阅读说明：本技术 一种基于快速热处理的酚醛树脂有序介孔薄膜制备方法 (Preparation method of phenolic resin ordered mesoporous film based on rapid thermal treatment ) 是由 赵镍 黄文超 齐福刚 刘应都 欧阳晓平 于 2019-10-29 设计创作，主要内容包括：本发明公开了一种基于快速热处理的酚醛树脂有序介孔薄膜制备方法,包括,a、获取酚醛树脂溶液和嵌段共聚物溶液；b、将a步骤获取的酚醛树脂溶液和嵌段共聚物溶液混合并制备得到含嵌段共聚物的酚醛树脂前驱体溶液；c、将步骤b中制备得到的含嵌段共聚物的酚醛树脂前驱体溶液经过机械搅拌处理后,再在亲水化基板上涂膜,之后再在100-140℃进行时效处理23至25小时,再在气氛保护的条件下进行退火,所述退火过程为多次循环地依次进行快速热处理和降温热处理,升温至390-410℃进行快速热处理,降温至240-260℃进行降温热处理,快速热处理的升降温速率为5-30℃/秒,每次快速热处理的保温时间为25-35秒,制备得到酚醛树脂有序介孔薄膜。(The invention discloses a preparation method of a phenolic resin ordered mesoporous film based on rapid thermal treatment, which comprises the following steps of a, obtaining a phenolic resin solution and a block copolymer solution; b. mixing the phenolic resin solution obtained in the step a with the block copolymer solution to prepare a phenolic resin precursor solution containing the block copolymer; c. and c, mechanically stirring the phenolic resin precursor solution containing the block copolymer prepared in the step b, coating a film on a hydrophilized substrate, performing aging treatment at the temperature of 140 ℃ for 23-25 hours at 100-.)

1. A preparation method of a phenolic resin ordered mesoporous film based on rapid thermal treatment is characterized by comprising the following steps of a, obtaining a phenolic resin solution and a block copolymer solution; b. mixing the phenolic resin solution obtained in the step a with the block copolymer solution to prepare a phenolic resin precursor solution containing the block copolymer; c. and c, mechanically stirring the phenolic resin precursor solution containing the block copolymer prepared in the step b, coating a film on a hydrophilized substrate, performing aging treatment at the temperature of 140 ℃ for 23-25 hours at 100-.

2. The method for preparing the ordered mesoporous phenolic resin film based on rapid thermal treatment according to claim 1, wherein the method comprises the following steps: step a, preparing a phenolic resin solution by adopting the following steps;

s1, mixing phenol and a sodium hydroxide solution at the temperature of 45-50 ℃, stirring and melting, and dropwise adding a formaldehyde solution at the temperature of 45-50 ℃ to obtain a phenolic aldehyde mixed solution;

s2, stirring the phenolic aldehyde mixed solution obtained in the step S1 at the temperature of 50-60 ℃ for 1 hour, cooling to room temperature, and adjusting the pH of the solution to be neutral to obtain a neutral phenolic aldehyde mixed solution;

and S3, performing rotary evaporation on the neutral phenolic mixed solution obtained in the step S2 to remove water, and then dissolving to obtain a phenolic resin solution.

3. The method for preparing the ordered mesoporous phenolic resin film based on rapid thermal treatment according to claim 2, wherein the method comprises the following steps: in step S1, the sodium hydroxide solution accounts for 25% by mass, and the formaldehyde solution accounts for 37% by mass.

4. The method for preparing the ordered mesoporous phenolic resin film based on rapid thermal treatment according to claim 2, wherein the method comprises the following steps: in step S3, the solvent of the phenolic resin solution is absolute ethyl alcohol.

5. The method for preparing the ordered mesoporous phenolic resin film based on rapid thermal treatment according to claim 1, wherein the method comprises the following steps: in the step a, the block copolymer Pluronic P123 is dissolved to prepare a block copolymer solution.

6. The method for preparing the ordered mesoporous phenolic resin film based on rapid thermal treatment according to claim 5, wherein the method comprises the following steps: the solvent of the block copolymer solution is absolute ethyl alcohol.

7. The method for preparing the ordered mesoporous phenolic resin film based on rapid thermal treatment according to claim 5, wherein the method comprises the following steps: the number average molecular weight of the block copolymer Pluronic P123 is 5800; the mass fraction of the block copolymer solution is in the range of 4.5 to 5%.

