CN111662468B - Method for preparing poly 4-methylpentene and porous silicon oxide microsphere composite film based on tape casting method - Google Patents

Method for preparing poly 4-methylpentene and porous silicon oxide microsphere composite film based on tape casting method Download PDF

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CN111662468B
CN111662468B CN201910172165.XA CN201910172165A CN111662468B CN 111662468 B CN111662468 B CN 111662468B CN 201910172165 A CN201910172165 A CN 201910172165A CN 111662468 B CN111662468 B CN 111662468B
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methylpentene
poly
film
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composite film
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CN111662468A (en
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高相东
杨京南
张彤彤
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds

Abstract

The invention relates to a method for preparing a poly 4-methylpentene and porous silicon oxide microsphere composite film based on a tape casting method, which comprises the following steps: (1) dissolving poly-4-methylpentene in an organic solvent to obtain a poly-4-methylpentene solution; (2) porous SiO2Uniformly dispersing the microspheres in a poly (4-methylpentene) solution to obtain a composite solution; (3) casting the composite solution into a film by adopting a casting method to obtain poly-4-methylpentene and porous SiO2And (3) microsphere composite films.

Description

Method for preparing poly 4-methylpentene and porous silicon oxide microsphere composite film based on tape casting method
Technical Field
The invention relates to poly 4-methylpentene (TPX) and porous SiO prepared based on a tape casting method2A microsphere composite film and a method belong to the field of organic composite film preparation. Specifically, a casting method is utilized to dope porous SiO with different grain diameters in a poly 4-methylpentene film2The microspheres are used for preparing the composite film, and the thickness of the film and the doping amount of the porous microspheres are regulated and controlled so as to realize the application in the infrared optical field. The preparation method can realize the preparation of TPX-SiO2The thickness of the microsphere composite film and the infrared optical performance can be controllably adjusted, the flatness of the surface of the film is ensured, and the problem of infirm bonding between the film and the substrate is solved. The method has the characteristics of stable and reliable process and simple operation, and is easy to popularize and apply.
Background
The organic composite film obtains new performance by doping inorganic particles into the traditional organic film, has the shape of the film and the characteristic function of the inorganic particles, and is a research hotspot in the field of new materials at present.
The chemical preparation methods of the existing organic composite films comprise an in-situ polymerization method, a sol-gel method, a solution casting method, an inorganic nanoparticle in-situ generation method, an intercalation method, a self-assembly method, a spin-coating method and the like. However, the above methods still have certain limitations, such as high cost and complex operation of the sol-gel method; the intercalation compounding method is difficult to find a solvent and the like of polymer and inorganic particle materials which meet the requirements; the spin coating method has a limited area of the film that can be prepared, and the film thickness can only reach hundreds of nanometers.
The tape casting method generally refers to a molding method in which a solvent, a dispersant, a binder, a plasticizer, etc. are added to ceramic powder to obtain uniformly dispersed stable slurry, and a film with a desired thickness is obtained on a tape casting machine. The prepared film has high repeatability and size consistency, and has the characteristics of high production efficiency and stable process, so that the film is widely applied to ceramic forming. However, there are few reports of the application of the casting method to the preparation of an organic composite film.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide poly 4-methylpentene and porous SiO2A preparation method of a microsphere composite film.
In one aspect, the present invention provides a poly-4-methylpentene and porous SiO2The preparation method of the microsphere composite film comprises the following steps:
(1) dissolving poly-4-methylpentene in an organic solvent to obtain a poly-4-methylpentene solution;
(2) porous SiO2Uniformly dispersing the microspheres in a poly (4-methylpentene) solution to obtain a composite solution;
(3) casting the composite solution into a film by adopting a casting method to obtain poly-4-methylpentene and porous SiO2And (3) microsphere composite films.
According to the invention, the TPX-SiO is prepared by adopting a tape casting method2Microsphere composite film capable of realizing TPX-SiO2The thickness of the microsphere composite film and the infrared optical performance can be controllably adjusted, the flatness of the surface of the film is ensured, the problem of infirm combination between the film and the substrate is solved, and the situation of warping and falling is avoided.The method has the characteristics of stable and reliable process and simple operation, and is easy to popularize and apply. The organic composite film has high emissivity in an atmospheric window (8-13 mu m), and can be used in the fields of radiation refrigeration, infrared heat insulation and the like.
Preferably, the porous SiO2The particle size of the microsphere is between 1 and 100 mu m, and the aperture is between 10 and 50 nm.
