CN113336773A - Spiro-bis-benzoxazole diamine, preparation method and application thereof, polyimide, preparation method and application thereof - Google Patents

Spiro-bis-benzoxazole diamine, preparation method and application thereof, polyimide, preparation method and application thereof Download PDF

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CN113336773A
CN113336773A CN202110726168.0A CN202110726168A CN113336773A CN 113336773 A CN113336773 A CN 113336773A CN 202110726168 A CN202110726168 A CN 202110726168A CN 113336773 A CN113336773 A CN 113336773A
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于有海
陈海权
钱广涛
陈春海
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Abstract

The invention belongs to the technical field of macromolecules, and particularly relates to spirobisbenzoxazole diamine, a preparation method and application thereof, polyimide, a preparation method and application thereof. Polyimide is prepared by adopting the spirobisbenzoxazole diamine provided by the invention as a monomer, and a spiro structure is introduced into a diamine structure, so that the obtained polyimide has excellent solubility and processability; meanwhile, the polyimide forms a microporous structure, and the gas permeability of the polyimide is improved.

Description

Spiro-bis-benzoxazole diamine, preparation method and application thereof, polyimide, preparation method and application thereof
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to spirobisbenzoxazole diamine, a preparation method and application thereof, polyimide, a preparation method and application thereof.
Background
Polyimide is a special engineering material with excellent weather resistance and solvent resistance, and is widely applied to the industries of electronics, electricians, aerospace, membrane separation and the like. Conventional polyimides exhibit excellent gas selectivity due to excellent rigid molecular skeleton and strong intermolecular interaction, but are inferior in heat resistance and mechanical properties; at the same time, the solubility and processability of conventional polyimides are reduced due to rigid molecular chains and tight molecular packing.
In the prior art, by introducing an aromatic heterocyclic structure into a main chain of a Polyimide molecule, the mechanical property and High temperature resistance of Polyimide can be effectively improved, wherein benzoxazole is taken as a typical rigid aromatic heterocyclic unit and is introduced into the main chain of the Polyimide molecule, so that the mechanical property and the heat resistance of the material can be obviously improved, for example, Chinese patent and literature 'Preparation and Properties of High-performance polymer fiber obtained from 5-Amino-2- (2-hydroxy-5-aminobenzene) -benzoxazole' with the publication number of CN108117653A is disclosed, wherein the prepared benzoxazole Polyimide has High glass transition temperature and excellent mechanical property. However, the obtained benzoxazole polyimide still has the defects of poor solubility and difficult processing, and the application in the field of gas separation membranes is limited due to low gas permeability.
Disclosure of Invention
The invention aims to provide spirobisbenzoxazole diamine, and polyimide prepared by using the spirobisbenzoxazole diamine as a reaction monomer has excellent solubility, easy processability and gas permeability.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides spirobisbenzoxazole diamine which has a structure shown in a formula I:
Figure BDA0003138726900000011
wherein R is-H, -CH3or-OH.
Preferably, the spirobisbenzoxazole diamine is a compound with a structure shown in a formula I-1, a formula I-2, a formula I-3, a formula I-4 or a formula I-5;
Figure BDA0003138726900000021
preferably, the spirobisbenzoxazole diamine is a compound with a structure shown in a formula I-6, a formula I-7, a formula I-8, a formula I-9 or a formula I-10;
Figure BDA0003138726900000022
Figure BDA0003138726900000031
the invention also provides a preparation method of the spirobisbenzoxazole diamine, which is characterized by comprising the following steps:
carrying out rearrangement reaction on bisphenol A and methanesulfonic acid to obtain an intermediate with a structure shown in a formula a;
carrying out a first condensation reaction on the intermediate with the structure shown in the formula a and benzyl chloride to obtain an intermediate with the structure shown in the formula b;
carrying out nitration reaction on the intermediate with the structure shown in the formula b to obtain an intermediate with the structure shown in the formula c;
carrying out a first catalytic hydrogenation reaction on the intermediate with the structure shown in the formula c to obtain an intermediate with the structure shown in the formula d;
carrying out acyl chlorination on a monomer with a structure shown as a formula e to obtain an intermediate with a structure shown as a formula f;
carrying out a second condensation reaction on the intermediate with the structure shown in the formula f and the intermediate with the structure shown in the formula d to obtain an intermediate with the structure shown in the formula g;
carrying out ring closing reaction on the intermediate with the structure shown in the formula g to obtain an intermediate with the structure shown in the formula h;
carrying out a second catalytic hydrogenation reaction on the intermediate with the structure shown in the formula h to obtain the spirobisbenzoxazole diamine;
Figure BDA0003138726900000032
Figure BDA0003138726900000041
the invention also provides application of the spirobisbenzoxazole diamine in the technical scheme or the spirobisbenzoxazole diamine prepared by the preparation method in the technical scheme in preparation of polyimide.
