阅读说明：本技术 一种具有光降解功能金属元素掺杂二氧化钛/含氟高分子薄膜复合材料的制备方法 (Preparation method of metal element-doped titanium dioxide/fluorine-containing polymer film composite material with photodegradation function ) 是由 余媛 于斌 朱海霖 何薇薇 薛淑滢 于 2020-12-08 设计创作，主要内容包括：本发明提供一种具有光降解功能金属元素掺杂二氧化钛/含氟高分子薄膜复合材料的制备方法,包括,将金属离子化合物干燥、研磨后,加入钛酸四丁酯溶液中均匀搅拌,制得金属离子-钛酸四丁酯混合溶液；将金属离子-钛酸四丁酯混合溶液进行水解反应,制备金属元素掺杂二氧化钛凝胶或胶体,进行高温干燥,制得金属元素掺杂二氧化钛晶体；将金属元素掺杂二氧化钛晶体加入液相研磨设备,得到含有金属元素掺杂二氧化钛/含氟高分子复配溶液,经过涂膜工艺制备含氟高分子薄膜。本发明在纳米二氧化钛制备过程中将银、锌、铜金属离子加入,参与二氧化钛晶型形成过程,结构稳定,没有析出的风险,可以用于制备功能纤维材料以及薄膜产品。(The invention provides a preparation method of a metal element doped titanium dioxide/fluorine-containing polymer film composite material with a photodegradation function, which comprises the steps of drying and grinding a metal ion compound, adding the metal ion compound into a tetrabutyl titanate solution, and uniformly stirring to prepare a metal ion-tetrabutyl titanate mixed solution; carrying out hydrolysis reaction on the metal ion-tetrabutyl titanate mixed solution to prepare metal element doped titanium dioxide gel or colloid, and drying at high temperature to prepare metal element doped titanium dioxide crystals; adding the metal element doped titanium dioxide crystal into liquid phase grinding equipment to obtain a metal element doped titanium dioxide/fluorine-containing polymer compound solution, and preparing the fluorine-containing polymer film by a film coating process. In the invention, silver, zinc and copper metal ions are added in the preparation process of the nano titanium dioxide to participate in the formation process of titanium dioxide crystal form, the structure is stable, the risk of precipitation is avoided, and the method can be used for preparing functional fiber materials and film products.)

1. A preparation method of a metal element doped titanium dioxide/fluorine-containing polymer film composite material with a photodegradation function is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,

preparing tetrabutyl titanate solution;

drying and grinding the metal ion compound, adding the metal ion compound into the tetrabutyl titanate solution, and uniformly stirring to prepare a metal ion-tetrabutyl titanate mixed solution;

carrying out hydrolysis reaction on the metal ion-tetrabutyl titanate mixed solution to prepare metal element doped titanium dioxide gel or colloid;

drying the metal ion doped titanium dioxide gel or colloid at high temperature to prepare a metal element doped titanium dioxide crystal;

adding the metal element doped titanium dioxide crystal into liquid phase grinding equipment to obtain a metal element doped titanium dioxide/fluorine-containing polymer compound solution, and preparing the fluorine-containing polymer film by a film coating process.

2. The method for preparing the photodegradation-functional metal element-doped titanium dioxide/fluorine-containing polymer thin film composite material according to claim 1, wherein the method comprises the following steps: the prepared tetrabutyl titanate solution comprises the following components,

selecting tetrabutyl titanate or titanium tetrachloride as a solute, ethanol or other alcohols as a solvent, wherein the mass fraction of the solute is 20-70%, and stirring in a homogenizing stirrer to prepare a tetrabutyl titanate solution, wherein the stirring speed is 500-1000 rpm, and the stirring time is 20-60 min.

3. The method for preparing the photodegradation-functional metal element-doped titanium dioxide/fluorine-containing polymer thin film composite material according to claim 1, wherein the method comprises the following steps: the metal ion compound is dried and ground, wherein,

the metal compound is one or more of zinc chloride/copper, zinc sulfate/copper and zinc nitrate/copper/silver;

the drying temperature is 80-130 ℃, the drying time is 3-6 h, and the dried powder is ground in a ball mill for 40-80 min.

