阅读说明：本技术 一种含螺环结构的四胺单体及其制备方法和应用、聚酰胺及其制备和应用 (Tetramine monomer containing spiro structure, preparation method and application thereof, polyamide, and preparation method and application thereof ) 是由 陈春海 王书丽 李莉 姚佳楠 周宏伟 赵晓刚 于 2020-04-14 设计创作，主要内容包括：本发明提供了一种含螺环结构的四胺单体及其制备方法和应用、聚酰胺及其制备和应用,属于气体膜分离技术领域。本发明将自具微孔聚合物(PIMs)中的螺环中心引入到四胺单体中,能够得到含脂肪族基团(亚甲基)、自具微孔结构的四胺单体。由所述四胺单体制成的聚酰胺薄膜具有气体对选择性高、渗透率高、溶解性好和选择性好等特点,同时具有优良的热学性能,可以作为新型聚酰胺气体分离膜。(The invention provides a tetramine monomer containing a spiro structure, a preparation method and application thereof, polyamide and preparation and application thereof, and belongs to the technical field of gas membrane separation. The invention introduces the spiro center in the Polymers (PIMs) with micropores into the tetramine monomer to obtain the tetramine monomer containing aliphatic groups (methylene) and having a micropore structure. The polyamide film prepared from the tetramine monomer has the characteristics of high gas pair selectivity, high permeability, good solubility, good selectivity and the like, has excellent thermal properties, and can be used as a novel polyamide gas separation film.)

1. A tetramine monomer containing a spiro structure has a structure shown in formula I:

wherein R is₁is-CH₃or-CF₃，R₂is-CH₂-or-CF₂-，R₃Is composed of

2. A tetraamine monomer as defined in claim 1, wherein the tetraamine monomer is:

3. the process for preparing a tetraamine monomer containing a spiro structure according to claim 1 or 2, comprising the steps of:

mixing an acid solution of acetone and an acid solution of catechol, and carrying out addition substitution reaction to obtain a spiro tetraphenol compound;

or mixing the acid solution of hexafluoroacetone, the acid solution of catechol and a reducing agent, and carrying out isomerization reaction to obtain a spiro tetraphenol compound;

mixing the spiro tetraphenol compound, the chloramide compound, a catalyst and a reaction solvent, and carrying out nucleophilic substitution reaction to obtain a tetramine monomer;

the chloramide compound has a structure of Cl-R₃-NH₂Wherein R is₃Is composed of

4. The preparation method according to claim 3, wherein the molar ratio of acetone in the acid solution of acetone to catechol in the acid solution of catechol is 1:2 to 5;

the acid in the acid solution of the acetone is hydrogen iodide, hydrogen fluoride, hydrogen chloride or hydrogen bromide, the concentration of the acetone in the acid solution of the acetone is 4-7 g/m L, the acid in the acid solution of the catechol is acetic acid or carbonic acid, and the concentration of the catechol in the acid solution of the catechol is 0.3-0.5 g/m L;

the temperature of the addition substitution reaction is 110-130 ℃, and the time is 10-12 h.

5. The production method according to claim 3, wherein the molar ratio of hexafluoroacetone in the acid solution of hexafluoroacetone to catechol in the acid solution of catechol is 1:2 to 5;

the acid in the hexafluoroacetone acid solution is hydrogen iodide, hydrogen fluoride or hydrogen chloride, and the concentration of the hexafluoroacetone in the hexafluoroacetone acid solution is 4-7 g/m L;

the reducing agent is hydrazine hydrate, zinc powder, magnesium powder, iron powder, stannous chloride, ferrous chloride or sodium borohydride;

the mass ratio of the hexafluoroacetone to the reducing agent is 1: 1.5-2;

the isomerization reaction is carried out at the temperature of 100-140 ℃ for 10-14 h.

6. The preparation method according to claim 3, wherein the molar ratio of the spirocyclic tetraphenol compound, the chloramide compound and the catalyst is 1: 4-7.2: 14-20;

the nucleophilic substitution reaction process comprises the steps of reacting for 30min at room temperature, then heating to 80-100 ℃ for reacting for 1h, and finally heating to 150-160 ℃ for reacting for 4-6 h.

7. Use of a tetramine monomer containing a spiro structure according to claim 1 or 2 or a tetramine monomer containing a spiro structure prepared by the preparation method according to any one of claims 3 to 6 in the preparation of polyamide.