The invention also provides polyimide, which has a structure shown in a formula II:
Figure BDA0003138726900000042
r is-H, -CH3or-OH;
and n is 40-60.
Preferably, the polyimide is a compound with a structure shown in a formula II-1, a formula II-2, a formula II-3, a formula II-4 or a formula II-5;
Figure BDA0003138726900000043
Figure BDA0003138726900000051
preferably, the polyimide is a compound with a structure shown in a formula II-6, a formula II-7 or a formula II-8;
Figure BDA0003138726900000052
the invention also provides a preparation method of the polyimide, which comprises the following steps:
performing polycondensation reaction on spiro-bis-benzoxazole diamine and hexafluoro-dianhydride to obtain the polyimide;
the spirobisbenzoxazole diamine is the spirobisbenzoxazole diamine in the technical scheme or the spirobisbenzoxazole diamine prepared by the preparation method in the technical scheme.
The invention also provides the application of the polyimide prepared by the preparation method in the technical scheme or the polyimide prepared by the preparation method in the technical scheme in gas separation.
The invention provides spirobisbenzoxazole diamine with a structure shown in a formula I. The spiro-bis-benzoxazole diamine provided by the invention is used as a monomer to prepare polyimide, a spiro structure is introduced into a molecular structure of benzoxazole diamine, so that effective accumulation of a molecular chain can be destroyed, and the solubility of polyimide is further improved on the basis of keeping heat resistance and mechanical properties, so that the processability of polyimide is improved; meanwhile, due to the introduction of the spiral ring structure, the polyimide can form a microporous structure, and the gas permeability of the polyimide is further improved.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of spirobisbenzoxazole diamine obtained in examples 1 to 3;
FIG. 2 is an IR spectrum of a polyimide film obtained by using the polyimide obtained in examples 1 to 3;
FIG. 3 is a graph showing the thermal stability of polyimide films produced using the polyimides obtained in examples 1 to 3;
FIG. 4 is a graph showing the glass transition temperature of polyimide films produced using the polyimides obtained in examples 1 to 3;
FIG. 5 is a drawing showing the tensile test of a polyimide film produced using the polyimide obtained in examples 1 to 3.
Detailed Description
The invention provides spirobisbenzoxazole diamine which has a structure shown in a formula I:
Figure BDA0003138726900000061
wherein R is-H, -CH3or-OH.
