the invention on methylene blue is more than 150mg/g, and the adsorbed methylene blue is completely decomposed after the titanium dioxide/polyimide composite material is irradiated by a 300W mercury lamp for 60 min.)

1. A preparation method of a titanium dioxide/polyimide composite material is characterized by comprising the following steps: the preparation method comprises the following steps:

(1) dissolving amphiphilic polyimide in an N-methyl pyrrolidone solution, stirring for 0.5-2 h at 30-80 ℃ to obtain a polyimide solution of 1-10 mg/mL, wherein the structural formula of the amphiphilic polyimide is shown as a formula I,

(2) adding sodium dodecyl sulfate into water to prepare a solution of 2-10 mg/mL, adding the solution into the solution obtained in the step (1), and stirring at room temperature for 0.5-2 h, wherein the volume ratio of the sodium dodecyl sulfate aqueous solution to the N-methyl pyrrolidone is 1: 5-15;

(3) adding glacial acetic acid into the solution obtained in the step (2), then adding butyl titanate, stirring at room temperature for 0.5-2 h, and continuing to react for 6-24 h, wherein the concentration of the butyl titanate is 10-100 mg/mL, and the volume ratio of the glacial acetic acid to the N-methyl pyrrolidone is 1: 20-100 parts of;

(4) pouring the product obtained in the step (3) into deionized water, precipitating, filtering, and then putting the product into a vacuum oven to dry for 4-12 hours at 40-80 ℃ to obtain the titanium dioxide/polyimide composite material, wherein the volume ratio of the N-methylpyrrolidone to the deionized water is 1: 2 to 10.

Technical Field

The invention relates to a preparation method of a titanium dioxide/polyimide composite material, belonging to the field of polymer composite materials. The titanium dioxide/polyimide composite material prepared by the invention can be used as a photocatalytic material to be applied to the fields of dye wastewater treatment, environmental management and the like.

Background

The continuous progress of global industrial technology in recent century makes the demands of various industries for heat-resistant, high-strength and light materials more urgent. Against this large background, a large number of polymers having aromatic or heterocyclic rings in the main chain have been produced, among which polyimides are distinguished among many polymers by their excellent heat resistance and mechanical properties. Since the 20 th century, polyimide was developed, and this polymer material with excellent properties has been developed, and has greatly promoted the development of the related industries. Polyimide is attracting attention because of its structural and functional diversity, synthetic process maturity, processing method diversity, excellent overall performance, and wide application fields.

Since the 21 st century, industrial innovation is continuously promoted, the modern society develops at a high speed, and the living standard of people is continuously improved. Therefore, the environmental problem, especially the problem of waste water treatment, has become a social problem which needs to be solved urgently. The treatment methods of dye wastewater are various and mainly divided into three categories: physical methods, chemical methods, and biological methods. The physical method can only gather the dyes together but can not completely eliminate the dyes, and the treatment of the dyes is incomplete and takes long time; the chemical method utilizes oxidation-reduction reaction to decompose macromolecular dyes into harmless micromolecules, and is convenient and quick to operate; biological methods utilize biological decomposition, which is costly to perform and requires high operating requirements. The invention provides a method for treating dye by adopting photocatalysis to develop mature titanium dioxide as a photocatalytic material. Based on the modification, the polyimide is modified, and the nano titanium dioxide with photocatalytic performance is grown in situ on the surface of the polyimide by adding a titanium dioxide precursor, namely butyl titanate, so that the high-temperature-resistant and corrosion-resistant composite material integrating photocatalysis and adsorption is formed. The method is simple and quick to operate, low in cost, green and environment-friendly, and can be used for industrial production.

Disclosure of Invention

The invention aims to provide a preparation method of a titanium dioxide/polyimide composite material aiming at the current situation that the existing adsorbing material for treating environmental pollution only adsorbs pollutants but does not decompose the pollutants. The preparation method specifically comprises the steps of utilizing the characteristics of hydrophilicity and hydrophobicity and oil solubility embodied by special functional groups of amphiphilic polyimide, carrying out self-assembly in a water/N-methyl pyrrolidone solution, adding titanium dioxide precursor butyl titanate into the solution while carrying out self-assembly, carrying out in-situ growth on nano titanium dioxide with photocatalytic performance on the surface of a polyimide assembly, filtering, and drying to finally obtain the titanium dioxide/polyimide composite material integrating adsorption and photocatalysis.

