Polysilsesquioxane / polyetheretherketone composite membrane, preparation method therefor and use thereof in organic mixed solvent separation

Abstract

Disclosed in the present invention are a polysilsesquioxane / polyetheretherketone composite membrane, a preparation method therefor, and a use thereof in organic mixed solvent separation. In view of the existing challenge of large-area deposition of defect-free polysilsesquioxane hybrid membranes on polymer substrates, provided is a novel membrane preparation method using a 1,2-bis(triethoxysilyl)ethane polysilsesquioxane precursor as a raw material for preparing a membrane material. From the perspectives of the simplicity of a membrane preparation process, the industrialization of a membrane separation technology, and the improvement of membrane preparation efficiency, a processing process is designed and optimized, thereby improving the membrane preparation efficiency while maintaining certain separation performance, and exhibiting excellent effects in the separation and recovery of methanol / toluene and methanol / dimethyl carbonate.

Description

A polysilsesquioxane / polyether ether ketone composite membrane, a preparation method thereof and application thereof in separation of organic mixed solvents TECHNICAL FIELD

[0001] The present application belongs to the field of membrane separation technology, and particularly relates to a polysilsesquioxane / polyether ether ketone composite membrane, a preparation method thereof and application thereof in separation of organic mixed solvents. BACKGROUND

[0002] Toluene is a widely used organic solvent, and is widely used in petroleum and chemical industries, such as paints, rubber, glue silicone sealant, ink, paint, disinfectant, leather tanning agent. However, in the industrial production process of toluene, for example, the alkylation reaction of benzene and methanol, the product stream contains a mixture of methanol and toluene, so how to effectively separate methanol / toluene is very important. Dimethyl carbonate (DMC) is a green solvent that combines cleanliness and safety, and it is a fuel additive and a chemical raw material that can replace phosgene and other harmful substances. Since methanol (MeOH) can produce dimethyl carbonate, efficient separation of azeotrope is essential for the development of dimethyl carbonate. The recovery of organic solvents including methanol can provide immediate cost savings and significant environmental benefits for many chemical manufacturing companies. However, many organic-organic mixtures produce azeotropic or near-boiling point mixtures, which cannot always be easily recovered by conventional distillation. On this basis, it is very important to develop an economical and effective separation technology for organic solvent separation.

[0003] Polyether ether ketone (Peek) is composed of repeating phenyl ether and benzophenone units, and due to its inherent structural properties, it exhibits strong chemical resistance in aggressive solvents. And as an aromatic polymer, Peek is known for its high operating temperature and chemical resistance, and its inherent properties are widely used in the synthesis of various separation membranes, especially in harsh conditions. And as an ultrafiltration membrane, Peek needs to reduce the pore size of the membrane surface to perform pervaporation separation of organic mixed solvents.

[0004] In recent decades, a variety of microporous materials such as polymers, inorganic and organic-inorganic hybrid materials have been extensively studied to obtain high-performance membranes for organic mixed solvent separation. Among them, the polysilsesquioxane hybrid membrane formed by the covalent combination of organic bridging groups with two silicon atoms dominates the research of silicon hybrid materials in PV and VP processes. This is mainly because the polysilsesquioxane network structure has amazing thermal stability and chemical stability, adjustable pore size and affinity, and superior peroxide selectivity. These ideal properties come from the uniform combination of different organic bridges in the polysilsesquioxane network through covalent bonds. Polysilsesquioxane has been proved to be a good precursor for preparing silicon-based organic-inorganic hybrid membranes. However, it has always been a great challenge to deposit large-area defect-free polysilsesquioxane hybrid membranes on polymer substrates.

[0005] All polysilsesquioxane hybrid membranes are prepared on inorganic carriers such as porous Al2O3 carriers with a pore size of about 200-1000 nm. The cost of these ceramic membranes is always higher than that of polymer-based membranes. Therefore, polysilsesquioxane-Al2O3 membranes with complex preparation process and high cost may not be suitable for large-scale industrial use. In order to overcome this potential drawback and also to realize the industrialization of membrane separation process as soon as possible, improve the efficiency of membrane preparation and shorten the membrane preparation time, it is currently a difficult problem to be solved to deposit large-area defect-free polysilsesquioxane hybrid membranes on existing polymer substrates. SUMMARY

[0006] This section is intended to summarize some aspects of the embodiments of the present application and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the abstract of the specification and the title of the application in order to avoid obscuring the purpose of this section, the abstract of the specification and the title of the application, and such simplifications or omissions cannot be used to limit the scope of the present application.