In the invention, the spirobisbenzoxazole diamine is preferably a compound having a structure shown in formula I-1, formula I-2, formula I-3, formula I-4 or formula I-5;
Figure BDA0003138726900000071
in the present invention, the spirobisbenzoxazole diamine is further preferably a compound having a structure represented by formula I-6, formula I-7, formula I-8, formula I-9 or formula I-10;
Figure BDA0003138726900000072
Figure BDA0003138726900000081
the invention also provides a preparation method of the spirobisbenzoxazole diamine in the technical scheme, which is characterized by comprising the following steps:
carrying out rearrangement reaction on bisphenol A and methanesulfonic acid to obtain an intermediate with a structure shown in a formula a;
carrying out a first condensation reaction on the intermediate with the structure shown in the formula a and benzyl chloride to obtain an intermediate with the structure shown in the formula b;
carrying out nitration reaction on the intermediate with the structure shown in the formula b to obtain an intermediate with the structure shown in the formula c;
carrying out a first catalytic hydrogenation reaction on the intermediate with the structure shown in the formula c to obtain an intermediate with the structure shown in the formula d;
carrying out acyl chlorination on a monomer with a structure shown as a formula e to obtain an intermediate with a structure shown as a formula f;
carrying out a second condensation reaction on the intermediate with the structure shown in the formula f and the intermediate with the structure shown in the formula d to obtain an intermediate with the structure shown in the formula g;
carrying out ring closing reaction on the intermediate with the structure shown in the formula g to obtain an intermediate with the structure shown in the formula h;
carrying out a second catalytic hydrogenation reaction on the intermediate with the structure shown in the formula h to obtain the spirobisbenzoxazole diamine;
Figure BDA0003138726900000082
Figure BDA0003138726900000091
in the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the synthetic route of the spirobisbenzoxazole diamine monomer is preferably as follows:
Figure BDA0003138726900000092
the invention carries out rearrangement reaction on bisphenol A and methanesulfonic acid to obtain an intermediate with a structure shown in a formula a;
Figure BDA0003138726900000101
in the present invention, the feed ratio of bisphenol A to methanesulfonic acid is preferably 9.0 to 11.0g/mL, more preferably 9.5 to 10.5g/mL, and still more preferably 10.0 g/mL. In the invention, the temperature of the rearrangement reaction is preferably 130-140 ℃, more preferably 132-138 ℃, more preferably 135 ℃, and the time is preferably 4-5 h, more preferably 4.2-4.8 h, more preferably 4.5 h.
In the present invention, the rearrangement reaction is preferably judged to be completed by TLC detection.
After the rearrangement reaction is completed, the solution obtained after the reaction is preferably recrystallized, filtered and dried to obtain the intermediate with the structure shown in the formula a. In the present invention, the recrystallization process is preferably performed by discharging the solution obtained from the reaction into ice water, and adding an equal volume of ethanol to perform recrystallization. The filtration and drying are not particularly limited in the present invention, and those well known to those skilled in the art can be used.
After obtaining the intermediate with the structure shown in the formula a, carrying out a first condensation reaction on the intermediate with the structure shown in the formula a and benzyl chloride to obtain an intermediate with the structure shown in the formula b;
Figure BDA0003138726900000102
in the present invention, the first condensation reaction is preferably carried out by mixing an intermediate having a structure represented by formula a, benzyl chloride, an acid-binding agent i, and an organic solvent i.
In the invention, the acid-binding agent I is preferably carbonate, and is further preferably one or more of sodium carbonate, sodium bicarbonate and potassium carbonate; when the acid-binding agent I is two or more of the above specific choices, the specific material ratio is not particularly limited in the present invention, and the acid-binding agent I may be mixed at any ratio. In a specific embodiment of the invention, the acid-binding agent I is specifically potassium carbonate.
In the present invention, the organic solvent i is preferably one or more selected from acetonitrile, pyridine and N, N-dimethylformamide, and when the organic solvent i is two or more selected from the above specific choices, the ratio of the specific substances in the present invention is not particularly limited, and the organic solvent i may be mixed at any ratio. In a particular embodiment of the invention, the organic solvent i is in particular acetonitrile.
In the invention, the molar ratio of the intermediate having the structure shown in formula a to benzyl chloride is preferably 0.3-0.5: 1, more preferably 0.35 to 0.45:1, and still more preferably 0.4: 1. In the present invention, the molar ratio of the benzyl chloride to the acid-binding agent i is preferably 1.0 to 1.2:1, and more preferably 1.1: 1. In the invention, the feeding ratio of the organic solvent I to the intermediate with the structure shown in the formula a is preferably 10-12 mL/g, and more preferably 11 mL/g.
The present invention does not require special means for such mixing, as would be known to one skilled in the art.
In the invention, the temperature of the first condensation reaction is preferably 70-80 ℃, more preferably 72-78 ℃, more preferably 75 ℃, and the time is preferably 10-12 h, more preferably 10.5-11.5 h, more preferably 11 h. In the present invention, the first condensation reaction is preferably carried out using a reflux apparatus.
