CN115536901B

CN115536901B - Preparation method of silica hybridization polyimide super-smooth surface material with good stability

Info

Publication number: CN115536901B
Application number: CN202211144232.5A
Authority: CN
Inventors: 张洪文; 杨丽; 吕程程; 买重阳; 郭雅雯; 赵烈伦; 姜彦�
Original assignee: Changzhou University
Current assignee: Changzhou University
Priority date: 2022-09-20
Filing date: 2022-09-20
Publication date: 2023-07-25
Anticipated expiration: 2042-09-20
Also published as: CN115536901A

Abstract

The invention belongs to the field of super-smooth surface materials, and relates to a preparation method of a silicon dioxide hybridization polyimide super-smooth surface material with good stability. Firstly, cetyl Trimethyl Ammonium Bromide (CTAB) is used as a template agent, urea is used as a silicon source hydrolysis agent, TEOS is used as a silicon source reagent, mesoporous silica (KCC-1) is obtained through reaction, and KH540 is used for modification. Then, by combining a respiratory pattern method, amino modified mesoporous silica, APT-PDMS, 3' -4,4' -biphenyl tetracarboxylic dianhydride (S-BPDA) and 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane (BAPP) are used as raw materials, and polyimide SLIPS with good stability is prepared by a two-step method. The static contact angle of the porous substrate can reach 152 degrees, water drops can slide on the surface of the porous substrate after oil filling, and the ultra-smooth surface has good stability, antifouling property and self-cleaning property.

Description

Preparation method of silica hybridization polyimide super-smooth surface material with good stability

Technical Field

The invention belongs to the field of super-smooth surface materials, and particularly relates to a preparation method of a silicon dioxide hybridization polyimide super-smooth surface material with good stability.

Background

The micro-nano porous material can be applied to the fields of optics, biomedicine, self-cleaning and the like, but in the application process, tiny-size pollutants can be deposited in gaps of a micro-nano structure to cause the surface of the porous material to lose self-cleaning performance, so that scientists are inspired by nepenthes to successfully prepare a liquid casting porous surface with lubrication effect, namely a 'super-slip surface' (SLIPS). SLIPS has excellent properties of self-cleaning, self-repairing, anti-icing, anti-fouling and the like, but for SLIPS materials, weak interaction between the matrix and the lubricant is an inherent disadvantage, and loss of surface lubricating oil can be caused, so that practical application of SLIPS is highly limited. In practical application, stability is an important factor, and the preparation of SLIPS with good stability has important significance.

Disclosure of Invention

The invention aims to provide a preparation method of a silica hybridization polyimide super-smooth surface material with good stability, and the obtained material has a porous structure.

In order to achieve the purpose of the invention, the technical scheme adopted is as follows:

a preparation method of a silica hybridization polyimide super-smooth surface material with good stability comprises the following steps:

(1) Preparation of APT-PDMS: with octamethyl cyclotetrasiloxane (D) ₄ ) And 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane as the reactive monomer with tetramethylammonium hydroxide ((Me) ₄ NOH) is used as a catalyst, and amino-terminated polydimethylsiloxane (APT-PDMS) is prepared through a ring-opening reaction.

Further, the ring-opening reaction temperature is generally 105.+ -. 5 ℃, and the reaction time is generally about 18.+ -. 0.5 h.

After the ring-opening reaction is finished, the reaction system is heated to the degradation temperature (generally 180+/-5 ℃) of the catalyst to degrade the catalyst, and then cooled to below 160+/-1 ℃ to remove low-boiling-point micromolecular impurities and other byproducts, so that colorless and sticky APT-PDMS liquid is obtained.

(2) KH540 modified mesoporous silica (KCC-1-NH) ₂ ) Is prepared from the following steps: cetyl Trimethyl Ammonium Bromide (CTAB), urea and Tetraethoxysilane (TEOS) are used as raw materials to react to obtain mesoporous silica (KCC-1). Modifying KCC-1 with KH540 to obtain KCC-1-NH ₂ 。

Further, 1g of cetyltrimethylammonium bromide and 0.5g of urea were weighed into 10mL of distilled water and stirred for 3 hours (typically 25 ℃); 2g of ethyl orthosilicate, 30mL of cyclohexane and 1.5mL of n-pentanol were mixed and sonicated for 30min. The mixture was then allowed to react for 4h (typically 80 ℃) and then refluxed for 24h (typically 60 ℃) and the white precipitate was collected and repeatedly washed three times with water and ethanol, followed by oven drying (the drying conditions may be: drying at 60 ℃) for 24 h) to give mesoporous silica.