8. A polyamide containing a spiropyran structure has a structure shown in formula II:

in the formula II, n is 80-105, n is an integer, and the number average molecular weight of the polyamide containing the spiropyran structure is (5-7) × 10⁴；

R₁is-CH₃or-CF₃，R₂is-CH₂-or-CF₂-，R₃Is composed of

AR includes

9. A process for producing a polyamide containing a spiropyran structure according to claim 8, comprising the steps of:

mixing the tetramine monomer, the tetraacid monomer, the reaction solvent, the potassium hydroxide, the triphenyl phosphite and the pyridine, carrying out polycondensation reaction, and washing with water to obtain polyamide;

the tetramine monomer is the tetramine monomer containing the spiro structure according to claim 1 or 2 or the tetramine monomer containing the spiro structure prepared by the preparation method according to any one of claims 3 to 6;

the tetracarboxylic acid monomer includes pyromellitic acid, 3',4,4' -biphenyltetracarboxylic acid, 3',4,4' -tetracarboxylic acid benzophenone, or 4,4' - (2,2, 2-trifluoro-1-trifluoromethyl) ethylenebis (1, 2-phthalic acid).

10. Use of the polyamide containing a spiro structure according to claim 8 or the polyamide containing a spiro structure produced by the production method according to claim 9 for a gas separation polyamide film.

Technical Field

The invention relates to the technical field of gas membrane separation, in particular to a tetramine monomer containing a spiro structure, a preparation method and application thereof, and polyamide, and a preparation method and application thereof.

Background

The membrane separation process is one of the emerging technologies with the most development potential since the 21 st century, has the advantages of high efficiency, environmental protection, simple and flexible operation and the like compared with the traditional separation method, and is widely applied to the separation of gases such as natural gas, hydrogen, nitrogen, oxygen, carbon dioxide and the like. In the aspect of selecting membrane separation materials, the polymer membrane material has better processability and is widely concerned. The polyamide has the advantages of excellent comprehensive performance, outstanding mechanical properties, good thermal stability, outstanding flame retardant performance, various synthesis and processing methods and the like, is outstanding in polymer materials and is the first choice of gas separation membrane materials, and becomes an indispensable part in material scientific research and industrial production. However, for aromatic polyamides with higher rigidity of molecular main chains, higher symmetry and stronger intermolecular forces, the free volume of molecular chains is smaller, the permeability coefficient of gas is lower, and the separation of gas is not facilitated; how to research a gas separation membrane which has high separation efficiency, environmental protection, low energy loss, safe operation, long service life and high mechanical performance is the key point of pursuit and attention.

The main problems of the existing polyamide gas separation membrane are that although the membrane has good selectivity and good processability, the molecular chain has high rigidity, low permeability and poor solubility and mechanical property.

Disclosure of Invention

The invention aims to provide a tetramine monomer containing a spiro structure, a preparation method and application thereof, polyamide and preparation and application thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a tetramine monomer containing a spiro structure, which has a structure shown in a formula I:

wherein R is₁is-CH₃or-CF₃，R₂is-CH₂-or-CF₂-，R₃Is composed of

Preferably, the tetramine monomer is:

the invention provides a preparation method of a tetramine monomer containing a spiro structure, which comprises the following steps:

mixing an acid solution of acetone and an acid solution of catechol, and carrying out addition substitution reaction to obtain a spiro tetraphenol compound;

or mixing the acid solution of hexafluoroacetone, the acid solution of catechol and a reducing agent, and carrying out isomerization reaction to obtain a spiro tetraphenol compound;

mixing the spiro tetraphenol compound, the chloramide compound, a catalyst and a reaction solvent, and carrying out nucleophilic substitution reaction to obtain a tetramine monomer;

the chloramide compound has a structure of Cl-R₃-NH₂Wherein R is₃Is composed of

Preferably, the molar ratio of acetone in the acetone acid solution to catechol in the catechol acid solution is 1: 2-5;

the acid in the acid solution of the acetone is hydrogen iodide, hydrogen fluoride, hydrogen chloride or hydrogen bromide, the concentration of the acetone in the acid solution of the acetone is 4-7 g/m L, the acid in the acid solution of the catechol is acetic acid or carbonic acid, and the concentration of the catechol in the acid solution of the catechol is 0.3-0.5 g/m L;

the temperature of the addition substitution reaction is 110-130 ℃, and the time is 10-12 h.