4. The method for preparing the photodegradation-functional metal element-doped titanium dioxide/fluorine-containing polymer thin film composite material according to any one of claims 1 to 3, wherein the method comprises the following steps: after drying and grinding the metal ion compound, adding the metal ion compound into tetrabutyl titanate solution, and uniformly stirring, wherein the stirring speed is 800-1400 rpm, and the stirring time is 40-80 min until no gel appears; the addition amount of the metal element-containing compound is 1:100 to 1:10 in terms of the molar ratio of the metal element to titanium in the tetrabutyl titanate solution.

5. The method for preparing the photodegradable metal element-doped titanium dioxide/fluorine-containing polymer thin film composite material according to any one of claims 1 to 3, wherein the method comprises the following steps: the hydrolysis reaction of the metal ion-tetrabutyl titanate mixed solution comprises the following steps,

and (2) dropwise adding the purified water into the metal ion-tetrabutyl titanate mixed solution, continuously stirring in the dropwise adding process, observing the solution phenomenon, and stopping dropwise adding the purified water until the colloid appears, wherein the adding amount of the purified water is 0.1-0.5% of the mass of the solution.

6. The method for preparing the photodegradable metal element-doped titanium dioxide/fluorine-containing polymer thin film composite material according to any one of claims 1 to 3, wherein the method comprises the following steps: the high-temperature drying of the metal ion doped titanium dioxide gel or colloid comprises the following steps,

and (3) putting the metal ion doped titanium dioxide gel or colloid into an oven, drying for 2-10 h at 80-120 ℃, roasting for 30-90 min at 300-450 ℃, and naturally cooling to obtain the metal element doped titanium dioxide crystal.

7. The method for preparing the photodegradable metal element-doped titanium dioxide/fluorine-containing polymer thin film composite material according to any one of claims 1 to 3, wherein the method comprises the following steps: adding the metal element doped titanium dioxide crystal into liquid phase grinding equipment, wherein the solid content is 0.1-10%, the temperature is 40-80 ℃, and grinding for 3-8 hours to obtain the metal element doped titanium dioxide/fluorine-containing polymer compound solution.

8. The method for preparing the photodegradation-functional metal element-doped titanium dioxide/fluorine-containing polymer thin film composite material according to claim 7, wherein the method comprises the following steps: the metal element doped titanium dioxide crystal is added into liquid phase grinding equipment, wherein,

the grinding liquid phase carrier is a fluorine-containing high polymer material solution which is an N, N-dimethylformamide or N-methylpyrrolidone solution containing polyvinylidene fluoride and polyethylene glycol, and the mass concentration of the polyvinylidene fluoride is 3-30%; the addition amount of the polyethylene glycol is 0-10% of the mass fraction of the polyvinylidene fluoride.

9. The method for preparing the photodegradable metal element-doped titanium dioxide/fluorine-containing polymer thin film composite material according to any one of claims 1 to 3, wherein the method comprises the following steps: the film coating process comprises the following steps of,

standing and degassing the metal element-containing titanium dioxide/fluorine-containing polymer compound solution at normal temperature, preparing a film by adopting a spin-coating method, coating the compound solution on a template, immersing the template in water, and standing for 10-40 min at 20-25 ℃ to obtain the metal element-containing titanium dioxide/fluorine-containing polymer film composite material with the photodegradation function.

Technical Field

The invention belongs to the field of preparation of nano composite functional materials, and particularly relates to a preparation method of a metal element doped titanium dioxide/fluorine-containing polymer film composite material with a photodegradation function.

Background

Along with the improvement of living standard of people, the quality requirement of people to living environment is higher and higher, and along with the attention of people to self health, more and more consumers realize that air quality has important influence to health. For example, the high content of VOC in the air can cause the occurrence of diseases, the high content of formaldehyde can cause the occurrence of high-risk diseases such as septicemia and the like. Therefore, there is an urgent market demand for the functionalization of filter materials.