[0007] In view of the above and / or problems existing in the prior art, the present application is proposed.

[0008] Therefore, the purpose of the present application is to overcome the deficiencies in the prior art and provide a polysilsesquioxane / polyether ether ketone composite membrane.

[0009] To solve the above technical problems, the present application provides the following technical solutions: composed of a support body, a transition layer and a polymeric sol layer;

[0010] The support body material is polyether ether ketone, the pore size is 1-100 nm, the transition layer has a shrinkage pore size function, the polymeric sol layer material is polysilsesquioxane polymeric sol, the transition layer is formed on the support body, and the polymeric sol layer is coated on the surface of the transition layer.

[0011] Still another object of the present application is to provide a preparation method of a polysilsesquioxane / polyether ether ketone composite film.

[0012] To solve the above technical problems, the present application provides the following technical solution: comprising,

[0013] The ethanol solvent and the polysilsesquioxane precursor are mixed, and after being fully dissolved, deionized water and hydrochloric acid are sequentially added, and a polymerization reaction is carried out in a constant-temperature water bath with stirring to obtain a polysilsesquioxane polymer sol;

[0014] The polysilsesquioxane polymer sol is coated on the polyether ether ketone support forming a transition layer by a doctor blade method to obtain a polysilsesquioxane / polyether ether ketone composite film.

[0015] The molar ratio of the polysilsesquioxane precursor, deionized water and hydrochloric acid is 1:6-240:0.2-1, and the mass fraction of the polysilsesquioxane polymer sol is 5-10wt%.

[0016] As a preferred solution of the preparation method of the polysilsesquioxane / polyether ether ketone composite film, the polysilsesquioxane precursor comprises one of 1,2-bis(triethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethylene, 1,2-bis(triethoxysilyl)acetylene, 1,2-bis(triethoxysilyl)methane and 1,8-bis(triethoxysilyl)octane.

[0017] As a preferred solution of the preparation method of the polysilsesquioxane / polyether ether ketone composite film, the stirring temperature of the constant-temperature water bath for the polymerization reaction is 30-80℃, and the stirring time is 1-5h.

[0018] As a preferred solution of the preparation method of the polysilsesquioxane / polyether ether ketone composite film, the method for forming the transition layer on the polyether ether ketone support comprises,

[0019] The aqueous piperazine solution and the organic 1,3,5-benzene tricarbonyl chloride solution are subjected to interfacial polymerization on the support or the polydimethylsiloxane or amino silicone oil on the support is subjected to plasma modification.

[0020] As a preferred solution of the preparation method of the polysilsesquioxane / polyether ether ketone composite film, the interfacial polymerization of the aqueous piperazine solution and the organic 1,3,5-benzene tricarbonyl chloride solution on the support comprises,

[0021] The water phase piperazine solution is poured on the surface of the polyether ether ketone support body after the support body is fixed, and the solution is left to react, and then the organic phase 1,3,5-benzene tricarbonyl chloride solution is poured after the excess liquid on the surface is removed by a roller, and the interfacial polymerization reaction is carried out, thereby forming a transition layer, wherein the concentration of the water phase piperazine solution is 0.5-2wt%, the residence time is 1-5min, the concentration of the organic phase 1,3,5-benzene tricarbonyl chloride solution is 0.01-0.1wt%, and the residence time is 1-5min.

[0022] The plasma modification of the polydimethylsiloxane or amino silicone oil on the support body is oxygen plasma modification, wherein the pressure of the plasma treatment is 15-25Pa, the treatment power is 150-250W, and the treatment time is 60-180s.

[0023] As a preferred scheme of the preparation method of the polysilsesquioxane / polyether ether ketone composite film, the polydimethylsiloxane polymer sol is coated on the polyether ether ketone support body forming a transition layer by a doctor blade method, which comprises,

[0024] The polyether ether ketone support body forming a transition layer is fixed, the polysilsesquioxane polymer sol is dropped on one end of the support body, and a layer of sol is uniformly coated by a doctor blade at a speed of 0.5-5cm / s, and the polysilsesquioxane / polyether ether ketone composite film is formed after calcination and drying.

[0025] As a preferred scheme of the preparation method of the polysilsesquioxane / polyether ether ketone composite film, the speed of the uniform coating is 0.5-5cm / s.