Preferably, the molar ratio of the hexafluoroacetone in the hexafluoroacetone acid solution to the catechol in the catechol acid solution is 1: 2-5;

the acid in the hexafluoroacetone acid solution is hydrogen iodide, hydrogen fluoride or hydrogen chloride, and the concentration of the hexafluoroacetone in the hexafluoroacetone acid solution is 4-7 g/m L;

the reducing agent is hydrazine hydrate, zinc powder, magnesium powder, iron powder, stannous chloride, ferrous chloride or sodium borohydride;

the mass ratio of the hexafluoroacetone to the reducing agent is 1: 1.5-2;

the isomerization reaction is carried out at the temperature of 100-140 ℃ for 10-14 h.

Preferably, the mol ratio of the spiro tetraphenol compound to the chloramide compound to the catalyst is 1: 4-7.2: 14-20;

the nucleophilic substitution reaction process comprises the steps of reacting for 30min at room temperature, then heating to 80-100 ℃ for reacting for 1h, and finally heating to 150-160 ℃ for reacting for 4-6 h.

The invention provides an application of the tetramine monomer containing the spiro structure in the technical scheme or the tetramine monomer containing the spiro structure prepared by the preparation method in the technical scheme in the preparation of polyamide.

The invention provides polyamide containing a spiropyran structure, which has a structure shown in a formula II:

in the formula II, n is 80-105, n is an integer, and the number average molecular weight of the polyamide containing the spiropyran structure is (5-7) × 10⁴；

R₁is-CH₃or-CF₃，R₂is-CH₂-or-CF₂-，R₃Is composed of

AR includes

The invention provides a preparation method of polyamide containing a spiropyran structure, which comprises the following steps:

mixing the tetramine monomer, the tetraacid monomer, the reaction solvent, the potassium hydroxide, the triphenyl phosphite and the pyridine, carrying out polycondensation reaction, and washing with water to obtain polyamide;

the tetramine monomer is the tetramine monomer containing the spiro structure in the technical scheme or the tetramine monomer containing the spiro structure prepared by the preparation method in the technical scheme;

the tetracarboxylic acid monomer includes pyromellitic acid, 3',4,4' -biphenyltetracarboxylic acid, 3',4,4' -tetracarboxylic acid benzophenone, or 4,4' - (2,2, 2-trifluoro-1-trifluoromethyl) ethylenebis (1, 2-phthalic acid).

The invention provides application of the polyamide containing the spiro structure in the technical scheme or the polyamide containing the spiro structure prepared by the preparation method in the technical scheme in a gas separation polyamide film.

The invention provides a tetramine monomer containing a spiro structure, wherein the spiro center in self-contained microporous Polymers (PIMs) is introduced into the tetramine monomer to obtain the tetramine monomer containing an aliphatic group (methylene) and self-contained microporous structure.

The invention provides polyamide containing a spiro structure, wherein the tetramine monomer containing the spiro structure is further polymerized with an aromatic tetracarboxylic acid monomer to obtain a polyamide film, the obtained polyamide film has a microporous structure and contains aliphatic groups, and the introduction of the spiro center increases the non-coplanarity of the polyamide and can improve the gas permeability. In addition, the existence of the microporous structure can facilitate the permeation of gas micromolecules, and the gas permeation capability of the polyamide film is improved; due to the aliphatic group (methylene) structure, the flexibility of the molecular chain of the polymer is improved, so that the solvent is easy to permeate, the problem of poor solubility of the traditional gas separation membrane caused by a rigid chain is solved, and the selectivity of the gas pair of the traditional gas separation membrane can be improved; the introduction of the aromatic tetracarboxylic acid monomer can increase the microporosity and rigidity of the polymer film, and further improve the gas permeability.

The invention provides a preparation method of the polyamide containing the spiro structure, potassium hydroxide is used as a nucleating agent, and the formation of the macrocyclic structure can be promoted; after the reaction is finished, the water washing method is adopted to remove the nucleation center, so that a crown structure similar to crown ether can be formed, the rotation of a polymer molecular chain can be prevented, and the permeability of gas in the polyamide film can be improved.

The polyamide film prepared from the tetramine monomer and the tetraacid monomer has the characteristics of high gas pair selectivity, high permeability, good solubility, good selectivity and the like, has excellent thermal properties, and can be used as a novel polyamide gas separation film.

Drawings

FIG. 1 is a nuclear magnetic spectrum of a tetramine monomer prepared in example 1;

FIG. 2 is an IR spectrum of a polyamide film made of the polyamide prepared in examples 3 to 6;

FIG. 3 is a graph showing nitrogen adsorption curves of polyamide films made of the polyamides prepared in examples 3 to 6.