At present, photocatalyst titanium dioxide and nano zinc oxide are adopted as photodegradation functional materials for wide application, but the titanium dioxide and the zinc oxide are excited by ultraviolet rays in light, the required energy is high, the application is limited to a certain extent, and the photodegradation efficiency is low under visible radiation.

Disclosure of Invention

This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.

The present invention has been made in view of the above-mentioned technical drawbacks.

Therefore, as one aspect of the invention, the invention overcomes the defects in the prior art and provides a preparation method of a titanium dioxide/fluorine-containing polymer film composite material doped with a metal element with a photodegradation function.

In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a titanium dioxide/fluorine-containing polymer film composite material doped with metal elements with photodegradation function comprises the steps of preparing tetrabutyl titanate solution; drying and grinding the metal ion compound, adding the metal ion compound into the tetrabutyl titanate solution, and uniformly stirring to prepare a metal ion-tetrabutyl titanate mixed solution; carrying out hydrolysis reaction on the metal ion-tetrabutyl titanate mixed solution to prepare metal element doped titanium dioxide gel or colloid; drying the metal ion doped titanium dioxide gel or colloid at high temperature to prepare a metal element doped titanium dioxide crystal; adding the metal element doped titanium dioxide crystal into liquid phase grinding equipment to obtain a metal element doped titanium dioxide/fluorine-containing polymer compound solution, and preparing the fluorine-containing polymer film by a film coating process.

As a preferable scheme of the preparation method of the photodegradation metal element doped titanium dioxide/fluorine-containing polymer film composite material, the preparation method comprises the following steps: the preparation method of the tetrabutyl titanate solution comprises the steps of selecting tetrabutyl titanate or titanium tetrachloride as a solute, ethanol or other alcohols as a solvent, stirring in a homogenizing stirrer to obtain the tetrabutyl titanate solution, wherein the mass fraction of the solute is 20-70%, the stirring speed is 500-1000 rpm, and the stirring time is 20-60 min.

As a preferable scheme of the preparation method of the photodegradation metal element doped titanium dioxide/fluorine-containing polymer film composite material, the preparation method comprises the following steps: drying and grinding the metal ion compound, wherein the metal compound is one or more of zinc chloride/copper, zinc sulfate/copper and zinc nitrate/copper/silver; the drying temperature is 80-130 ℃, the drying time is 3-6 h, and the dried powder is ground in a ball mill for 40-80 min.

As a preferable scheme of the preparation method of the photodegradation metal element doped titanium dioxide/fluorine-containing polymer film composite material, the preparation method comprises the following steps: after drying and grinding the metal ion compound, adding the metal ion compound into tetrabutyl titanate solution, and uniformly stirring, wherein the stirring speed is 800-1400 rpm, and the stirring time is 40-80 min until no gel appears; the addition amount of the metal element-containing compound is 1:100 to 1:10 in terms of the molar ratio of the metal element to titanium in the tetrabutyl titanate solution.

As a preferable scheme of the preparation method of the photodegradation metal element doped titanium dioxide/fluorine-containing polymer film composite material, the preparation method comprises the following steps: the hydrolysis reaction of the metal ion-tetrabutyl titanate mixed solution comprises the steps of dropwise adding purified water into the metal ion-tetrabutyl titanate mixed solution, continuously stirring in the dropwise adding process, observing the solution phenomenon, and stopping dropwise adding the purified water until colloid appears, wherein the adding amount of the purified water is 0.1-0.5% of the mass of the solution.

As a preferable scheme of the preparation method of the photodegradation metal element doped titanium dioxide/fluorine-containing polymer film composite material, the preparation method comprises the following steps: the metal ion doped titanium dioxide gel or colloid is dried at high temperature, and the method comprises the steps of drying the metal ion doped titanium dioxide gel or colloid in an oven at 80-120 ℃ for 2-10 hours, roasting at 300-450 ℃ for 30-90 min, and naturally cooling to obtain the metal element doped titanium dioxide crystal.