[0026] As a preferred scheme of the preparation method of the polysilsesquioxane / polyether ether ketone composite film, the temperature of the calcination and drying is 50-200℃, and the time is 15-60min.

[0027] Another object of the present application is to provide an application of the polysilsesquioxane / polyether ether ketone composite film in separating organic mixed solvents.

[0028] As a preferred scheme of the application of the polysilsesquioxane / polyether ether ketone composite film in separating organic mixed solvents, the polysilsesquioxane / polyether ether ketone composite film separates organic mixed solvents by pervaporation, wherein the separation system of the organic mixed solvents comprises methanol / toluene and methanol / dimethyl carbonate.

[0029] The present application has the following beneficial effects:

[0030] The present application aims at the problem that the prior art is difficult to deposit a defect-free polysilsesquioxane hybrid film on a polymer substrate in a large area, and a new film forming method is provided by using 1,2-bis(triethoxysilyl)ethane as a polysilsesquioxane silicon precursor, forming a transition layer on a polyether ether ketone (Peek) support, and then coating a polysilsesquioxane polymeric sol on the transition layer, and the sol-gel preparation process is changed, a polysilsesquioxane / polyether ether ketone composite film with a smooth surface and no defects is prepared by using a doctor blade method, the processing technology is optimized, the film forming efficiency is improved, and the polysilsesquioxane / polyether ether ketone composite film has excellent effects on the separation and recovery of methanol / toluene and methanol / dimethyl carbonate. BRIEF DESCRIPTION OF DRAWINGS

[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative labor. Among them:

[0032] Fig. 1 is a schematic diagram of the film forming method of the polysilsesquioxane / polyether ether ketone composite film prepared in embodiment 1 of the present application.

[0033] Fig. 2 is a schematic diagram of the membrane separation mechanism of the polysilsesquioxane / polyether ether ketone composite film prepared in embodiment 1 of the present application. DETAILED DESCRIPTION

[0034] In order to make the above-mentioned purposes, features and advantages of the present application more apparent and easy to understand, the specific embodiments of the present application will be described in detail in the following with reference to the embodiment description.

[0035] In the following description, many specific details are set forth in order to provide a thorough understanding of the present application, but the present application can also be implemented in other ways different from those described herein, and those skilled in the art can make similar generalizations without departing from the connotation of the present application, therefore the present application is not limited by the specific embodiments disclosed below.

[0036] Secondly, the "one embodiment" or "embodiment" referred to herein means that the specific features, structures or characteristics can be included in at least one implementation of the present application. "In one embodiment" appearing in different places in the specification does not mean the same embodiment, nor is it an embodiment that is separate or alternative to other embodiments.

[0037] The raw materials used in the present application are commercially available in the art without special description, and the support polyether ether ketone used has a pore size of 50 nm.

[0038] Embodiment 1

[0039] Referring to the flow chart of FIG. 1, the present embodiment provides a preparation method of a composite membrane with polyether ether ketone (Peek) as a support body, and the structure of the 1,2-bis(triethoxysilyl)ethane (BTESE) precursor used is shown as Formula I,

[0040] The specific steps are as follows:

[0041] 1) Preparation of a composite silicon polymeric sol:

[0042] 1,2-bis(triethoxysilyl)ethane: deionized water: hydrochloric acid = 1:60:0.2;

[0043] 5.93 g of an ethanol solution and 3.05 g of deionized water are mixed, and after being fully dissolved, 0.02 g of hydrochloric acid, 1 g of a polysilsesquioxane precursor are sequentially added, and a polymerization reaction is carried out by stirring in a constant-temperature water bath at 40°C for 2 h to obtain a composite silicon polymeric sol (BTESE sol) with a mass fraction of 10 wt%;

[0044] 2) Preparation of a transition layer:

[0045] 1 g of anhydrous piperazine and 99 g of deionized water are mixed, and stirring is carried out at room temperature until complete dissolution to obtain a water-phase piperazine solution with a mass fraction of 1 wt%;

[0046] 0.01 g of 1,3,5-benzene tricarbonyl chloride and 20 g of n-hexane are mixed, and stirring is carried out at room temperature until complete dissolution to obtain an organic-phase 1,3,5-benzene tricarbonyl chloride solution with a mass fraction of 0.05 wt%.