Detailed Description

The invention provides a tetramine monomer containing a spiro structure, which has a structure shown in a formula I:

wherein R is₁is-CH₃or-CF₃，R₂is-CH₂-or-CF₂-，R₃Is composed of

In the present invention, the tetraamine monomer is preferably:

the invention provides a preparation method of a tetramine monomer containing a spiro structure, which comprises the following steps:

mixing an acid solution of acetone and an acid solution of catechol, and carrying out addition substitution reaction to obtain a spiro tetraphenol compound;

or mixing the acid solution of hexafluoroacetone, the acid solution of catechol and a reducing agent, and carrying out isomerization reaction to obtain a spiro tetraphenol compound;

mixing the spiro tetraphenol compound, the chloramide compound, a catalyst and a reaction solvent, and carrying out nucleophilic substitution reaction to obtain a tetramine monomer;

the chloramide compound has a structure of Cl-R₃-NH₂Wherein R is₃Is composed of

In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known in the art.

The method comprises the steps of mixing an acid solution of acetone and an acid solution of catechol, and carrying out an addition substitution reaction to obtain the spiro tetraphenol compound, wherein the molar ratio of the acetone in the acid solution of acetone to the catechol in the acid solution of catechol is preferably 1: 2-5, more preferably 1: 3-4. in the invention, the acid in the acid solution of acetone is preferably hydrogen iodide, hydrogen fluoride, hydrogen chloride or hydrogen bromide, the concentration of the acetone in the acid solution of acetone is preferably 4-7 g/m L, more preferably 5-6 g/m L. in the invention, the acid solution of acetone is preferably obtained by adding an acid water solution with the mass concentration of 99% to the acetone, and the acid in the acid solution of acetone is used as a catalyst for the substitution reaction.

In the invention, the acid in the acid solution of the catechol is preferably acetic acid or carbonic acid, the concentration of the catechol in the acid solution of the catechol is preferably 0.3-0.5 g/m L, and more preferably 0.35-0.45 g/m L.

The process of mixing the acid solution of acetone and the acid solution of catechol in the present invention is not particularly limited, and the raw materials may be mixed uniformly according to a process well known in the art.

The addition substitution reaction is preferably carried out under the protection of nitrogen, and the addition substitution reaction is preferably carried out by heating and refluxing. In the invention, the temperature of the addition substitution reaction is preferably 110-130 ℃, more preferably 120-125 ℃, and the time is preferably 10-12 h, more preferably 11 h.

After the addition substitution reaction is finished, preferably cooling the obtained material to room temperature to obtain a supersaturated solution, carrying out hydrothermal treatment on the supersaturated solution at 200-240 ℃ and under the high temperature and high pressure of 1 MPa-0.5 GPa by using a hydrothermal crystallization method to precipitate a white microcrystalline compound, filtering the obtained microcrystalline compound, and then alternately washing the microcrystalline compound with glacial acetic acid and dichloromethane for three times to obtain the spiro tetraphenol compound; the spirocyclic tetraphenol compound is a methyl-containing spirocyclic tetraphenol compound.

In the present invention, the process of the addition substitution reaction is as follows:

in another embodiment of the present invention, a hexafluoroacetone acid solution, a catechol acid solution and a reducing agent are mixed and subjected to an isomerization reaction to obtain a spiro tetraphenol compound, wherein the molar ratio of hexafluoroacetone to catechol in the hexafluoroacetone acid solution is preferably 1:2 to 5, more preferably 1:3 to 4. in the present invention, the acid in the hexafluoroacetone acid solution is preferably hydrogen iodide, hydrogen fluoride or hydrogen chloride, the concentration of hexafluoroacetone in the hexafluoroacetone acid solution is preferably 4 to 7g/m L, more preferably 5 to 6g/m L. in the present invention, the hexafluoroacetone acid solution is preferably obtained by adding an acid aqueous solution having a mass concentration of 99% to hexafluoroacetone, and the acid in the hexafluoroacetone acid solution functions as a catalyst for a substitution process.

In the present invention, the acid solution of catechol is completely the same as the acid solution of catechol used in the above addition substitution process, and is not described herein again; the acid in the acid solution of catechol acts as a catalyst for the reaction buckle.

