阅读说明：本技术 基于流延法制备聚4-甲基戊烯与多孔氧化硅微球复合薄膜的方法 (Method for preparing poly 4-methylpentene and porous silicon oxide microsphere composite film based on tape casting method ) 是由 高相东 杨京南 张彤彤 于 2019-03-07 设计创作，主要内容包括：本发明涉及基于流延法制备聚4-甲基戊烯与多孔氧化硅微球复合薄膜的方法,包括以下步骤：(1)将聚4-甲基戊烯溶于有机溶剂中,得到聚4-甲基戊烯溶液；(2)将多孔SiO<Sub>2</Sub>微球均匀分散于聚4-甲基戊烯溶液中,得到复合溶液；(3)采用流延法将复合溶液流延成膜,得到聚4-甲基戊烯与多孔SiO<Sub>2</Sub>微球复合薄膜。(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 SiO 2 Uniformly 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 SiO 2 And (3) microsphere composite films.)

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;

(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.

2. The method of claim 1, wherein the porous SiO₂The particle size of the microsphere is between 1 and 100 mu m, and the aperture is between 10 and 50 nm.

3. The production method according to claim 1 or 2, wherein in the composite thin film, porous SiO is contained₂The mass percentage of the microspheres is 2-30%.

4. The production method according to any one of claims 1 to 3, wherein the composite film has a thickness of 10 to 100 μm.

5. The method according to any one of claims 1 to 4, wherein the composite film has an emissivity in the atmospheric window of 0.9 or more.

6. The production method according to any one of claims 1 to 5, characterized in that the organic solvent is cyclohexane.

7. The production method according to any one of claims 1 to 6, wherein porous SiO is formed₂The method of uniformly dispersing the microspheres in the poly-4-methylpentene solution involves ultrasonication of the cells.

8. The production method according to any one of claims 1 to 7, wherein the step (3) includes:

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.

9. The production method according to claim 8, wherein the height of the doctor blade is controlled to be 5mm or less.

10. A producing method according to claim 8 or 9, characterized in that the casting speed is 10 to 20 mm/s.

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 comprisesCan realize the control 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 and improve the performance of the composite film, and meanwhile, the stability and repeatability of the process also 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 a porous film uniformly dispersed in the poly 4-methylpentene filmSiO₂And (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 organic 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, the film thickness is instead comparable to the microsphere particle sizeShowing a higher emissivity.

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). The thickness of the TPX-SiO with a continuous and controllable smooth surface can be obtained by adjusting the height of a scraper of a casting machine₂The 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.