The preparation method of the titanium dioxide/polyimide composite material is characterized by comprising the following steps: the preparation method comprises the following steps:

(1) dissolving amphiphilic polyimide with a structural formula shown in figure 1 in an N-methyl pyrrolidone solution, and stirring at 30-80 ℃ for 0.5-2 h to obtain 1-10 mg/mL polyimide solution;

(2) adding sodium dodecyl sulfate into water to prepare a solution of 2-10 mg/mL, adding the solution into the solution obtained in the step (1), and stirring at room temperature for 0.5-2 h, wherein the volume ratio of the sodium dodecyl sulfate aqueous solution to the N-methyl pyrrolidone is 1: 5-15;

(3) adding glacial acetic acid into the solution obtained in the step (2), then adding butyl titanate, stirring at room temperature for 0.5-2 h, and continuing to react for 6-24 h, wherein the concentration of the butyl titanate is 10-100 mg/ml, and the volume ratio of the glacial acetic acid to the N-methyl pyrrolidone is 1: 20-100 parts of;

(4) pouring the product obtained in the step (3) into deionized water, precipitating, filtering, and then putting the product into a vacuum oven to dry for 4-12 hours at 40-80 ℃ to obtain the titanium dioxide/polyimide composite material, wherein the volume ratio of the N-methylpyrrolidone to the deionized water is 1: 2 to 10.

The invention has the beneficial effects that: according to the invention, the self-assembly behavior of the amphiphilic polyimide in the water/N-methyl pyrrolidone solution is utilized, the titanium dioxide precursor butyl titanate is added into the solution during self-assembly, and the nano titanium dioxide with photocatalytic performance is grown in situ on the surface of the polyimide assembly, so that the titanium dioxide/polyimide composite material integrating adsorption and photocatalysis is finally obtained. The preparation method has the advantages of simplicity, rapidness, low cost, high-efficiency and stable performance, easiness in separation and recovery and the like, and is easy to realize industrialization. The titanium dioxide/polyimide composite material prepared by the invention has excellent adsorption performance on organic pollutants, wherein the adsorption performance on methylene blue is more than 150mg/g, and the adsorbed methylene blue is completely decomposed after the light source is a 300W mercury lamp for irradiating for 60 min.

Drawings

FIG. 1 is a schematic view of the structure of an amphiphilic polyimide used in the present invention

FIG. 2 is an SEM image of a titanium dioxide/polyimide composite material prepared by the invention

Detailed Description

The following examples of the preparation process of the present invention are presented, but the following examples are illustrative of the present invention and do not constitute any limitation to the claims of the present invention.

Example 1

(1) Dissolving 100mg of amphiphilic polyimide in 100mL of N-methylpyrrolidone solution, and stirring for 1h at 50 ℃ to obtain 1mg/mL of polyimide solution, wherein the structural formula of the amphiphilic polyimide is shown in the attached figure 1;

(2) adding 40mg of sodium dodecyl sulfate into 20mL of water to prepare a solution of 2mg/mL, then adding the solution into the solution obtained in the step (1), and stirring at room temperature for 0.5 h;

(3) adding 2mL of glacial acetic acid into the solution obtained in the step (2), then adding 1.2g of butyl titanate, stirring at room temperature for 1h, and continuing to react for 8h, wherein the concentration of the butyl titanate is 10 mg/mL;

(4) and (4) pouring the product obtained in the step (3) into 500mL of deionized water, precipitating, filtering, and then putting into a vacuum oven to dry for 6 hours at 60 ℃ to obtain the titanium dioxide/polyimide composite material. An SEM image of the titanium dioxide/polyimide composite material prepared by the invention is shown in figure 2, the composite material has excellent adsorption performance on organic pollutants, wherein the adsorption performance on methylene blue is 180mg/g, and the adsorbed methylene blue is completely decomposed after being irradiated for 60min under the irradiation of a 300W mercury lamp as a light source.