Ultrasonically dispersing KH540, ethanol and water to obtain uniform mixed solution, simultaneously ultrasonically dispersing mesoporous silica in toluene, then pouring the mixed solution for reflux reaction (reaction temperature is 80 ℃ generally for 24 hours), taking precipitate, washing with ethanol for multiple times, and drying in an oven (drying condition is preferably that the solution is placed at 80 ℃ for 24 hours) to obtain KCC-1-NH ₂ 。

(3) Preparation of polyamic acid: weighing KCC-1-NH by taking dimethylacetamide (DMAc) as solvent ₂ APT-PDMS, 2' -bis [4- (4-aminophenoxyphenyl) phenyl ]]Preparation of polyamic acid, KCC-1-NH, from propane (BAPP) and 3,3'-4,4' -biphenyltetracarboxylic dianhydride (S-BPDA) ₂ Is KCC-1-NH ₂ APT-PDMS, 2' -bis [4- (4-aminophenoxyphenyl) phenyl ]]10-40% of the total mass of propane and 3,3'-4,4' -biphenyl tetracarboxylic dianhydride.

Further, KCC-1-NH with a set proportion is weighed ₂ Appropriate amount of APT-PDMS, 2' -bis [4- (4-aminophenoxyphenyl) phenyl ]]Propane (BAPP) is dissolved in DMAc solution (the mass of the solution is controlled to be 12-15 wt%) and stirred to be fully dissolved (stirring is generally carried out for 30 min), then 3,3'-4,4' -biphenyl tetracarboxylic dianhydride (S-BPDA) is added in three times to ensure full reaction (generally added every half hour), the system is placed in a vacuum state and reacted at room temperature for 3-3.5h, and the polyamic acid is obtained by drying, wherein the drying temperature is preferably 100 ℃.

(4) Preparation of the ultra-smooth surface: the polyamide acid powder is dissolved in toluene or chloroform, the concentration is controlled to be 30-50 mg/mL, a porous substrate is prepared on a glass sheet by self-assembly through a respiration pattern method, then the porous substrate is solidified at 100-300 ℃, and finally the ultra-smooth surface is obtained by filling dimethyl silicone oil.

Further, the self-assembly is performed in a constant temperature water tank at a temperature of 40 to 50 ℃ for at least one hour.

Compared with the prior art, the invention has the beneficial effects that:

the invention uses KCC-1-NH ₂ APT-PDMS, 2' -bis [4- (4-aminophenoxyphenyl) phenyl ]]Propane (BAPP) and 3,3'-4,4' -biphenyl tetracarboxylic dianhydride (S-BPDA) are used as raw materials to prepare polyamide acid with a mesoporous silica cross-linked network structure, and then the ultra-smooth surface of the silica hybrid polyimide with a closed pore structure is obtained through a respiratory pattern method, and a single independent micron closed pore structure is formed on the ultra-smooth surface. KCC-1-NH ₂ The polyimide is introduced into a polyimide main chain, so that the oil storage and oil locking capability of SLIPS is improved, and the polyimide has a certain potential in improving the service life of SLIPS. In addition by changing KCC-1-NH ₂ The surface morphology of the porous substrate can be controlled by the ratio of the polymer concentration, the solvent and other conditions for preparing the respiratory chart. Compared with the common open-cell structure, the closed-cell structure of the ultra-smooth surface of the mesoporous silica hybrid polyimide is more beneficial to improving the stability of SLIPS lubricating oil.

Drawings

FIG. 1 is a method for synthesizing KCC-1-NH according to step (2) of example 1 ₂ Is a reaction formula (I);

FIG. 2 is a structural formula of the silica hybrid polyimide of example 1;

FIG. 3 is an infrared spectrum of the silica hybrid polyimide of example 1;

FIG. 4 is KCC-1 and KCC-1-NH ₂ Scanning electron microscope images and contact angle diagrams (a.KCC-1 b.KCC-1-NH) of porous substrates prepared in different proportions ₂ At a ratio of 10% c.KCC-1-NH ₂ The proportion is 25%, the conditions for preparing the breathing patterns of b and c are 30mg/mL, and chloroform is used as a solvent);

FIG. 5 is KCC-1-NH ₂ SLIPS stability performance test charts with different ratios.

Detailed Description

The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.