Preferably, in the organic composite film, porous SiO2The mass percentage of the microspheres is 2-30%.
By adjusting porous SiO2The emissivity of the organic composite film can be adjusted by the doping amount and/or the grain diameter of the microspheres.
Preferably, the thickness of the organic composite film is 10 to 100 μm.
Preferably, the emissivity of the organic composite film in an atmospheric window can reach more than 0.9.
Preferably, the organic solvent is cyclohexane.
Preferably, porous SiO is used2The method of uniformly dispersing the microspheres in the poly-4-methylpentene solution involves ultrasonication of the cells.
Preferably, step (3) comprises:
pouring the composite solution on a substrate, and scraping the surface solution of the substrate by using a scraper of a casting machine;
and removing the organic solvent in the scraped solution to obtain the film.
Preferably, the height of the scraper is controlled below 5 mm.
Preferably, the casting speed is 10 to 20 mm/s.
Preferably, the obtained substrate with the composite solution scraped on the casting machine is placed in air, and the organic solvent is waited to volatilize into a film at room temperature.
The invention adopts the tape casting method to prepare the organic composite film, and obtains the TPX-SiO with continuously controllable thickness, smooth surface and strong combination of the film and the substrate2Porous microsphere composite films. Based on the process, by changing the porous SiO2The mixing amount of the microspheres and the height of the scraper can adjust the performance of the composite filmAnd the stability and repeatability of the process ensure the accuracy of the experiment.
Drawings
FIG. 1 shows poly-4-methylpentene (TPX) -SiO with uniform and controllable thickness according to an embodiment of the present invention2The structure of the microsphere composite film is shown schematically.
FIG. 2 shows TPX-SiO in accordance with one embodiment of the present invention2Microstructure diagram of porous microsphere composite film.
FIG. 3 shows a porous SiO film according to an embodiment of the present invention2A microscopic picture of the pore structure of the microspheres.
FIGS. 4-8 show SiO films of different thicknesses and different particle sizes in accordance with embodiments of the present invention2Porous microspheres and different amounts of poly-4-methylpentene (TPX) -SiO2And (3) an infrared test spectrum of the porous microsphere composite film.
Fig. 9 is an infrared test spectrum of a substrate.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting thereof.
Organic composite film
Disclosed herein is TPX-SiO2Porous microsphere composite films (organic composite films for short). FIG. 1 is a schematic view of the structure of the organic composite thin film. As shown in FIG. 1, the organic composite film comprises a poly 4-methylpentene film and porous SiO uniformly dispersed in the poly 4-methylpentene film2And (3) microspheres.
Porous SiO2The microspheres are preferably uniform in particle size and regular in shape. Porous SiO2The particle size of the microspheres can be regulated and controlled between 1 and 100 mu m. The particle size range corresponds to the atmospheric window wave band, and the influence rule of the particle size on the infrared emissivity is convenient to study. More preferably, porous SiO2The particle size of the microspheres is 5-20 μm. By adjusting porous SiO2The emissivity of the organic composite film can be adjusted by the doping amount of the microspheres.
Porous SiO2The pore diameter of the microsphere can be regulated and controlled between 10nm and 50 nm.
In the organic fieldIn composite films, porous SiO2The mixing amount (mass percentage) of the microspheres can be 2-30%. Within the range of the doping amount, the infrared emissivity of the composite film can be ensured, and the flexibility (SiO) of the film can be ensured2Too much content can make the film brittle). In view of the emissivity of the organic composite film, the more the doping amount is, the better the doping amount is within the doping amount range of 2-30%. In a preferred embodiment, porous SiO2The mixing amount (mass percentage) of the microspheres is 13-26%. By adjusting porous SiO2The emissivity of the organic composite film can be adjusted by the doping amount of the microspheres.
The thickness of the organic composite film is continuously controllable, for example between 10 and 100 μm. By regulating the thickness of the organic composite film, the porous SiO in the composite film can be regulated and controlled2The quantity of the microspheres and the distribution density of the microspheres are adjusted and controlled, so that the infrared performance of the composite film is regulated and controlled. If the thickness of the organic composite film is too thin, porous SiO can be accommodated therein2The small space of the microspheres can not only reduce the infrared emission performance of the composite film, but also cause that the microspheres cannot be successfully wrapped in the film even when the thickness of the film is smaller than the particle size of the microspheres; if the thickness of the organic composite film is too thick, it will not matter to increase the burden of raw material cost on the one hand, and to increase the thickness under the condition that the emissivity requirement is reached on the other hand. More preferably, the thickness is continuously controllable between 50-100 μm. For thicknesses greater than 10 microns, the greater the thickness the better, but when the thickness is 10 microns, where the film thickness is comparable to the microsphere particle size, higher emissivity is exhibited instead.