As a preferable scheme of the preparation method of the photodegradation metal element doped titanium dioxide/fluorine-containing polymer film composite material, the preparation method comprises the following steps: adding the metal element doped titanium dioxide crystal into liquid phase grinding equipment, wherein the solid content is 0.1-10%, the temperature is 40-80 ℃, and grinding for 3-8 hours to obtain the metal element doped titanium dioxide/fluorine-containing polymer compound solution.

As a preferable scheme of the preparation method of the photodegradation metal element doped titanium dioxide/fluorine-containing polymer film composite material, the preparation method comprises the following steps: adding the metal element doped titanium dioxide crystal into liquid phase grinding equipment, wherein a grinding liquid phase carrier is a fluorine-containing high polymer material solution which is an N, N-dimethylformamide or N-methylpyrrolidone solution containing polyvinylidene fluoride and polyethylene glycol, and the mass concentration of the polyvinylidene fluoride is 3-30%; the addition amount of the polyethylene glycol is 0-10% of the mass fraction of the polyvinylidene fluoride.

As a preferable scheme of the preparation method of the photodegradation metal element doped titanium dioxide/fluorine-containing polymer film composite material, the preparation method comprises the following steps: the coating process comprises the steps of standing and degassing a metal element-containing titanium dioxide/fluorine-containing polymer compound solution at normal temperature, preparing a film by adopting a spin-coating method, coating the compound solution on a template, immersing the template in water, and standing for 10-40 min at 20-25 ℃ to obtain the metal element-containing titanium dioxide/fluorine-containing polymer film composite material with the photodegradation function.

The invention has the beneficial effects that:

the invention realizes the preparation of titanium dioxide nano particles doped with metal elements such as silver, zinc, copper and the like, has simple method and controllable nano material particle size, improves the absorption of titanium dioxide in a visible light region by doping, increases the photodegradation efficiency, has certain viscosity of a PEG and PVDF mixed solution, can add prepared nano powder into liquid phase grinding equipment for dispersion, prepares a fluorine-containing stable film with certain porosity and photodegradation function by a film coating mode, and the porosity can be regulated and controlled by the content of PEG or PVP, thereby increasing the functionality of the PVDF film and increasing the added value of products.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:

FIG. 1 is a surface topography of a PVDF film at 3% PEG content.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.

Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.

Example 1:

the embodiment provides a preparation method of a metal element doped titanium dioxide/fluorine-containing polymer film composite material with a photodegradation function, which comprises the following steps:

(1) weighing 1000 g of tetrabutyl titanate, dissolving in 1000 g of ethanol, and stirring for 40min at the stirring speed of 1000 rpm;

(2) drying zinc chloride at 120 ℃ for 4h, and then putting the zinc chloride into a liquid phase ball mill for grinding, wherein the liquid phase grinding medium is ethanol, so as to form a homogeneous zinc chloride ethanol colloid;

(3) the zinc chloride ethanol colloid was then added dropwise to an ethanol solution of tetrabutyl titanate, zinc: the molar ratio of titanium is 1:30, stirring is continuously carried out for 60min in the dripping process, no gel appears, purified water is slowly dripped at the moment, the solution state is observed, the dripping is stopped when the gel appears, and the adding amount of the purified water is 0.2 percent at the moment;

(4) drying the gel in an oven at 100 ℃ for 6h to remove most of the solvent to form a blue crystal, placing the gel in a high-temperature oven to roast at 400 ℃ for 60min, and removing the residual solvent to form a crystal;

(5) crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 0.1 percent of the mass of the solution, the PVDF accounts for 3 percent of the mass of the solution, and the PEG accounts for 0 percent of the mass of the PVDF.

(6) Standing and degassing the titanium dioxide/fluorine-containing polymer compound solution containing the metal element at normal temperature, preparing a film in a knife coating mode, immersing the film in water, and standing for 30min at 25 ℃ to obtain the film.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 1.

TABLE 1 photodegradability of zinc-doped nano-titanium dioxide PVDF film

At this time, the film forming property was not good, so that a uniform film was prepared by first adjusting the PVDF content.