The invention is further described in detail below in connection with the examples:

example 1:

(1) Preparation of APT-PDMS

29.7g of D ₄ And 2.5g of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane were added to a three-necked flask, followed by 0.6g of (Me) ₄ NOH as catalyst in drying N ₂ Ring opening is carried out in the atmosphere of 105 ℃ and the reaction condition is carried out for 18 hours, after the reaction is carried out, the reaction system is heated to 180 ℃ to degrade the catalyst, the temperature is reduced to below 160 ℃ to remove low-boiling point micromolecular impurities and other byproducts, and the colorless sticky amino-terminated polydimethylsiloxane (APT-PDMS) liquid is obtained.

(2)KCC-1-NH ₂ Is prepared from

1g of cetyltrimethylammonium bromide and 0.5g of urea were weighed and dissolved in 10mL of distilled water, and stirred at room temperature for 3 hours; 2g of ethyl orthosilicate, 30mL of cyclohexane and 1.5mL of n-pentanol were mixed and sonicated for 30min. The mixture was then reacted at 80℃for 4h, refluxed at 60℃for 24h, the white precipitate was collected and repeatedly washed three times with water and ethanol each, and oven dried at 60℃for 24h to give mesoporous silica.

5.37g KH540, 19.3g ethanol and 1.43g water are mixed for 30min ultrasonic treatment, meanwhile, 0.6g mesoporous silica is weighed and dispersed in 10mL toluene for 30min ultrasonic treatment, then KH540, ethanol and water are poured into toluene, reflux is carried out for 24h at 80 ℃, precipitate is taken and washed three times by ethanol, and amino modified mesoporous silica is obtained after drying for 24h at 80 ℃.

(3) Preparation of Polyamic acid (KCC-1-NH) ₂ The ratio of (C) is 10%)

0.2894g of KCC-1-NH was weighed out ₂ 1.5768g of APT-PDMS, 0.4310g of 2,2' -bis [4- (4-aminophenoxyphenyl) phenyl)]Propane (BAPP) was dissolved in 24mL of DMAc solution (12 wt%) and stirred for 30min, then 0.5938g of 3,3'-4,4' -biphenyltetracarboxylic dianhydride (S-BPDA) was added three times, the system was reacted at room temperature under vacuum for three hours to obtain polyamic acid, and the obtained polyamic acid was put into a vacuum oven at 100 ℃.

(4) Preparation of ultra-slippery surfaces

30mg of solid powder is weighed and placed in 1mL of chloroform, after ultrasonic treatment is carried out to fully disperse the solid powder, the solution is dripped on a cleaned glass substrate, the self-assembly is carried out in a constant temperature water tank at 40 ℃ for one hour, and the obtained porous substrate is subjected to short-temperature high-temperature solidification: 100. 200 and 300 ℃ for 1 hour each. And finally, pouring the polydimethylsiloxane oil, and vertically placing the glass sheet for at least 12 hours to obtain the PI ultra-smooth surface.

FIG. 1 shows the synthesis of KCC-1-NH ₂ Is a reaction scheme of (2).

FIG. 2 is a structural formula of a silica hybrid polyimide.

FIG. 3 is SiO ₂ -infrared spectrogram of PDMS-PI. At 1771cm ^-1 1718cm ^-1 Asymmetric and symmetric absorption peaks of carbonyl on imine ring appear at 1380cm ^-1 The C-N stretching vibration peak on the imine ring appears at 1010cm ^-1 And 1069cm ^-1 A telescopic vibration absorption peak of si—o appears.

In FIG. 4 a is an SEM image of mesoporous silica of example 1, KCC-1 has a spherical shape as a whole, a matte surface, a wrinkled shape, and a uniform particle size.

In fig. 4 b is an SEM image of the porous substrate of example 1, the pores formed are smaller in size, densely distributed, and isolated from adjacent pores by the membranous surface, so that a single independent microstructure is formed, the contact angle is as high as 145 °, the sliding angle after silicone oil is poured in is 2 °, and the self-cleaning property is good.

FIG. 5 b shows the oil lock ratio curve of SLIPS of example 1 at various times, wherein the oil lock ratio after 60min was 67.58%.

Example 2

(1) APT-PDMS preparation method was as in example 1

(2)KCC-1-NH ₂ The preparation method is the same as in example 1

(3) Polyamic acid was prepared in the same manner as in example 1

(4) Preparation of ultra-slippery surfaces

40mg of solid powder is weighed and placed in 1mL of chloroform, after ultrasonic treatment is carried out to fully disperse the solid powder, the solution is dripped on a cleaned glass substrate, the self-assembly is carried out in a constant temperature water tank at 40 ℃ for one hour, and the obtained porous substrate is subjected to short-temperature high-temperature solidification: 100. 200 and 300 ℃ for 1 hour each. And finally, pouring the polydimethylsiloxane oil, and vertically placing the glass sheet for at least 12 hours to obtain the PI ultra-smooth surface.