In the present invention, the first condensation reaction is preferably judged to be complete by TLC detection.
After the first condensation reaction is finished, the invention preferably carries out post-treatment on the reaction product; the post-treatment process preferably comprises pulping, suction filtration, extraction, rotary evaporation, suction filtration and drying in sequence. In the present invention, the beating preferably includes pouring the solution obtained after the reaction into water to carry out beating, to obtain a slurry. The amount of water added in the present invention is not particularly limited, and those skilled in the art will appreciate.
The process of the suction filtration is not particularly limited in the present invention, and those familiar to those skilled in the art can be used.
In the present invention, the extraction is preferably carried out by adding methylene chloride. The addition amount of the dichloromethane is not particularly required in the invention, and the dichloromethane can be prepared by adopting the method well known by the technical personnel in the field.
The process of the rotary evaporation is not particularly limited in the present invention, and may be those well known to those skilled in the art.
In the present invention, the suction filtration drying is preferably performed by adding ethanol during the suction filtration. The invention has no special requirement on the addition amount of the ethanol, and the ethanol is prepared by adopting the method well known by the technical personnel in the field. The conditions of the suction filtration and drying are not particularly limited in the present invention, and those well known to those skilled in the art can be used.
After obtaining the intermediate with the structure shown in the formula b, carrying out nitration reaction on the intermediate with the structure shown in the formula b to obtain an intermediate with the structure shown in the formula c;
Figure BDA0003138726900000121
in the present invention, the course of the nitration reaction preferably comprises: mixing the intermediate with the structure shown in the formula b and first acetic acid to obtain an acetic acid solution; mixing the second acetic acid, the concentrated nitric acid and the concentrated sulfuric acid to obtain mixed acid liquid; and mixing the acetic acid solution with the mixed acid solution to carry out nitration reaction.
The invention mixes the intermediate with the structure shown in the formula b and the first acetic acid to obtain the acetic acid solution.
In the present invention, the concentration of the first acetic acid is preferably 17.5 mol/L. In the invention, the feeding ratio of the first acetic acid to the intermediate with the structure of the formula b is preferably 5-8 mL/g, and more preferably 6-7 mL/g.
According to the invention, the second acetic acid, the concentrated nitric acid and the concentrated sulfuric acid are mixed to obtain the mixed acid liquid.
In the present invention, the concentration of the second acetic acid is preferably 17.5 mol/L. In the present invention, the concentration of the concentrated nitric acid is preferably 14.5 mol/L. In the present invention, the concentration of the concentrated sulfuric acid is preferably 18.4 mol/L.
In the present invention, the volume ratio of the second acetic acid, the concentrated nitric acid, and the concentrated sulfuric acid is preferably 2: 1-2: 0.7 to 1.3, and more preferably 2:1.27: 0.8.
After the acetic acid solution and the mixed acid liquid are obtained, the acetic acid solution and the mixed acid liquid are mixed to carry out nitration reaction.
In the invention, the molar ratio of nitric acid to the intermediate with the structure shown in the formula b in the concentrated nitric acid is preferably 12-18: 1, more preferably 13 to 17: 1, more preferably 15 to 16: 1. in the invention, the molar ratio of sulfuric acid to the intermediate with the structure shown in the formula b in the concentrated sulfuric acid is preferably 10-15: 1, more preferably 11 to 14: 1, more preferably 12 to 13: 1.
in the invention, the temperature of the nitration reaction is preferably 20-30 ℃, more preferably 22-28 ℃, and more preferably 25-26 ℃; the time is preferably 10 to 12 hours, and more preferably 10 to 11 hours.
In the present invention, the nitration reaction is preferably judged to be complete by TLC detection. The present invention does not require special means for such mixing, as would be known to one skilled in the art.