In the disclosure, the organic composite film has high emissivity in an atmospheric window (8-13 mu m), and porous SiO is changed2The mixing amount and/or the grain diameter of the microspheres can keep the emissivity at 0.9 or above, and the microsphere is particularly suitable for the infrared optics field.
Preparation method of organic composite film
The inventor finds that the general preparation method of the organic composite film is not suitable for the composite film, so that in the disclosure, a film with larger area and thickness is prepared by adopting a tape casting method, the surface flatness of the film is ensured, and the problem that the film is not firmly combined with a substrate is also solved. In the method, the tape casting method is applied to the preparation of the organic composite film, so that the poly-4-methylpentene and porous silicon oxide microsphere composite film with high repeatability, continuously controllable thickness and smooth surface is obtained. The method is described in detail below.
Dissolving poly-4-methylpentene in an organic solvent to obtain a poly-4-methylpentene solution. The organic solvent is a low boiling point (e.g. boiling point below 100 ℃) nonpolar organic solvent, and can be selected from cyclohexane, cyclohexene, chloroform, etc. Preferably, cyclohexane is selected as the solvent in consideration of toxicity and solubility, etc. To ensure that the poly-4-methylpentene is completely dissolved in the organic solvent and is in a homogeneous solution, it may be heated with stirring. The heating temperature can be 0-90 ℃, and the stirring time can be 0.5-3 hours. The mass ratio of poly 4-methylpentene to cyclohexane may be 1: 20-1: 50, the solution with proper viscosity can be obtained by adopting the mass ratio, and the subsequent film forming speed is ensured to be moderate, so that the composite film with a smooth and uniform surface is obtained.
Porous SiO2The microspheres are uniformly dispersed in the poly 4-methylpentene solution to obtain a composite solution. The method of uniform dispersion may be ultrasonic cell disruption. The cells may be agitated prior to disruption by ultrasound. In one example, porous SiO is added to a solution of poly-4-methylpentene2Magnetically stirring the microspheres for 0.5-1h at normal temperature, and ultrasonically breaking the cells for 1-5min to obtain a composite solution.
Porous SiO2Microspheres may be commercially available, for example, from Suzhou knoyi microsphere technologies, Inc.
After the height of a scraper of a casting machine is adjusted, the composite solution is quickly poured on a substrate, and a film is formed on the casting machine in a casting mode. Specifically, the solution on the surface of the substrate is scraped by a doctor blade of a casting machine to be spread over the substrate and to be uniform in thickness.
The height of the scraper can be controlled between 0mm and 5mm, so that a composite film with ideal thickness can be obtained, and the thickness is larger and is in a micron scale (compared with a spin coating method which can only prepare a film with the thickness of about hundreds of nm). By adjusting the doctor blade of the casting machineThe height of the cutter can obtain the TPX-SiO with continuously controllable thickness and smooth surface2The porous microsphere composite film is, for example, made to have a thickness controllable in the range of 10 to 100 μm. In addition, the casting speed of the casting machine is controlled to be 10-20mm/s, so that the composite solution is uniformly and completely covered on the surface of the substrate.
The substrate may be a flat and smooth surface material, including but not limited to one of a glass slide, a glass plate, a monocrystalline silicon wafer, sapphire, an aluminum plate, and the like. The substrate may be pre-treated prior to use. In one example, the pre-processing of the substrate includes: and (3) ultrasonically cleaning the substrate in deionized water and ethanol in sequence, wherein each time is 1-30 minutes, and drying the substrate in an oven for later use. By the pretreatment, the bonding force of the substrate and the film can be improved.
And removing the organic solvent in the scraped solution to obtain the film. In one example, the resulting substrate with the composite solution scraped on a casting machine is placed in air and left to evaporate the organic solvent to form a film at room temperature. The film forming time may be 0 to 2 hours, for example, until the organic solvent is completely volatilized.