[0047] The polyether ether ketone (Peek) support body is fixed on a membrane assembly for interfacial polymerization (a conventional container for fixing a membrane), the water-phase piperazine solution (1 wt%) is poured into the membrane assembly, the residence time is 3 min, then a roller is used to remove excess liquid on the surface of the support body, next the organic-phase 1,3,5-benzene tricarbonyl chloride solution (0.05 wt%) is poured into the membrane assembly, the residence time is 5 min, and in this way, the interfacial polymerization reaction is completed to form a transition layer;

[0048] 3) Preparation of a polysilsesquioxane / polyether ether ketone (Peek) membrane:

[0049] The polysilsesquioxane sol solution is loaded on the surface of the support body on which the transition layer is formed by using a doctor blade method, specifically, the Peek support body is fixed on a glass plate by using adhesive tape, 200 μL of the BTESE sol (10 wt%) is dropped on one end of the support body, then a doctor blade is used to uniformly scrape a layer at a speed of 2 cm / s, the thickness is about 300 nm, and the Peek support body after scraping is calcined and dried at 120°C for 25 min to obtain a polysilsesquioxane / polyether ether ketone organic silicon composite membrane with polyether ether ketone (Peek) as a support body.

[0050] Example 2

[0051] The difference between the present comparative example and Example 1 is that the transition layer in the preparation process is modified by oxygen plasma, the modification pressure is set to 20 Pa, the power is 200 W, and the time is 120 s, and the other process parameters are the same as those in Example 1, thereby obtaining the polysilsesquioxane / polyether ether ketone composite film of the present comparative example.

[0052] Example 3

[0053] The difference between the present comparative example and Example 1 is that the transition layer in the preparation process is modified by oxygen plasma, the modification pressure is set to 20 Pa, the power is 200 W, and the time is 120 s, and the other process parameters are the same as those in Example 1, thereby obtaining the polysilsesquioxane / polyether ether ketone composite film of the present comparative example.

[0054] Comparative Example 1

[0055] The difference between the present comparative example and Example 1 is that the modification step of the transition layer is omitted, i.e., step 2) is omitted, and the other steps are the same as those in Example 1, thereby obtaining the polysilsesquioxane / polyether ether ketone composite film of the present comparative example.

[0056] Comparative Example 2

[0057] The difference between the present comparative example and Example 1 is that the calcination and drying temperature in step 3) of the preparation process is adjusted to 50°C, and the other process parameters are the same as those in Example 1, thereby obtaining the polysilsesquioxane / polyether ether ketone composite film of the present comparative example.

[0058] Separation test:

[0059] The membranes prepared in Examples 1-3 and Comparative Examples 1 and 2 were used for methanol / toluene and methanol / dimethyl carbonate pervaporation demethanization, and the inlet pressure was controlled at 100 KPa and the test temperature was 50°C. The feed liquid composition was 10% methanol and 90% toluene, and 10% methanol and 90% dimethyl carbonate, and the methanol flux and separation factor were determined, and the results are shown in Table 1.

[0060] Table 1

[0061] As can be seen from Table 1, the change of the transition layer also significantly affects the separation effect of the membrane. The plasma modification of polydimethylsiloxane can activate the surface of PDMS, improve the hydrophilicity, enhance the interaction of the interface and make the monolayer molecules more easily diffuse to the surface, so that the surface of the PDMS matrix is modified, and finally the methanol molecules can permeate the membrane in large quantities, increasing the permeation flux of methanol. The plasma modification of amino silicone oil can react with BTESE through the amine group in the amino silicone oil, thereby enhancing the hydrophilicity of the membrane and promoting the permeation of methanol through the membrane. The interfacial polymerization can prepare an ultrathin polymer layer with a nanoscale, and the pore size of the transition layer and the thickness of the membrane can be adjusted by changing the time of the organic phase, so that the size of the membrane can be better controlled, which is beneficial to reducing the pore size of the membrane and making the top layer BTESE have better separation performance. In addition, as can be seen from Figure 2, due to the adjustment of the pore size, the methanol molecules with smaller pore size can permeate the membrane, while the toluene or dimethyl carbonate molecules with larger pore size cannot permeate the membrane.

[0062] After the polysilsesquioxane sol is coated on the Peek support, different calcination temperatures have a certain influence on the separation performance of the membrane. Low-temperature calcination can increase the content of Si-OH groups on the surface of the membrane and increase the pore size, so that the methanol molecules can more easily pass through the membrane, thereby increasing the permeation flux of methanol.