Example 2

(1) Dissolving 1000mg of amphiphilic polyimide in 100mL of N-methylpyrrolidone solution, and stirring for 1h at 50 ℃ to obtain 10mg/mL of polyimide solution, wherein the structural formula of the amphiphilic polyimide is shown in the attached figure 1;

(2) adding 40mg of sodium dodecyl sulfate into 20mL of water to prepare a solution of 2mg/mL, then adding the solution into the solution obtained in the step (1), and stirring at room temperature for 0.5 h;

(3) adding 2mL of glacial acetic acid into the solution obtained in the step (2), then adding 1.2g of butyl titanate, stirring at room temperature for 1h, and continuing to react for 8h, wherein the concentration of the butyl titanate is 10 mg/mL;

(4) and (4) pouring the product obtained in the step (3) into 500mL of deionized water, precipitating, filtering, and then putting into a vacuum oven to dry for 6 hours at 60 ℃ to obtain the titanium dioxide/polyimide composite material. The titanium dioxide/polyimide composite material prepared by the invention has excellent adsorption performance on organic pollutants, wherein the adsorption performance on methylene blue is 216mg/g, and the adsorbed methylene blue is completely decomposed after being irradiated for 60min under the irradiation of a 300W mercury lamp as a light source.

Example 3

(1) Dissolving 100mg of amphiphilic polyimide in 100mL of N-methylpyrrolidone solution, and stirring for 1h at 50 ℃ to obtain 1mg/mL of polyimide solution, wherein the structural formula of the amphiphilic polyimide is shown in the attached figure 1;

(2) adding 200mg of sodium dodecyl sulfate into 20mL of water to prepare a solution of 10mg/mL, then adding the solution into the solution obtained in the step (1), and stirring at room temperature for 0.5 h;

(3) adding 2mL of glacial acetic acid into the solution obtained in the step (2), then adding 1.2g of butyl titanate, stirring at room temperature for 1h, and continuing to react for 8h, wherein the concentration of the butyl titanate is 10 mg/mL;

(4) and (4) pouring the product obtained in the step (3) into 500mL of deionized water, precipitating, filtering, and then putting into a vacuum oven to dry for 6 hours at 60 ℃ to obtain the titanium dioxide/polyimide composite material. The titanium dioxide/polyimide composite material prepared by the invention has excellent adsorption performance on organic pollutants, wherein the adsorption performance on methylene blue is 176mg/g, and the adsorbed methylene blue is completely decomposed after being irradiated for 60min under the irradiation of a 300W mercury lamp as a light source.

Example 4

(1) Dissolving 100ng of amphiphilic polyimide in 100mL of N-methylpyrrolidone solution, stirring at 50 ℃ for 1h to obtain 1mg/mL of polyimide solution, wherein the structural formula of the amphiphilic polyimide is shown in figure 1,

(2) adding 40mg of sodium dodecyl sulfate into 20mL of water to prepare a solution of 2mg/mL, then adding the solution into the solution obtained in the step (1), and stirring at room temperature for 0.5 h;

(3) adding 2mL of glacial acetic acid into the solution obtained in the step (2), then adding 6g of butyl titanate, stirring at room temperature for 1h, and continuing to react for 8h, wherein the concentration of the butyl titanate is 50 mg/mL;

(4) and (4) pouring the product obtained in the step (3) into 500mL of deionized water, precipitating, filtering, and then putting into a vacuum oven to dry for 6 hours at 60 ℃ to obtain the titanium dioxide/polyimide composite material. The titanium dioxide/polyimide composite material prepared by the invention has excellent adsorption performance on organic pollutants, wherein the adsorption performance on methylene blue is 166mg/g, and the adsorbed methylene blue is completely decomposed after being irradiated for 60min under the irradiation of a 300W mercury lamp as a light source.

Example 5

(1) Dissolving 100ng of amphiphilic polyimide in 100mL of N-methylpyrrolidone solution, stirring at 50 ℃ for 1h to obtain 1mg/mL of polyimide solution, wherein the structural formula of the amphiphilic polyimide is shown in figure 1,

(2) adding 40mg of sodium dodecyl sulfate into 20mL of water to prepare a solution of 2mg/mL, then adding the solution into the solution obtained in the step (1), and stirring at room temperature for 0.5 h;

(3) adding 2mL of glacial acetic acid into the solution obtained in the step (2), then adding 1.2g of butyl titanate, stirring at room temperature for 1h, and continuing to react for 8h, wherein the concentration of the butyl titanate is 10 mg/mL;

(4) and (4) pouring the product obtained in the step (3) into 1000mL of deionized water, precipitating, filtering, and then putting into a vacuum oven to dry for 8 hours at 80 ℃ to obtain the titanium dioxide/polyimide composite material. The titanium dioxide/polyimide composite material prepared by the invention has excellent adsorption performance on organic pollutants, wherein the adsorption performance on methylene blue is 184mg/g, and the adsorbed methylene blue is completely decomposed after being irradiated for 60min under the irradiation of a 300W mercury lamp as a light source.