The obtained organic composite film has a smooth surface, is firmly combined with a substrate, and does not have the situation of warping and falling. The obtained organic composite film has an area of 3-50cm2. The composite film has high emissivity in an atmospheric window (8-13 mu m), and can be used in the fields of radiation refrigeration, infrared heat insulation and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) TPX-SiO prepared by the invention2The thickness of the porous microsphere composite film can be controlled to be 10-100 mu m, the surface of the film is smooth, the film is firmly combined with the substrate, and the film warping and falling-off conditions do not exist. The film stability is improved through the compounding of the organic polymer and the inorganic particles, and the film has infrared optical performance, and the emissivity in an atmospheric window (8-13 mu m) can reach 0.9 or above;
(2) compared with other chemical preparation methods of organic composite films, the tape casting method provided by the invention has the characteristics of simple operation, low cost, stable process, high repeatability and the like.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. In the following examples, poly-4-methylpentene was purchased from Mitsui chemical corporation of Japan and was designated as MX-004.
In the following embodiments, the emissivity test method is as follows: fourier transform infrared spectrometer.
Example 1
(1) Dissolution of the polymer poly-4-methylpentene (TPX). The specific process is as follows: cyclohexane is selected as a solvent of the poly-4-methylpentene, and the mixture is fully stirred under the heating and stirring conditions, wherein the mass of the poly-4-methylpentene is 0.23g, the mass of the cyclohexane is 3.83g, the water bath temperature is set to 65 ℃, and the stirring time is 40 min.
(2) And (4) preprocessing the substrate. Wherein the pre-treatment of the substrate comprises: firstly, the substrate is sequentially subjected to ultrasonic cleaning in deionized water and ethanol, the duration time of each time is 10 minutes, and the substrate is dried in an oven. The substrate is a material with a smooth surface. The substrate chosen was an FTO glass plate (3X 4cm) with a thickness of 2.3 mm.
(3) And (4) preparing a composite solution. 0.0600g of porous SiO was added to the poly-4-methylpentene solution2Microspheres with a particle size of 10 μm and a pore size of 20nm (purchased from Suzhou knoyi microsphere science and technology Co., Ltd., type silica gel chromatography filler, the microstructure diagram of which is shown in FIG. 3) were stirred at room temperature for 1 hour, and then cells were disrupted by ultrasonic waves for 3min to obtain a composite solution.
(4) And (4) casting the composite solution. And quickly pouring the composite solution onto a substrate, and casting on a casting machine, wherein the height of a scraper of the casting machine is set to be 3.5mm, and the casting speed is 10 mm/s.
(5) And (4) film forming. And (3) placing the substrate with the composite solution in the flow casting manner in the air, without additional treatment, and waiting for 1h at room temperature until the organic solvent is basically completely volatilized to obtain the composite film with a smooth surface and without warping and dropping. Fig. 2 shows a microstructure of the obtained composite film, and it can be seen that the composite film is firmly bonded to the substrate, and the film is still tightly attached to the substrate after sample preparation and impact.
The composite film with flat surface has a thickness of 50 μm and an area of 12cm2The emissivity test result is shown in fig. 4, and it can be seen that the emissivity of the composite film in the wave band of 8-13 μm is as high as 0.9, and the composite film has a good infrared emission effect.
Example 2
(1) Dissolution of the polymer poly-4-methylpentene (TPX). The specific process is as follows: cyclohexane is selected as a solvent of the poly-4-methylpentene, and the mixture is fully stirred under the heating and stirring conditions, wherein the mass of the poly-4-methylpentene is 0.25g, the mass of the cyclohexane is 4.17g, the water bath temperature is set to 65 ℃, and the stirring time is 40 min.
(2) And (4) preprocessing the substrate. Wherein the pre-treatment of the substrate comprises: firstly, the substrate is sequentially subjected to ultrasonic cleaning in deionized water and ethanol, the duration time of each time is 10 minutes, and the substrate is dried in an oven. The substrate is a material with a smooth surface. The substrate chosen was an FTO glass plate (3X 4cm) with a thickness of 2.3 mm.
(3) And (4) preparing a composite solution. 0.0663g of porous SiO were added to the poly-4-methylpentene solution2Microspheres with a particle size of 10 μm and a pore size of 20nm (purchased from Suzhou knoyi microsphere science and technology Co., Ltd., type silica gel chromatography filler) were stirred at room temperature for 1 hour, and then cells were disrupted by ultrasonic waves for 3min to obtain a composite solution.
(4) And (4) casting the composite solution. And quickly pouring the composite solution onto a substrate, and casting on a casting machine, wherein the height of a scraper of the casting machine is set to be 3.0mm, and the casting speed is 15 mm/s.