Example 2:

the embodiment provides a preparation method of a metal element doped titanium dioxide/fluorine-containing polymer film composite material with a photodegradation function, which comprises the following steps:

(1) weighing 1000 g of tetrabutyl titanate, dissolving in 1000 g of ethanol, and stirring for 40min at the stirring speed of 1000 rpm;

(2) drying zinc chloride at 120 ℃ for 4h, and then putting the zinc chloride into a liquid phase ball mill for grinding, wherein the liquid phase grinding medium is ethanol, so as to form a homogeneous zinc chloride ethanol colloid;

(3) the zinc chloride ethanol colloid was then added dropwise to an ethanol solution of tetrabutyl titanate, zinc: the molar ratio of titanium is 1:30, stirring is continuously carried out for 60min in the dripping process, no gel appears, purified water is slowly dripped at the moment, the solution state is observed, the dripping is stopped when the gel appears, and the adding amount of the purified water is 0.2 percent at the moment.

(4) Drying the gel in an oven at 100 ℃ for 6h to remove most of the solvent to form a blue crystal, and then placing the gel in a high-temperature oven to roast for 60min at 400 ℃, and removing the residual solvent to form a crystal;

(5) crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 0.1 percent of the mass of the solution, the PVDF accounts for 6 percent of the mass of the solution, and the PEG accounts for 0 percent of the mass of the PVDF.

(6) Standing and degassing the titanium dioxide/fluorine-containing polymer compound solution containing the metal element at normal temperature, preparing a film in a knife coating mode, immersing the film in water, and standing for 30min at 25 ℃ to obtain the film.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 2.

TABLE 2 photodegradability of zinc-doped nano-titanium dioxide PVDF film

The film uniformity was still insufficient and the PVDF content continued to increase.

Example 3:

the embodiment provides a preparation method of a metal element doped titanium dioxide/fluorine-containing polymer film composite material with a photodegradation function, which comprises the following steps:

(1) weighing 1000 g of tetrabutyl titanate, dissolving in 1000 g of ethanol, and stirring for 40min at the stirring speed of 1000 rpm;

(2) drying zinc chloride at 120 ℃ for 4h, and then putting the zinc chloride into a liquid phase ball mill for grinding, wherein the liquid phase grinding medium is ethanol, so as to form a homogeneous zinc chloride ethanol colloid;

(3) the zinc chloride ethanol colloid was then added dropwise to an ethanol solution of tetrabutyl titanate, zinc: the molar ratio of titanium is 1:30, stirring is continuously carried out for 60min in the dripping process, no gel appears, purified water is slowly dripped at the moment, the solution state is observed, the dripping is stopped when the gel appears, and the adding amount of the purified water is 0.2 percent at the moment;

(4) drying the gel in an oven at 100 ℃ for 6h to remove most of the solvent to form a blue crystal, placing the gel in a high-temperature oven to roast at 400 ℃ for 60min, and removing the residual solvent to form a crystal;

(5) crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 0.1 percent of the mass of the solution, the PVDF accounts for 10 percent of the mass of the solution, and the PEG accounts for 0 percent of the mass of the PVDF.

(6) Standing and degassing the titanium dioxide/fluorine-containing polymer compound solution containing the metal element at normal temperature, preparing a film in a knife coating mode, immersing the film in water, and standing for 30min at 25 ℃ to obtain the film.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 3.

TABLE 3 photodegradability of zinc-doped nano-titanium dioxide PVDF film

At this time, a uniform film was obtained.

Example 4:

the process in step (5) of this example is different from that of example 3, and the rest is the same as example 3:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 0.1 percent of the mass ratio of the solution, the PVDF accounts for 15 percent of the mass ratio of the solution, and the PEG accounts for 0 percent of the mass ratio of the PVDF

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 4.

TABLE 4 photodegradability of zinc-doped nano-titanium dioxide PVDF film

The film uniformity is better at this time.

Example 5:

the process in step (5) of this example is different from that of example 3, and the rest is the same as example 3:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 0.1 percent of the mass ratio of the solution, the PVDF accounts for 20 percent of the mass ratio of the solution, and the PEG accounts for 0 percent of the mass ratio of the PVDF

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 5.