[0063] The modification of the transition layer on the surface of the Peek membrane can achieve the purpose of reducing the surface pore size. For the modification of the transition layer, we adopted three different modification methods. First, the water phase piperazine solution and the organic phase 1,3,5-benzene tricarbonyl chloride solution are subjected to interfacial polymerization reaction on the surface of the Peek membrane. Second, the polydimethylsiloxane (PDMS) is subjected to plasma modification on the surface of the Peek membrane and reacts with oxygen ions. Finally, the amino silicone oil is subjected to plasma modification on the surface of the Peek membrane. The above three methods are used to form a transition layer to reduce the pore size on the surface of the Peek membrane.

[0064] Interfacial polymerization is a method of using two highly reactive monomers or prepolymers (usually polyamines and polyacyl chlorides) to undergo polymerization reaction at the interface of two immiscible solvents (aqueous phase and organic phase), thereby forming an ultrathin layer on the porous support. The most common method of interfacial polymerization for preparing composite membranes is to react the water phase piperazine solution with the organic phase 1,3,5-benzene tricarbonyl chloride solution. Since interfacial polymerization can prepare an ultrathin polymer layer with a nanoscale, the membrane prepared by this method has high selectivity and permeability at low pressure, so it has attracted much attention and attention in the field of membrane separation.

[0065] Example 4

[0066] The difference between the present example and Example 1 is that the residence time of the organic phase 1,3,5-benzene tricarbonyl chloride solution in the membrane module in step 3) of Example 1 is adjusted to 1 min, 3 min and 7 min, respectively, and the rest of the process parameters are the same as those of Example 1, to obtain different polysilsesquioxane / polyether ether ketone composite membranes of the present example. The membrane performance is tested according to the above separation test method, and compared with Example 1. The results are shown in Table 2.

[0067] Table 2

[0068] As can be seen from Table 2, the residence time of the organic phase is crucial to the pore size of the transition layer of the membrane. When the residence time is 5 min, it can be seen that the separation factor is the largest, which indicates that the transition layer is completely formed and fills the surface pores of the Peek, so that the top layer has better separation performance. When the residence time is 1 min and 3 min, although there is a certain separation performance, the separation factor is too low, which indicates that the residence time is too short, resulting in that the formed transition layer cannot completely fill the surface pores of the Peek.

[0069] Example 5

[0070] The difference between the present example and Example 1 is that the concentration of BTESE in the preparation process is adjusted to 0, 5 wt%, 7.5 wt% and 12.5 wt%, respectively, and the rest of the process parameters are the same as those of Example 1, to obtain polysilsesquioxane / polyether ether ketone composite membranes of the present example. The membrane performance is tested according to the above separation test method, and compared with Example 1. The results are shown in Table 3.

[0071] Table 3

[0072] As can be seen from Table 3, whether it is a methanol / toluene or a methanol / dimethyl carbonate separation system, the membrane material prepared in Example 1 of the present application has the best separation selectivity. When the concentration of BTESE sol in the membrane preparation process is changed to 7.5 wt%, the methanol flux is slightly improved, but the selectivity is greatly reduced. When the concentration of BTESE sol is changed to 5 wt%, both the flux and the separation factor are significantly reduced. This is because the reduction of the concentration of BTESE sol cannot completely fill the surface pores of the Peek with a transition layer, resulting in defects in the membrane, so that both the flux and the separation factor are reduced.

[0073] In summary, the application provides a preparation method of polysilsesquioxane / polyether ether ketone composite membrane for separating organic mixed solvents by pervaporation, aiming at the problem of depositing a defect-free hybrid silica film on a large area of a polymer substrate, a new film preparation method is proposed from the aspects of simplicity of film preparation process, industrialization of membrane separation technology and improvement of film preparation efficiency, the processing technology is designed and optimized, the film preparation efficiency is improved, and the separation performance is also certain, which has excellent effect on the separation and recovery of methanol / toluene and methanol / dimethyl carbonate.

[0074] It should be noted that the above examples are only used to illustrate the technical solutions of the present application and are not limiting. Although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solutions of the present application can be modified or replaced equivalently without departing from the spirit and scope of the technical solutions of the present application, which should be covered in the scope of the claims of the present application.