(5) And (4) film forming. And (3) placing the substrate with the composite solution in the flow casting mode in the air, without additional treatment, and waiting for 1h at room temperature until the organic solvent is basically completely volatilized to obtain the composite film with a flat surface and no warping and falling (as shown in figure 2).
The composite film with flat surface has a thickness of 35 μm and an area of 12cm2The emissivity test result is shown in fig. 5, and it can be seen that the emissivity of the composite film is only 0.87 at most in the wavelength band of 8-13 μm, and is reduced when compared with the composite film with a thickness of 50 μm.
Example 3
(1) Dissolution of the polymer poly-4-methylpentene (TPX). The specific process is as follows: cyclohexane is selected as a solvent of the poly-4-methylpentene, and the mixture is fully stirred under the heating and stirring conditions, wherein the mass of the poly-4-methylpentene is 0.22g, the mass of the cyclohexane is 3.67g, the water bath temperature is set to 65 ℃, and the stirring time is 40 min.
(2) And (4) preprocessing the substrate. Wherein the pre-treatment of the substrate comprises: firstly, the substrate is sequentially subjected to ultrasonic cleaning in deionized water and ethanol, the duration time of each time is 10 minutes, and the substrate is dried in an oven. The substrate is a material with a smooth surface. The substrate chosen was an FTO glass plate (3X 4cm) with a thickness of 2.3 mm.
(3) And (4) preparing a composite solution. 0.0663g of porous SiO were added to the poly-4-methylpentene solution2Microspheres with a particle size of 5 μm and a pore size of 10nm (purchased from Suzhou knoyi microsphere science and technology Co., Ltd., type silica gel chromatography filler) were stirred at room temperature for 1 hour, and then cells were disrupted by ultrasonic waves for 3min to obtain a composite solution.
(4) And (4) casting the composite solution. And quickly pouring the composite solution onto a substrate, and casting on a casting machine, wherein the height of a scraper of the casting machine is set to be 3.5mm, and the casting speed is 20 mm/s.
(5) And (4) film forming. And (3) placing the substrate with the composite solution in the flow casting mode in the air, without additional treatment, and waiting for 1h at room temperature until the organic solvent is basically completely volatilized to obtain the composite film with a flat surface and no warping and falling (as shown in figure 2).
The composite film with flat surface has a thickness of 50 μm and an area of 12cm2The emissivity test result is shown in fig. 6, and it can be seen that the emissivity is high in the whole band, which is up to 0.9 or more.
Example 4
(1) Dissolution of the polymer poly-4-methylpentene (TPX). The specific process is as follows: cyclohexane is selected as a solvent of the poly-4-methylpentene, and the mixture is fully stirred under the heating and stirring conditions, wherein the mass of the poly-4-methylpentene is 0.23g, the mass of the cyclohexane is 3.83g, the water bath temperature is set to 65 ℃, and the stirring time is 40 min.
(2) And (4) preprocessing the substrate. Wherein the pre-treatment of the substrate comprises: firstly, the substrate is sequentially subjected to ultrasonic cleaning in deionized water and ethanol, the duration time of each time is 10 minutes, and the substrate is dried in an oven. The substrate is a material with a smooth surface. The substrate chosen was an FTO glass plate (3X 4cm) with a thickness of 2.3 mm.
(3) And (4) preparing a composite solution. 0.0061g of porous SiO is added into the solution of poly-4-methylpentene2Microspheres with a particle size of 10 μm and a pore size of 20nm (purchased from Suzhou knoyi microsphere science and technology Co., Ltd., type silica gel chromatography filler) were stirred at room temperature for 1 hour, and then cells were disrupted by ultrasonic waves for 3min to obtain a composite solution.
(4) And (4) casting the composite solution. And quickly pouring the composite solution onto a substrate, and casting on a casting machine, wherein the height of a scraper of the casting machine is set to be 3.5mm, and the casting speed is 11 mm/s.
(5) And (4) film forming. And (3) placing the substrate with the composite solution in the flow casting mode in the air, without additional treatment, and waiting for 1h at room temperature until the organic solvent is basically completely volatilized to obtain the composite film with a flat surface and no warping and falling (as shown in figure 2).
The composite film with flat surface has a thickness of 50 μm and an area of 12cm2The emissivity test results are shown in fig. 7, and it can be seen that the emissivity is distributed between 0.2 and 0.9, which is slightly inferior to that of example 1, mainly due to the different amount of the added silica microspheres.