TABLE 5 photodegradability of zinc-doped nano-titanium dioxide PVDF film

The film uniformity is better at this time.

Example 6:

the process in step (5) of this example is different from that of example 3, and the rest is the same as example 3:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 0.1 percent of the mass ratio of the solution, the PVDF accounts for 25 percent of the mass ratio of the solution, and the PEG accounts for 0 percent of the mass ratio of the PVDF

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 6.

TABLE 6 photodegradability of zinc-doped nano-titanium dioxide PVDF film

It can be seen that when the content of PVDF reaches 25%, the photodegradation efficiency is reduced to some extent, and the specific surface area is reduced due to the increase of the thickness, and the photodegradation nano-functional powder is less exposed on the surface of the film, which leads to the reduction of the photodegradation efficiency, so the content of PVDF is preferably determined to be 20% in the present invention.

Example 7:

the process in step (5) of this example is different from that of example 5, and the rest is the same as example 5:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 0.5 percent of the mass of the solution, the PVDF accounts for 20 percent of the mass of the solution, and the PEG accounts for 0 percent of the mass of the PVDF.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 7.

TABLE 7 photodegradability of zinc-doped nano-titanium dioxide PVDF film

At the moment, the film uniformity is better, and the photodegradation efficiency is improved.

Example 8:

the process in step (5) of this example is different from that of example 5, and the rest is the same as example 5:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 1% of the solution by mass, the PVDF accounts for 20% of the solution by mass, and the PEG accounts for 0% of the PVDF by mass.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 8.

TABLE 8 photodegradability of zinc-doped nano-titanium dioxide PVDF film

At the moment, the film uniformity is better, and the photodegradation efficiency is improved.

Example 9:

the process in step (5) of this example is different from that of example 5, and the rest is the same as example 5:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 2% of the solution by mass, the PVDF accounts for 20% of the solution by mass, and the PEG accounts for 0% of the PVDF by mass.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 9.

TABLE 9 photodegradability of zinc-doped nano-titanium dioxide PVDF film

At the moment, the film uniformity is better, and the photodegradation efficiency is improved.

Example 10:

the process in step (5) of this example is different from that of example 5, and the rest is the same as example 5:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 4% of the solution by mass, the PVDF accounts for 20% of the solution by mass, and the PEG accounts for 0% of the PVDF by mass.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 10.

TABLE 10 photodegradability of zinc-doped nano-titanium dioxide PVDF film

At the moment, the film uniformity is better, and the photodegradation efficiency is improved.

Example 11:

the process in step (5) of this example is different from that of example 5, and the rest is the same as example 5:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 6% of the solution by mass, the PVDF accounts for 20% of the solution by mass, and the PEG accounts for 0% of the PVDF by mass.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 11.

TABLE 11 photodegradability of zinc-doped nano-titanium dioxide PVDF film

At this time, the uniformity of the film is poor, and the improvement range of the photodegradation efficiency is not large, so that the data of example 9 and example 10 are measured, and the addition amount of the photodegradation functional powder is determined to be 3%.

Example 12:

the process in step (5) of this example is different from that of example 5, and the rest is the same as example 5:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 3% of the solution by mass, the PVDF accounts for 20% of the solution by mass, and the PEG (PEG-200) accounts for 1% of the PVDF by mass.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 12.

TABLE 12 photodegradability of zinc-doped nano-titanium dioxide PVDF film

At the moment, the film uniformity is better, and the photodegradation efficiency is improved.

Example 13:

the process in step (5) of this example is different from that of example 5, and the rest is the same as example 5:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 3% of the solution by mass, the PVDF accounts for 20% of the solution by mass, and the PEG (PEG-200) accounts for 3% of the PVDF by mass.

The zinc-doped nano titanium dioxide PVDF film is shown in figure 1.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 13.

TABLE 13 photodegradability of zinc-doped nano-titanium dioxide PVDF film

At the moment, the film uniformity is better, and the photodegradation efficiency is improved.