After the nitration reaction is finished, the invention preferably carries out post-treatment on the reaction product; the post-treatment preferably comprises washing, extraction, rotary evaporation, precipitation, suction filtration and drying which are sequentially carried out. In the present invention, the washing is preferably carried out by adding water to the reaction product. The invention has no special requirement on the washing times, and can remove redundant acid in the reaction product. In the present invention, the extraction is preferably carried out by adding methylene chloride. The amount of the dichloromethane to be added is not particularly limited in the present invention, and those known to those skilled in the art may be used. In the present invention, the precipitation is preferably carried out by adding petroleum ether. The addition amount of the petroleum ether is not particularly required in the invention, and the petroleum ether can be prepared by the method well known by the technical personnel in the field. The present invention does not specifically limit the parameters of the conditions for the rotary evaporation and suction filtration drying, and the conditions are well known to those skilled in the art.
After obtaining the intermediate with the structure shown in the formula c, carrying out a first catalytic hydrogenation reaction on the intermediate with the structure shown in the formula c to obtain an intermediate with the structure shown in the formula d;
Figure BDA0003138726900000131
in the present invention, the first catalytic hydrogenation process preferably comprises: and (3) mixing the intermediate with the structure shown in the formula c, a hydrogenation catalyst I and an organic solvent II to perform a first catalytic hydrogenation reaction.
In the invention, the hydrogenation catalyst I is preferably one or more of palladium carbon, platinum carbon, active nickel and rhodium carbon; when the hydrogenation catalyst i is two or more of the above specific choices, the present invention does not specifically limit the ratio of the specific substances, and the specific substances may be mixed at any ratio. In a specific embodiment of the present invention, the hydrogenation catalyst i is specifically palladium on carbon.
In the invention, the organic solvent II is preferably one or more of tetrahydrofuran, ethanol, methanol, isopropanol and 1, 4-dioxane; when the organic solvent ii is two or more of the above specific choices, the specific ratio of the specific substances in the present invention is not particularly limited, and the organic solvent ii may be mixed at any ratio. In a specific embodiment of the present invention, the organic solvent ii is specifically ethanol.
The present invention does not require special means for such mixing, as would be known to one skilled in the art.
In the invention, the mass ratio of the hydrogenation catalyst I to the intermediate with the structure shown in the formula c is preferably 0.1-0.15: 1, more preferably 0.11 to 0.13: 1. in the invention, the feeding ratio of the organic solvent II to the intermediate with the structure shown in the formula c is preferably 10-12 mL/g, and more preferably 10-11 mL/g.
In the invention, the temperature of the first catalytic hydrogenation is preferably 40-100 ℃, more preferably 50-90 ℃, and more preferably 60-80 ℃; the time is preferably 4 to 8 hours, and more preferably 5 to 6 hours.
In the present invention, the first catalytic hydrogenation reaction is preferably carried out in an autoclave. In the present invention, the first catalytic hydrogenation reaction is preferably carried out by introducing hydrogen into an autoclave to carry out a pressure reaction. In the present invention, the pressure of the pressure reaction is preferably 0.5 to 3.0MPa, more preferably 1.0 to 2.5MPa, and still more preferably 1.5 to 2.0 MPa. In the present invention, it is also preferable to carry out gas replacement three times by introducing nitrogen into the autoclave before introducing hydrogen.
In the present invention, the first catalytic hydrogenation reaction is preferably judged to be completed by TLC detection.
After the first catalytic hydrogenation reaction is finished, the invention preferably carries out post-treatment on the reaction product; the post-treatment preferably comprises a first filtration, a cooling crystallization, a second filtration and a drying, which are carried out in sequence. In the present invention, the first filtration preferably results in a catalyst and a filtrate; cooling and crystallizing the filtrate. In the present invention, the catalyst obtained by filtration is preferably recovered and used. The cooling crystallization, the second filtration and the drying are not particularly limited in the present invention, and those well known to those skilled in the art can be used.
The method comprises the following steps of carrying out acyl chlorination on a monomer with a structure shown as a formula e to obtain an intermediate with a structure shown as a formula f;
Figure BDA0003138726900000141
in the present invention, the process of the acyl chlorination reaction preferably comprises: mixing a monomer with a structure shown as a formula e, thionyl chloride and N, N-dimethylformamide to perform acyl chlorination reaction.