Example 5
(1) Dissolution of the polymer poly-4-methylpentene (TPX). The specific process is as follows: cyclohexane is selected as a solvent of the poly-4-methylpentene, and the mixture is fully stirred under the heating and stirring conditions, wherein the mass of the poly-4-methylpentene is 0.25g, the mass of the cyclohexane is 4.17g, the water bath temperature is set to 65 ℃, and the stirring time is 40 min.
(2) And (4) preprocessing the substrate. Wherein the pre-treatment of the substrate comprises: firstly, the substrate is sequentially subjected to ultrasonic cleaning in deionized water and ethanol, the duration time of each time is 10 minutes, and the substrate is dried in an oven. The substrate is a material with a smooth surface. The substrate chosen was an FTO glass plate (3X 4cm) with a thickness of 2.3 mm.
(3) And (4) preparing a composite solution. 0.0663g of porous SiO were added to the poly-4-methylpentene solution2Microspheres with a particle size of 10 μm and a pore size of 20nm (purchased from Suzhou knoyi microsphere science and technology Co., Ltd., type silica gel chromatography filler) were stirred at room temperature for 1 hour, and then cells were disrupted by ultrasonic waves for 3min to obtain a composite solution.
(4) And (4) casting the composite solution. And quickly pouring the composite solution onto a substrate, and casting on a casting machine, wherein the height of a scraper of the casting machine is set to be 2.6mm, and the casting speed is 11 mm/s.
(5) And (4) film forming. And (3) placing the substrate with the composite solution in the flow casting mode in the air, without additional treatment, and waiting for 1h at room temperature until the organic solvent is basically completely volatilized to obtain the composite film with a flat surface and no warping and falling (as shown in figure 2).
The composite film with flat surface has a thickness of 10 μm and an area of 12cm2The emissivity test result is shown in fig. 8, and it can be seen that the emissivity of the material is distributed between 0.8 and 0.9 in a wave band of 8 to 13 μm, and the whole material is high.
FIG. 9 shows an infrared test spectrum of the substrate used in the above embodiment, which shows that the substrate has a very low infrared emissivity within a wavelength band of 8-13 μm, which is not more than 0.3, and further shows that the composite film indeed has a significant infrared emission performance.
The invention adopts a tape casting method to prepare poly 4-methylpentene (TPX) -SiO with continuously controllable thickness and smooth surface2Porous microsphere composite films. The invention can ensure the surface smoothness of the composite film and the stability and repeatability of the process. Compared with the traditional chemical preparation methods such as sol-gel, in-situ polymerization and the like, the tape casting method has the characteristics of simple operation, low equipment requirement, stable and reliable process and easy popularization and application.

Claims (6)

1. Poly-4-methylpentene and porous SiO2The preparation method of the microsphere composite film is characterized by comprising the following steps:
(1) dissolving poly-4-methylpentene in an organic solvent to obtain a poly-4-methylpentene solution;
(2) porous SiO2Uniformly dispersing the microspheres in a poly (4-methylpentene) solution to obtain a composite solution; the porous SiO2The particle size of the microspheres is between 5 and 20 mu m, and the pore diameter is between 10 and 50 nm;
(3) casting the composite solution into a film by adopting a casting method to obtain poly-4-methylpentene and porous SiO2A microsphere composite film;
porous SiO in the composite film2The mass percentage of the microspheres is 13-26%;
the thickness of the composite film is controllable between 10 and 100 mu m;
the distribution density of the porous silica microspheres and the particle size of the porous silica microspheres are regulated and controlled by regulating and controlling the doping amount of the porous silica microspheres and the thickness of the composite film, so that the infrared performance of the composite film is controllably regulated;
the emissivity of the composite film in an atmospheric window of 8-13 mu m is 0.8-0.9 or more than 0.9.
2. The method according to claim 1, wherein the organic solvent is cyclohexane.
3. The method of claim 1, wherein the porous SiO is formed by2The method of uniformly dispersing the microspheres in the poly-4-methylpentene solution involves ultrasonication of the cells.
4. The method according to claim 1, wherein the step (3) comprises:
pouring the composite solution on a substrate, and scraping the surface solution of the substrate by using a scraper of a casting machine;
and removing the organic solvent in the scraped solution to obtain the film.
5. The production method according to claim 4, wherein the height of the doctor blade is controlled to be 5mm or less.
6. A production method according to claim 4, wherein the casting speed is 10 to 20 mm/s.
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