Example 14:

the process in step (5) of this example is different from that of example 5, and the rest is the same as example 5:

crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 3% of the solution by mass, the PVDF accounts for 20% of the solution by mass, and the PEG (PEG-200) accounts for 6% of the PVDF by mass.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 14.

TABLE 14 photodegradability of zinc-doped nano-titanium dioxide PVDF film

At the moment, the film uniformity is better, the photodegradation efficiency is not improved basically, which shows that the specific surface area of the film can not be increased by increasing the amount of PEG, so that the photodegradation efficiency is not increased.

Example 15:

the embodiment provides a preparation method of a metal element doped titanium dioxide/fluorine-containing polymer film composite material with a photodegradation function, which comprises the following steps:

(1) weighing 1000 g of tetrabutyl titanate, dissolving in 1000 g of ethanol, and stirring for 40min at the stirring speed of 1000 rpm;

(2) drying copper chloride at 120 ℃ for 4h, and then putting the copper chloride into a liquid phase ball mill for grinding, wherein the liquid phase grinding medium is ethanol, so as to form a homogeneous zinc chloride ethanol colloid;

(3) the copper chloride ethanol colloid was then added dropwise to the ethanol solution of tetrabutyl titanate, copper: the molar ratio of titanium is 1:30, stirring is continuously carried out for 60min in the dripping process, no gel appears, purified water is slowly dripped at the moment, the solution state is observed, the dripping is stopped when the gel appears, and the adding amount of the purified water is 0.2 percent at the moment;

(4) drying the gel in an oven at 100 deg.C for 6h to remove most of the solvent, forming blue crystal, and calcining in a high temperature oven at 400 deg.C for 60min, at which time the remaining solvent is removed to form crystals.

(5) Crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 3% of the solution by mass, the PVDF accounts for 20% of the solution by mass, and the PEG (PEG-200) accounts for 3% of the PVDF by mass.

(6) Standing and degassing the titanium dioxide/fluorine-containing polymer compound solution containing the metal element at normal temperature, preparing a film in a knife coating mode, immersing the film in water, and standing for 30min at 25 ℃ to obtain the film.

TABLE 15 photodegradability of copper-doped nano-titanium dioxide PVDF film

The film has better uniformity and the copper doping efficiency is slightly higher than that of the zinc doping.

Example 16:

the embodiment provides a preparation method of a metal element doped titanium dioxide/fluorine-containing polymer film composite material with a photodegradation function, which comprises the following steps:

(1) weighing 1000 g of tetrabutyl titanate, dissolving in 1000 g of ethanol, and stirring for 40min at the stirring speed of 1000 rpm;

(2) drying silver nitrate at 120 ℃ for 4h, and then putting the silver nitrate into a liquid phase ball mill for grinding, wherein the liquid phase grinding medium is ethanol, so as to form homogeneous silver nitrate ethanol colloid;

(3) the silver nitrate ethanol colloid was then added dropwise to the ethanol solution of tetrabutyl titanate, silver: the molar ratio of titanium is 1:30, stirring is continuously carried out for 60min in the dripping process, no gel appears, purified water is slowly dripped at the moment, the solution state is observed, the dripping is stopped when the gel appears, and the adding amount of the purified water is 0.2 percent at the moment.

(4) Drying the gel in an oven at 100 deg.C for 6h to remove most of the solvent, making the gel into crystal, and baking in a high temperature oven at 400 deg.C for 60min, at which time removing the residual solvent to form crystal.

(5) Crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 3% of the solution by mass, the PVDF accounts for 20% of the solution by mass, and the PEG (PEG-200) accounts for 3% of the PVDF by mass.

(6) Standing and degassing the titanium dioxide/fluorine-containing polymer compound solution containing the metal element at normal temperature, preparing a film in a knife coating mode, immersing the film in water, and standing for 30min at 25 ℃ to obtain the film. The photodegradation test was performed according to QB/T2761-2006.