In the present invention, the process of mixing the acid solution of hexafluoroacetone, the acid solution of catechol, and the reducing agent is preferably to mix the acid solution of hexafluoroacetone and the acid solution of catechol first, and then add the reducing agent to the resulting mixture.

In the invention, the reducing agent is preferably hydrazine hydrate, zinc powder, magnesium powder, iron powder, stannous chloride, ferrous chloride or sodium borohydride; the mass ratio of the hexafluoroacetone to the reducing agent is preferably 1: 1.5-2, and more preferably 1: 1.6-1.8.

The isomerization reaction is preferably carried out under the condition of heating reflux, the temperature of the isomerization reaction is preferably 100-140 ℃, more preferably 110-130 ℃, and the time of the isomerization reaction is preferably 10-14 h, more preferably 12-13 h. In the isomerization reaction process, structural rearrangement occurs, carbonyl double bonds on hexafluoroacetone are unfolded, and isomerization is performed to form rings.

After the isomerization reaction is finished, preferably cooling the obtained material to room temperature to obtain a supersaturated solution, continuously reacting for 2 hours, carrying out hydrothermal treatment on the supersaturated solution at the temperature of 220-260 ℃ and under the high temperature and high pressure of 1 MPa-0.5 GPa by using a hydrothermal crystallization method to separate out a white microcrystalline compound, filtering the obtained microcrystalline compound, and then alternately washing the microcrystalline compound with glacial acetic acid and dichloromethane for three times to obtain a spiro tetraphenol compound; the spiro-tetraphenol compound is a trifluoromethyl-containing spiro-tetraphenol compound. The invention recrystallizes the generated product through hydrothermal treatment, and purifies the product.

In the present invention, the isomerization reaction proceeds as follows:

after obtaining the spiro-tetraphenol compound, the invention mixes the spiro-tetraphenol compound, the chloramide compound, the catalyst and the reaction solvent to carry out nucleophilic substitution reaction, thus obtaining the tetramine monomer.

In the invention, the chloramide compound has a structure of Cl-R₃-NH₂Wherein R is₃Is composed of

In the invention, the molar ratio of the spirocyclic tetraphenol compound, the chloramide compound and the catalyst is preferably 1: 4-7.2: 14-20, and more preferably 1: 5-6: 15-18. In the present invention, the catalyst preferably includes sodium carbonate, potassium carbonate, cesium fluoride or lithium carbonate.

In the present invention, the reaction solvent preferably includes N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; the amount of the reaction solvent is preferably such that the total solid content of a reaction system obtained by mixing the spiro tetraphenol compound, the chloroamide compound, the catalyst and the reaction solvent is 15-20%.

The process of mixing the spiro tetraphenol compound, the chloramide compound, the catalyst and the reaction solvent is not particularly limited in the present invention, and the raw materials can be uniformly mixed according to the process well known in the art.

In the present invention, the nucleophilic substitution reaction is preferably performed under nitrogen protection conditions; the nucleophilic substitution reaction process comprises the steps of firstly reacting at room temperature for 30min, then heating to 80-100 ℃ for reacting for 1h, and finally heating to 150-160 ℃ for reacting for 4-6 h; the heating rate of the heating is preferably 5-10 ℃/min, and more preferably 6-8 ℃/min.

After the nucleophilic substitution reaction is completed, the obtained system is preferably cooled to room temperature, then the system is discharged into deionized water, the deionized water is used for extraction, the organic phase is taken and added with magnesium sulfate for drying, and the mixture is decompressed, concentrated and separated out to obtain the tetramine monomer. The process of discharging, extracting, drying and concentrating under reduced pressure is not particularly limited in the invention, and the process can be carried out according to the process well known in the field.

In the present invention, the nucleophilic substitution reaction proceeds as follows:

in the nucleophilic substitution reaction process, the hydroxyl on the tetraphenol compound reacts with chlorine on the chloramide under the action of a catalyst to remove hydrogen chloride.

The invention provides an application of the tetramine monomer containing the spiro structure in the technical scheme or the tetramine monomer containing the spiro structure prepared by the preparation method in the technical scheme in the preparation of polyamide.