8. The method for preparing the ordered mesoporous phenolic resin film based on rapid thermal treatment according to claim 1, wherein the method comprises the following steps: in the step c, the glass substrate is firstly immersed into a mixed solution of concentrated sulfuric acid and aqueous hydrogen peroxide solution with the volume ratio of 7:3, then the mixed solution is heated to 60-100 ℃ and is kept for 30-60 minutes, and the hydrophilization substrate with the surface hydrophilization treatment is obtained.

9. The method for preparing the ordered mesoporous phenolic resin film based on rapid thermal treatment according to claim 1, wherein the method comprises the following steps: in step c, the hydrophilized substrate is coated with a film by spin coating.

10. The method for preparing the ordered mesoporous phenolic resin film based on rapid thermal treatment according to claim 1, wherein the method comprises the following steps: during annealing in the step c, the times of repeatedly heating and cooling are 5-50 times;

the shielding gas used for atmosphere protection was argon.

Technical Field

The invention relates to a film preparation method in the field of materials, in particular to a preparation method of a phenolic resin ordered mesoporous film based on rapid thermal treatment.

Background

The mesoporous material is a porous solid material with the pore size of 2-50 nanometers. Because of the characteristics of larger specific surface area, larger pore volume, better thermal stability, continuous and adjustable pore size, easy modification of the pore surface and the like, the porous material is valued by people in the aspects of chemistry, life science, material science, biology and the like. The mesoporous film does not have the non-directional disadvantage of the traditional powder mesoporous material, so that the mesoporous film has wide application in the aspects of separation membranes, optics, microelectronic components, photoelectric equipment arrangement and the like.

Rapid Thermal Processing (RTP) refers to a Thermal Processing method with a very fast temperature rise rate and a short heat preservation time, and the temperature rise rate can reach 10-100 ℃/second. The rapid heat treatment has the advantages of easily controlled heat source, high temperature rise speed, convenient sample introduction and the like, and an infrared halogen lamp or a resistance rod is adopted for heating. The current and power are high during heating. Can greatly save the heat treatment time and reduce the production cost.

The traditional inorganic material for preparing the mesoporous film has the following defects: difficult processing, no high temperature resistance of homopolymer films, easy softening, overlong preparation period and the like. Therefore, it is very important to select a material that has good properties and is easy to process. The phenolic resin can realize the controllability of molecular weight and can form polymers with narrower molecular weight distribution, so that the preparation of the ordered mesoporous film by adopting the phenolic resin has important significance in both theoretical research and practical application. The conventional methods for preparing the phenolic resin mesoporous film comprise a hard template method, a pulling method and the like, but the methods respectively have the limitations of difficult template agent removal, long heat treatment processing period and the like, and the template agent can be removed in a short time by adopting the method. Meanwhile, the phenolic resin mesoporous film is prepared by adopting rapid thermal treatment, so that the preparation period of the phenolic resin mesoporous film can be greatly shortened, the cost is reduced, the deformation and collapse rate of the mesopores is low, and the utilization efficiency of the mesopores is increased.

Disclosure of Invention

Aiming at the defects of the prior art, the technical problems to be solved by the invention are as follows: how to provide a method for preparing the phenolic resin ordered mesoporous film based on rapid thermal treatment, which has simple process method, short processing time and can more thoroughly remove the template agent.

In order to solve the technical problems, the invention adopts the following technical scheme:

a preparation method of a phenolic resin ordered mesoporous film based on rapid thermal treatment is characterized by comprising the following steps of a, obtaining a phenolic resin solution and a block copolymer solution; b. mixing the phenolic resin solution obtained in the step a with the block copolymer solution to prepare a phenolic resin precursor solution containing the block copolymer; c. and c, mechanically stirring the phenolic resin precursor solution containing the block copolymer prepared in the step b, coating a film on a hydrophilized substrate, performing aging treatment at the temperature of 100-140 ℃ for 23-25 hours (preferably 24 hours), annealing under the atmosphere protection condition, wherein the annealing process comprises multiple times of cyclic rapid heat treatment and temperature reduction heat treatment in turn, heating to 390-410 ℃ for rapid heat treatment, cooling to 240-260 ℃ for temperature reduction heat treatment, cooling to 250 ℃ for temperature reduction heat treatment, the temperature rise and fall rate of the rapid heat treatment is 5-30 ℃/s, and the heat preservation time of each rapid heat treatment is 25-35 seconds (preferably 30 seconds), so as to prepare the phenolic resin ordered mesoporous film.