The porous substrate prepared in example 2 had a static contact angle of 137 deg., and a slip angle of 5 deg. after being filled with simethicone.

Example 3

(1) APT-PDMS preparation method was the same as in example 1

(2)KCC-1-NH ₂ The preparation method is the same as in example 1

(3) Preparation of Polyamic acid

1.1570g of KCC-1-NH was weighed out ₂ 0.7112g of APT-PDMS, 0.4310g of 2,2' -bis [4- (4-aminophenoxyphenyl) phenyl)]Propane (BAPP) was dissolved in 24mL of DMAc solution (12 wt%) and stirred for 30min, then 0.5938g of 3,3'-4,4' -biphenyltetracarboxylic dianhydride (S-BPDA) was added three times, the system was reacted at room temperature under vacuum for three hours to obtain polyamic acid, and the obtained polyamic acid was put into a vacuum oven at 100 ℃.

(4) Preparation of the ultra-smooth surface as in example 1

The porous substrate prepared in example 3 had a static contact angle of 151 ° and a sliding angle of 6 ° after being filled with simethicone.

In fig. 5 d is the lock oil ratio curve of SLIPS of example 3 at different times, the lock oil ratio after 60min being 45.71%.

Example 4

(1) APT-PDMS preparation method was the same as in example 1

(2)KCC-1-NH ₂ The preparation method is the same as in example 1

(3) Preparation of Polyamic acid was carried out as in example 1

(4) Preparation of ultra-slippery surfaces

30mg of solid powder is weighed and placed in 1mL of toluene, after the solid powder is fully dispersed by ultrasonic treatment, the solution is dripped on a cleaned glass substrate, the solution is subjected to self-assembly in a constant temperature water tank at 50 ℃ for one hour, and the obtained porous substrate is subjected to short-temperature high-temperature solidification: 100. 200 and 300 ℃ for 1 hour each. And finally, pouring the polydimethylsiloxane oil, and vertically placing the glass sheet for at least 12 hours to obtain the PI ultra-smooth surface.

The porous substrate prepared in example 4 had a static contact angle of 135℃and a slip angle of 7℃after being filled with dimethicone.

Example 5

(1) APT-PDMS preparation method was the same as in example 1

(2)KCC-1-NH ₂ The preparation method is the same as in example 1

(3) Preparation of Polyamic acid

0.7236g of KCC-1-NH was weighed out ₂ 1.1461g of APT-PDMS, 0.4310g of 2,2' -bis [4- (4-aminophenoxyphenyl) phenyl)]Propane (BAPP) was dissolved in 24mL of DMAc solution (12 wt%) and stirred for 30min, then 0.5938g of 3,3'-4,4' -biphenyltetracarboxylic dianhydride (S-BPDA) was added three times, the system was reacted at room temperature under vacuum for three hours to obtain polyamic acid, and the obtained polyamic acid was put into a vacuum oven at 100 ℃.

(4) The preparation method of the ultra-smooth surface is the same as in example 1

The porous substrate prepared in example 5 had a static contact angle of 152℃and a slip angle of 3℃after being filled with simethicone.

In FIG. 4 c, the SEM image of a porous substrate of example 5, the surface of the substrate consisted of about 3 μm large pores and numerous small pores, the junction of the large pores and the large pores was formed by stacking numerous small pores, the contact angle was 152℃and the sliding angle after pouring silicone oil was 3 ℃.

FIG. 5 c shows the oil lock ratio curve of SLIPS of example 5 at various times, with a lock ratio of 53.3% after 60 minutes.

Comparative example 1

(1) The APT-PDMS was prepared in the same manner as in example 1

(2)KCC-1-NH ₂ The preparation method is the same as in example 1

(3) Polyamic acid was prepared in the same manner as in example 1

(4) Preparation of ultra-slippery surfaces

55mg of solid powder is weighed and placed in 1mL of chloroform, after ultrasonic treatment is carried out to fully disperse the solid powder, the solution is dripped on a cleaned glass substrate, the self-assembly is carried out in a constant temperature water tank at 40 ℃ for one hour, and the obtained porous substrate is subjected to short-temperature high-temperature solidification: 100. 200 and 300 ℃ for 1 hour each. And finally, pouring the polydimethylsiloxane oil, and vertically placing the glass sheet for at least 12 hours to obtain the PI ultra-smooth surface.