TABLE 16 photodegradability of silver-doped nano-titanium dioxide PVDF film

At the moment, the film uniformity is better, the difference between the silver doping efficiency and the zinc is not great, and the main reason for analysis is that the color of the crystal generated by copper doping is darker, and the absorption efficiency of the crystal to visible light is higher.

According to the invention, metal elements such as silver, zinc, copper and the like are used for doping titanium dioxide, metal ions such as silver, zinc, copper and the like are added in the preparation process of nano titanium dioxide to participate in the formation process of titanium dioxide crystal form, and then a doped crystal structure is formed in the later high-temperature oxidation process, so that the structure is stable, has no risk of precipitation, is safe and reliable to the environment, has no pollution, and can be used for preparing functional fiber materials and film products.

Example 17:

the embodiment provides a preparation method of a metal element doped titanium dioxide/fluorine-containing polymer film composite material with a photodegradation function, which comprises the following steps:

(1) weighing 1000 g of tetrabutyl titanate, dissolving in 1000 g of ethanol, and stirring for 40min at the stirring speed of 1000 rpm;

(2) drying zinc chloride at 120 ℃ for 4h, and then putting the zinc chloride into a liquid phase ball mill for grinding, wherein the liquid phase grinding medium is ethanol, so as to form a homogeneous zinc chloride ethanol colloid;

(3) the zinc chloride ethanol colloid was then added dropwise to an ethanol solution of tetrabutyl titanate, zinc: the molar ratio of titanium is 1:20, stirring is continuously carried out for 60min in the dripping process, no gel appears, purified water is slowly dripped at the moment, the solution state is observed, and the process is stopped when the gel appears;

(4) drying the gel in an oven at 100 ℃ for 6h to remove most of the solvent to form a blue crystal, placing the gel in a high-temperature oven to roast at 400 ℃ for 60min, and removing the residual solvent to form a crystal;

(5) crushing the crystals by a crusher, adding the crushed crystals into a DMF (dimethyl formamide) solution of PVDF, and dispersing by a liquid phase grinding device: grinding for 8 hours at the temperature of 60 ℃ to obtain a titanium dioxide/fluorine-containing polymer compound solution doped with metal elements; wherein the crystal powder accounts for 3% of the solution by mass, the PVDF accounts for 20% of the solution by mass, and the PEG (PEG-200) accounts for 3% of the PVDF by mass.

(6) Standing and degassing the titanium dioxide/fluorine-containing polymer compound solution containing the metal element at normal temperature, preparing a film in a knife coating mode, immersing the film in water, and standing for 30min at 25 ℃ to obtain the film.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 17.

TABLE 17 photodegradability of zinc-doped nano-titanium dioxide PVDF film

Example 18:

the process in step (3) of this example is different from that of example 17, and the rest of the steps are the same as those of example 17:

the zinc chloride ethanol colloid was then added dropwise to an ethanol solution of tetrabutyl titanate, zinc: the molar ratio of titanium is 1:80, stirring is continuously carried out for 60min in the dripping process, no gel appears, at the moment, pure water is slowly dripped, the solution state is observed, and the process is stopped when the gel appears.

The photodegradation test was performed according to QB/T2761-2006, and the results are shown in Table 18.

TABLE 18 photodegradability of zinc-doped nano-titanium dioxide PVDF film

It can be seen that too high content of doped metal elements can cause serious damage to the titanium dioxide crystal structure, no crystal formation, and too little doping amount can not form uniform defects, which is not beneficial to improving the photodegradation efficiency.

The invention realizes the preparation of titanium dioxide nano particles doped with metal elements such as silver, zinc, copper and the like, has simple method and controllable nano material particle size, improves the absorption of titanium dioxide in a visible light region by doping, increases the photodegradation efficiency, has certain viscosity of a PEG and PVDF mixed solution, can add prepared nano powder into liquid phase grinding equipment for dispersion, prepares a fluorine-containing stable film with certain porosity and photodegradation function by a film coating mode, and the porosity can be regulated and controlled by the content of PEG or PVP, thereby increasing the functionality of the PVDF film and increasing the added value of products.

It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.