Thus, compared with the prior art, the method comprises the steps of mixing phenolic resin with block copolymer to form phenolic resin precursor solution containing the block copolymer, coating a film on a hydrophilized substrate to form a mesoporous structure, stabilizing the mesoporous structure through multiple cycles of 'rapid heat treatment-cooling-rapid heat treatment' and removing the template agent block copolymer Pluronic P123, thereby obtaining the mesoporous structure only containing the phenolic resin.

High molecular weight polymer having a glass transition temperature (T)_g) The glass state is formed, the polymer is hard and brittle in the glass state, the tensile rate of the high molecular chain of the glass state is very low, and the polymer can be broken to a very small extent; when the temperature is higher than the glass transition temperature, the high molecular polymer is gradually softened and enters a high elastic state; raising the temperature above the polymerWhen the melting point of the polymer is higher than the melting point of the polymer, the high molecular polymer is melted and generates viscous flow; when the temperature is further raised, the decomposition point of the high molecular weight polymer is exceeded, and the high molecular weight polymer is decomposed.

The method controls the temperature to be higher than the decomposition temperature of the pluronic P123 (the decomposition temperature range of the pluronic P123 is approximately 150-242 ℃) and higher than the glass transition temperature of the phenolic resin (the glass transition temperature of the phenolic resin is a range value and is in a range of 116-242 ℃) through multiple cycles of 'rapid heat treatment-cooling-rapid heat treatment', and the temperature is lower than the carbonization temperature of the phenolic resin (the carbonization degree of the phenolic resin is smaller below 400 ℃); because the heat preservation time is short, the mesoporous film carbon skeleton is not decomposed, and through repeated circulation, the Pluronic P123 is thoroughly decomposed, the deformation of the mesoporous film carbon skeleton is reduced, and the excessive carbonization of the phenolic resin is avoided.

The rapid heat treatment has a high heating rate (the heating rate can reach 10-100 ℃/second), can save a large amount of processing time compared with the traditional heating process (1 ℃/minute), saves time cost and economic cost; because the phenolic resin can generate viscous flow when the duration time is too long at a higher temperature (about 400 ℃), the heat treatment heat preservation time is controlled to be about 30 seconds, and the decomposition process of the template agent pluronic P123 is always carried out through repeated circulation of heating and cooling of multiple times of heat treatment, and the viscous flow of the phenolic resin is blocked, so that the template agent pluronic P123 can be removed, the order degree of mesopores can be ensured, and the collapse degree of the mesopores in the removal process of the template agent can be controlled.

Compared with the prior art, the method has the advantages of simple process, short processing time, low cost and good template agent removing effect. The test result shows that: the phenolic resin mesoporous film prepared by the method is of a hexagonal stacking ordered structure.

Preferably, the temperature is raised to 400 ℃ for rapid heat treatment, and the temperature is lowered to 250 ℃ for temperature-lowering heat treatment.

Therefore, the temperature selection of the rapid heat treatment and the cooling heat treatment is more reasonable, and the quality of the prepared phenolic resin ordered mesoporous film is better.

As optimization, the phenolic resin solution is prepared in the step a by adopting the following steps; s1, mixing phenol and a sodium hydroxide solution at the temperature of 45-50 ℃, stirring and melting, and dropwise adding a formaldehyde solution at the temperature of 45-50 ℃ to obtain a phenolic aldehyde mixed solution; s2, stirring the phenolic aldehyde mixed solution obtained in the step S1 at the temperature of 50-60 ℃ for 1 hour, cooling to room temperature, and adjusting the pH of the solution to be neutral to obtain a neutral phenolic aldehyde mixed solution; and S3, performing rotary evaporation on the neutral phenolic mixed solution obtained in the step S2 to remove water, and then dissolving to obtain a phenolic resin solution.

Thus, the prepared phenolic resin solution has better performance.

In step S1, the sodium hydroxide solution is preferably 25% by mass and the formaldehyde solution is preferably 37% by mass.