Comparative example 1 is mainly different from example 1 in that: the polymer concentration was varied during the preparation of the breath map. The polymer concentration in example 1 was 30mg/mL; comparative example 1 the polymer concentration was 55mg/mL.

The porous substrate prepared in comparative example 1 had a static contact angle of 130℃and a sliding angle of 13℃after being impregnated with simethicone.

Comparative example 2

(1) APT-PDMS preparation method was the same as in example 1

(2)KCC-1-NH ₂ The preparation method is the same as in example 1

(3) Polyamic acid was prepared in the same manner as in example 1

(4) Preparation of ultra-slippery surfaces

Weighing 20mg of solid powder, putting the solid powder into 1mL of toluene, carrying out ultrasonic treatment to fully disperse the solid powder, then dripping the solution on a cleaned glass substrate, respectively carrying out self-assembly in a constant-temperature water tank at 50 ℃ for one hour, and carrying out short-temperature high-temperature curing on the obtained porous substrate: 100. 200 and 300 ℃ for 1 hour each. And finally, pouring the polydimethylsiloxane oil, and vertically placing the glass sheet for at least 12 hours to obtain the PI ultra-smooth surface.

Comparative example 2 is mainly different from example 4 in that: the polymer concentration varies. The polymer concentration in example 4 was 30mg/mL; the polymer concentration of comparative example 2 was 20mg/mL.

The porous substrate prepared in comparative example 2 had a static contact angle of 127 ° and a sliding angle of 12 ° after being filled with simethicone.

Comparative example 3

(1) APT-PDMS preparation the same as in example 1

(2)KCC-1-NH ₂ The preparation method is the same as in example 1

(3) Preparation of Polyamic acid

1.4470g of KCC-1-NH was weighed out ₂ 0.4222g of APT-PDMS, 0.4310g of 2,2' -bis [4- (4-aminophenoxyphenyl) phenyl)]Propane (BAPP) was dissolved in 24mL of DMAc solution (12 wt%) and stirred for 30min, then 0.5938g of 3,3'-4,4' -biphenyltetracarboxylic dianhydride (S-BPDA) was added three times, the system was reacted at room temperature under vacuum for three hours to obtain polyamic acid, and the obtained polyamic acid was put into a vacuum oven at 100 ℃.

Comparative example 3 is mainly different from example 1 in that: KCC-1-NH ₂ Is different in ratio. KCC-1-NH in example 1 ₂ The ratio of (2) is 10%; KCC-1-NH in comparative example 3 ₂ The proportion of (2) is 50%.

The porous substrate prepared in comparative example 3 had a static contact angle of 149℃and a slip angle of 15℃after being impregnated with simethicone.

In addition, the applicant has made the following comparative tests:

comparison of KCC-1-NH ₂ Stability properties of SLIPS prepared in different proportions. FIG. 4 is a schematic diagram of four KCC-1-NH groups ₂ SLIPS stability test of different proportions (polymer concentration is 30mg/mL in respiratory chart preparation process, solvent is chloroform), high shear force is simulated, rotation is carried out for 60min at 3000rpm, oil locking rate is represented by recording every 10min, KCC-1-NH ₂ The oil lock ratio of 10% was the highest, demonstrating that the stability of this SLIPS was the best.

Based on the verification of the above examples and comparative examples, the present invention was carried out in KCC-1-NH ₂ APT-PDMS, 2' -bis [4- (4-aminophenoxy) benzeneBase group]Propane (BAPP) and 3,3'-4,4' -biphenyl tetracarboxylic dianhydride (S-BPDA) are used as raw materials, reaction conditions are regulated, and the ultra-smooth surface of the silicon dioxide hybridization polyimide with a closed pore structure is obtained through a respiration pattern method. Under certain conditions, the ultra-slip surface may form a single, independent, micron closed cell structure. KCC-1-NH ₂ The stable performance of SLIPS is improved by introducing the polyimide main chain. SLIPS sliding angle prepared within a certain condition range<10 degrees, and has good stability, self-cleaning property, antifouling property and the like.

Comparison of KCC-1-NH ₂ The contact angle of porous substrates prepared with respirators, with different ratios, different polymer concentrations, different solvents, and the slip angle of SLIPS obtained after oiling are shown in tables 1, 2. Taken together, KCC-1-NH ₂ The SLIPS prepared by using chloroform as a solvent and having a polymer concentration of 30mg/mL has the advantages of optimal performance, a sliding angle of 2 degrees, a contact angle of 145 degrees of a porous substrate before oil filling and good hydrophobic performance.