The invention provides polyamide containing a spiropyran structure, which has a structure shown in a formula II:

in the formula II, n is 80-105, n is an integer, and the number average molecular weight of the polyamide containing the spiropyran structure is (5-7) × 10⁴；

R₁is-CH₃or-CF₃，R₂is-CH₂-or-CF₂-，R₃Is composed of

AR includes

In the invention, n is preferably 85-100, more preferably 90-95, and the number average molecular weight of the polyamide containing the spiropyran structure is preferably (5.5-6.5) × 10⁴。

In the present invention, the polyamide containing a spiropyran structure preferably includes:

the invention provides a preparation method of polyamide containing a spiropyran structure, which comprises the following steps:

mixing the tetramine monomer, the tetraacid monomer, the reaction solvent, the potassium hydroxide, the triphenyl phosphite and the pyridine, carrying out polycondensation reaction, and washing with water to obtain polyamide;

the tetramine monomer is the tetramine monomer containing the spiro structure in the technical scheme or the tetramine monomer containing the spiro structure prepared by the preparation method in the technical scheme;

the tetracarboxylic acid monomer includes pyromellitic acid, 3',4,4' -biphenyltetracarboxylic acid, 3',4,4' -tetracarboxylic acid benzophenone, or 4,4' - (2,2, 2-trifluoro-1-trifluoromethyl) ethylenebis (1, 2-phthalic acid).

The method comprises the steps of mixing the tetramine monomer, the tetraacid monomer, the reaction solvent, the potassium hydroxide, the triphenyl phosphite and the pyridine, carrying out polycondensation reaction, and washing with water to obtain the polyamide. In the invention, the mole ratio of the tetramine monomer, the tetraacid monomer, the potassium hydroxide, the triphenyl phosphite and the pyridine is preferably 1:1: 5-6: 7-8: 10-13, and more preferably 1:1:5.5:7.5: 11-12.5; the dosage of the reaction solvent is preferably based on that the total solid content of the reaction system obtained by mixing is 15-20%. In the present invention, the potassium hydroxide acts as a nucleating agent, which promotes the formation of macrocyclic structures; the triphenyl phosphite serves as a catalyst, and the pyridine serves as a dehydrating agent.

The mixing process is not particularly limited in the present invention, and the raw materials can be uniformly mixed according to a process well known in the art. In the present invention, the process of the polycondensation reaction preferably includes: refluxing the mixed materials under a heating condition (150-200 ℃ for 5-8 h), then closing stirring, stopping heating and refluxing, adding potassium hydroxide (used as a pH regulator) into the obtained reaction system to control the pH value of the reaction solution to be 12-14, continuously heating and refluxing for 4-6 h, further performing polycondensation, then naturally cooling, discharging the obtained viscous polyamide into deionized water, alternately refluxing and washing with ethanol and deionized water for three times, fully removing residual solvent and potassium hydroxide used for reaction, and decompressing at 100 ℃ for 12h to obtain the polyamide.

In the polycondensation reaction process, potassium hydroxide is used as a nucleating agent, so that the formation of a macrocyclic structure can be promoted; after the reaction is finished, the nucleation center (potassium ions in potassium hydroxide) is removed by adopting a water washing method, the structure similar to crown ether can be guaranteed to be formed, the multi-ring structure similar to crown ether is formed by polymerization through the polymerization method, the chain spacing of the polymer can be further increased, and the gas permeability is improved. Meanwhile, the crown ether has a crown-like structure with a large volume unit; the introduction of a crown ether-like structure into the polymer can increase the chain pitch of the polymer, prevent the rotation of the polymer molecular chains, increase the gas permeability of the gas in the polymer film, and further increase the gas permeability of the polyamide film.

The invention provides application of polyamide containing a spiro structure in a gas separation polyamide film or polyamide containing a spiro structure prepared by the preparation method in the technical scheme, and the application method is not particularly limited, and the polyamide containing a spiro structure is directly prepared into the polyamide film for gas separation, the invention is not particularly limited to the method for preparing the polyamide film from the polyamide containing a spiro structure according to the well-known process in the field, in the embodiment of the invention, the method for preparing the polyamide film from the polyamide containing a spiro structure is that the polyamide containing a spiro structure is dissolved in a trichloromethane solution by 15%, insoluble substances are removed by filtering through a 0.45μm Teflon filter to obtain a uniform polyamide solution, the solution is uniformly coated on a clean 9cm × 9cm glass plate by a scraper, the glass plate is placed at normal temperature for 48 hours, then the glass plate is placed in a vacuum oven for 12 hours, the glass plate is naturally cooled, the obtained polyamide film is immersed in an inert solvent, the solid content in the obtained film is eliminated, and the obtained film is dried again in the vacuum oven to obtain the trichloromethane film with the preferred concentration of no organic solvent, and the trichloromethane is dried in the vacuum oven.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.