In step S3, the solvent of the phenolic resin solution is absolute ethyl alcohol. Thus, the ethanol is a good solvent for the phenolic resin, can well dissolve the phenolic resin, and can make sodium chloride (NaCl) generated by the neutralization of hydrochloric acid and sodium hydroxide precipitate; the absolute ethanol as a solvent is easily removed during the subsequent spin coating and heat treatment.

Preferably, the block copolymer solution is prepared by dissolving the block copolymer Pluronic P123 in the step a.

Preferably, the solvent of the block copolymer solution is absolute ethyl alcohol. Thus, ethanol is a good solvent for the polypropylene oxide block of the block copolymer pluronic P123 and a poor solvent for the polyethylene oxide block, so that the block copolymer can be microphase separated; and the absolute ethyl alcohol as a solvent is easily removed during the subsequent spin coating and heat treatment processes.

For optimization, the number average molecular weight of the block copolymer pluronic P123 is 5800; the mass fraction of the block copolymer solution is in the range of 4.5 to 5%.

In the step c, the glass substrate is firstly immersed into a mixed solution of concentrated sulfuric acid and aqueous hydrogen peroxide solution with the volume ratio of 7:3, then the mixed solution is heated to 60-100 ℃ and is kept for 30-60 minutes, and the hydrophilized substrate with the surface hydrophilization treatment is obtained. Therefore, game residues and dust on the surface of the substrate can be washed away, and the substrate is cleaner; meanwhile, the phenolic resin is easier to spin-coat on the substrate.

Preferably, spin coating is used to coat the hydrophilized substrate with a film in step c. Thus, the coating on the hydrophilized substrate by adopting the spin coating method can ensure that the thickness of the coating is more uniform, and the quality of the phenolic resin ordered mesoporous film is improved.

As optimization, the times of repeatedly heating and cooling are 5-50 times.

Thus, the carbon skeleton of the mesoporous film is partially decomposed due to short heat preservation time; through repeated circulation, the decomposition of the pluronic P123 is thorough, and the deformation of the mesoporous film carbon skeleton is reduced. The times of repeated heating and cooling and the time of each heat preservation are more reasonable, and the growth of the preparation time is shortened; the template agent P123 is removed, the order degree of mesopores can be ensured, and the collapse degree of the mesopores in the template agent removing process can be controlled.

Preferably, the protective gas used for atmosphere protection is argon.

Thus, the argon is used as the protective gas for atmosphere protection, so that the high polymer material can be prevented from being burnt at high temperature and carbonized under the environment containing oxygen; compared with the adoption of various mixed shielding gases and the like, the argon gas adopted has the advantages of economy, safety and good protection effect.

Drawings

In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:

FIG. 1 is a small-angle X-ray diffraction one-dimensional diagram of a mesoporous phenolic resin film prepared in example 1 of the present invention.

FIG. 2 is a grazing incidence small-angle X-ray scattering two-dimensional diagram of the mesoporous phenolic resin film prepared in example 1 of the present invention.

Fig. 3 is a small-angle X-ray diffraction one-dimensional diagram of the phenolic resin mesoporous thin film prepared in example 2 of the present invention.

FIG. 4 is a grazing incidence small-angle X-ray scattering two-dimensional graph of the mesoporous phenolic resin film prepared in example 2 of the present invention.

FIG. 5 is a grazing incidence small-angle X-ray scattering two-dimensional graph of the mesoporous phenolic resin film prepared in example 3 of the present invention.

FIG. 6 is a grazing incidence small-angle X-ray scattering two-dimensional graph of the mesoporous phenolic resin film prepared in example 4 of the present invention.

FIG. 7 is a solid nuclear magnetic resonance spectrum of the mesoporous phenolic resin film prepared by the present invention.

FIG. 8 is a solid NMR spectrum of a mesoporous phenolic resin film prepared by a conventional process in accordance with the present invention.

Fig. 9 shows that the phenolic resin mesoporous film sample prepared in example 4 of the present invention is in two cases: 1. only aging; 2. and comparing the test results of small-angle X-ray diffraction after aging, performing circulating annealing for 25 times.

Fig. 10 is a comparison of the small-angle X-ray diffraction test result of the phenolic resin mesoporous film sample prepared in example 4 of the present invention after being cyclically annealed for 25 times and the small-angle X-ray diffraction test result of the phenolic resin mesoporous film sample prepared in the conventional process.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

Reference will now be made in detail to the preferred embodiments of the present invention