TABLE 1 KCC-1-NH ₂ Porous substrate static contact angle with different proportions, different polymer concentration and different solvent

TABLE 2 KCC-1-NH ₂ Slip angle of SLIPS with different proportions, different polymer concentrations and different solvents

The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.

Claims

1. A preparation method of a silica hybridization polyimide super-smooth surface material with good stability is characterized by comprising the following steps: the method comprises the following steps:

(1) Preparation of APT-PDMS: octamethyl cyclotetrasiloxane and 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane monomer are used, tetramethyl ammonium hydroxide is used as a catalyst, a ring-opening reaction is carried out, after the ring-opening reaction is finished, the reaction system is heated to the degradation temperature of the catalyst to degrade the catalyst, and then the temperature is reduced to remove low-boiling impurities and byproducts, so that colorless sticky amino-terminated polydimethylsiloxane is obtained;

（2）KCC-1-NH ₂ is prepared from the following steps: taking CTAB, urea and TEOS as raw materials, and reacting to obtain mesoporous silica KCC-1; modifying KCC-1 with KH540 to obtain KCC-1-NH ₂ ;

(3) Preparation of polyamic acid: weighing KCC-1-NH by taking DMAc as solvent ₂ APT-PDMS, 2' -bis [4- (4-aminophenoxyphenyl) phenyl ]]Preparing polyamide acid from propane and 3,3'-4,4' -biphenyl tetracarboxylic dianhydride, controlling the solid content of solution to be 12-15wt%, drying to obtain polyamide acid powder, KCC-1-NH ₂ Is KCC-1-NH ₂ APT-PDMS, 2' -bis [4- (4-aminophenoxyphenyl) phenyl ]]10-40% of the total mass of propane and 3,3'-4,4' -biphenyl tetracarboxylic dianhydride;

(4) Preparation of the ultra-smooth surface: adding polyamide acid powder into toluene or chloroform, controlling the concentration to be 30-50 mg/mL, preparing a porous substrate on a glass sheet by a respiration pattern method, then solidifying at 100-300 ℃, and finally pouring dimethyl silicone oil to obtain the ultra-smooth surface.

2. The method for preparing the silica hybrid polyimide super-smooth surface material with good stability according to claim 1, which is characterized in that: step (1) cooling to 160+/-1 ^o And C or less.

3. The method for preparing the silica hybrid polyimide super-smooth surface material with good stability according to claim 2, which is characterized in that: the ring-opening reaction temperature in the step (1) is 105+/-5 ^o C, the reaction time is 18+/-0.5 h, and the degradation temperature of the catalyst is 180+/-5 ^o C。

4. The method for preparing the silica hybrid polyimide super-smooth surface material with good stability according to claim 1, which is characterized in that: the specific steps of the step (2) comprise: 1g of cetyltrimethylammonium bromide and 0.5. 0.5g urea were weighed into 10mL distilled water and stirred at room temperature for 3h; mixing 2. 2g ethyl orthosilicate, 30. 30mL cyclohexane and 1.5. 1.5mL n-amyl alcohol, and performing ultrasonic treatment for 30 min; the mixture is then brought to 80 ^o C for 4h,60 ^o C reflux 24h, collecting white precipitate, repeatedly washing with water and ethanol three times each, at 60 ^o Drying 24-h by a baking oven to obtain mesoporous silica;

mixing KH540, ethanol 19.3g and water 1.43g for 30min, simultaneously dispersing mesoporous silica 0.6g in toluene 10mL for 30min, and then pouring KH540, ethanol and water into toluene 80 ^o C reflux 24h, taking precipitate, washing with ethanol three times, at 80 ^o And C, drying 24 and h to obtain the amino modified mesoporous silica.

5. The method for preparing the silica hybrid polyimide super-smooth surface material with good stability according to claim 1, which is characterized in that: the specific steps of the step (3) comprise: weighing KCC-1-NH with a set proportion ₂ APT-PDMS, 2' -bis [4- (4-aminophenoxyphenyl) phenyl ]]Propane is dissolved in DMAc solution, then 3,3'-4,4' -biphenyl tetracarboxylic dianhydride is added in three times, and the system is reacted for 3-3.5 hours at room temperature under vacuum state to obtain polyamide acid.