Claims

1. A polysilsesquioxane / polyether ether ketone composite film, characterized by: The support body, the transition layer and the polymeric sol layer are formed; The support body material is polyether ether ketone, the pore size is 1-100 nm, the transition layer has a shrinkage pore size function, the polymeric sol layer material is polysilsesquioxane polymeric sol, the transition layer is formed on the support body, and the polymeric sol layer is coated on the surface of the transition layer.

2. The method for producing a polysilsesquioxane / polyether ether ketone composite film according to claim 1, characterized by: Comprise, The ethanol solvent and the polysilsesquioxane precursor are mixed, and after being fully dissolved, deionized water and hydrochloric acid are sequentially added, and a polymerization reaction is performed through constant temperature water bath stirring to obtain polysilsesquioxane polymeric sol. The polysilsesquioxane polymeric sol is coated on the polyether ether ketone support body on which the transition layer is formed through a doctor blade method to obtain a polysilsesquioxane / polyether ether ketone composite film. The molar ratio of the polysilsesquioxane precursor, deionized water and hydrochloric acid is 1:6-240:0.2-1, and the mass fraction of the polysilsesquioxane polymeric sol is 5-10 wt%.

3. The method for producing a polysilsesquioxane / polyether ether ketone composite film according to claim 2, characterized by: The polysilsesquioxane precursor comprises one of 1,2-bis(triethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethylene, 1,2-bis(triethoxysilyl)acetylene, 1,2-bis(triethoxysilyl)methane and 1,8-bis(triethoxysilyl)octane.

4. The method for producing a polysilsesquioxane / polyether ether ketone composite film according to claim 2, characterized by: The stirring temperature of the constant temperature water bath stirring for the polymerization reaction is 30-80 DEG C, and the stirring time is 1-5 h.

5. The method for producing a polysilsesquioxane / polyether ether ketone composite film according to claim 2, characterized by: The transition layer forming method on the polyether ether ketone support body comprises, The water phase piperazine solution and the organic phase 1,3,5-benzene tricarbonyl chloride solution are subjected to interfacial polymerization on the support body or the polydimethylsiloxane or amino silicone oil on the support body is subjected to plasma modification.

6. The method for producing a polysilsesquioxane / polyether ether ketone composite film according to claim 5, characterized by: The water phase piperazine solution and the organic phase 1,3,5-benzene tricarbonyl chloride solution are subjected to interfacial polymerization on the support body, comprising, After the polyether ether ketone support body is fixed, the water phase piperazine solution is poured on the surface of the polyether ether ketone support body and stays for reaction, the surface excess liquid is removed by a roller, the organic phase 1,3,5-benzene tricarbonyl chloride solution is poured, stays for interfacial polymerization and forms a transition layer, wherein the concentration of the water phase piperazine solution is 0.5-2 wt%, the staying time is 1-5 min, the concentration of the organic phase 1,3,5-benzene tricarbonyl chloride solution is 0.01-0.1 wt%, and the staying time is 1-5 min; The polydimethylsiloxane or amino silicone oil on the support body is subjected to oxygen plasma modification, wherein the pressure of the plasma treatment is 15-25 Pa, the treatment power is 150-250 W, and the treatment time is 60-180 s.

7. The method for producing a polysilsesquioxane / polyether ether ketone composite film according to claim 2, characterized by: The polysilsesquioxane polymeric sol is coated on the polyether ether ketone support body on which the transition layer is formed through a doctor blade method, comprising, The polyether ether ketone support body on which the transition layer is formed is fixed, the polysilsesquioxane polymeric sol is dropped on one end of the support body, a doctor blade is used to uniformly coat a layer of sol at a thickness of 200-500 nm, and after calcination and drying, a polysilsesquioxane / polyether ether ketone composite film is formed.

8. The method for producing a polysilsesquioxane / polyether ether ketone composite film according to claim 7, characterized by: The uniform coating speed is 0.5-5 cm / s.

9. The method for producing a polysilsesquioxane / polyether ether ketone composite film according to claim 7, characterized by: The calcination and drying temperature is 50-200 DEG C, and the time is 15-60 min.

10. Use of the polysilsesquioxane / polyether ether ketone composite film prepared by the production method according to any one of claims 2 to 9 in separating organic mixed solvents, characterized in that: The polysilsesquioxane / polyether ether ketone composite membrane separates organic mixed solvents by pervaporation, wherein the separation system of the organic mixed solvents includes methanol / toluene, methanol / dimethyl carbonate.

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