In the present invention, the charge ratio of the thionyl chloride to the monomer having the structure represented by formula e is preferably 5.0 to 6.0mL/g, and more preferably 5.5 mL/g. In the invention, the volume ratio of the N, N-dimethylformamide to the thionyl chloride is preferably 0.02-0.05: 1, more preferably 0.03 to 0.04: 1.
in the invention, the temperature of the acyl chlorination reaction is preferably 50-80 ℃, more preferably 55-75 ℃, and more preferably 60-70 ℃; the time is preferably 4 to 6 hours, more preferably 4.5 to 5.5 hours, and still more preferably 5 hours.
In the present invention, the acid chlorination reaction is preferably judged to be completed by TLC detection. The present invention does not require special means for such mixing, as would be known to one skilled in the art.
After the acyl chlorination reaction is finished, the invention preferably removes impurities and purifies reaction products. In the invention, the mode of impurity removal and purification is preferably that the solution obtained after the reaction is subjected to rotary evaporation. The rotary evaporation is not specially limited, and redundant thionyl chloride in the solution can be removed. After the impurity removal and purification, the invention preferably comprises the step of repeatedly precipitating and rotary evaporating the reaction product by using tetrahydrofuran to obtain a tetrahydrofuran solution containing the intermediate with the structure shown in the formula f. In the invention, the concentration of the tetrahydrofuran solution containing the intermediate with the structure shown in the formula f is preferably 2-5 g/mL, and more preferably 3-4 g/mL. The invention has no special requirements on the times of precipitation and rotary evaporation, and can obtain pure tetrahydrofuran solution.
After an intermediate with a structure shown in a formula f is obtained, carrying out a second condensation reaction on the intermediate with the structure shown in the formula f and the intermediate with the structure shown in the formula d to obtain an intermediate with a structure shown in a formula g;
Figure BDA0003138726900000151
in the present invention, the process of the second condensation reaction preferably includes: mixing an intermediate with a structure shown in a formula d, an organic solvent III and an acid-binding agent II to obtain a mixed solution; and (c) mixing the solution containing the intermediate tetrahydrofuran with the structure shown in the formula f with the mixed solution to perform a second condensation reaction.
The method comprises the step of mixing an intermediate with a structure shown in a formula d, an organic solvent III and an acid-binding agent II to obtain a mixed solution.
In the invention, the organic solvent III is preferably one or more of tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; when the organic solvent iii is two or more of the above specific choices, the specific material ratio in the present invention is not particularly limited, and the organic solvent iii may be mixed at any ratio. In a specific embodiment of the present invention, the organic solvent iii is tetrahydrofuran.
In the invention, the acid-binding agent II is preferably one or more of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate and potassium carbonate; when the acid-binding agent ii is two or more of the above specific choices, the present invention does not specifically limit the proportion of the specific substances, and the specific substances may be mixed at any proportion. In a specific embodiment of the present invention, the acid-binding agent ii is specifically triethylamine.
In the invention, the feeding ratio of the organic solvent III to the intermediate with the structure shown in the formula d is preferably 6-10 mL/g, and more preferably 7-9 mL/g. In the invention, the molar ratio of the acid-binding agent II to the intermediate with the structure shown in the formula d is preferably 2.0-2.5: 1, more preferably 2.1 to 2.4: 1, more preferably 2.2 to 2.3: 1.
the mixing method is not particularly limited, and those known to those skilled in the art can be used. The invention also preferably comprises cooling the mixed solution. In the invention, the temperature after temperature reduction is preferably 9-11 ℃.
In the invention, the tetrahydrofuran solution containing the intermediate with the structure shown in the formula f is mixed with the mixed solution to carry out a second condensation reaction.
In the invention, the molar ratio of the intermediate with the structure shown in the formula d to the intermediate with the structure shown in the formula f is preferably 2.0-2.5: 1, more preferably 2.1 to 2.4: 1, more preferably 2.2 to 2.3: 1.
in the present invention, the mixing is preferably performed by dropping a solution of tetrahydrofuran containing an intermediate having a structure represented by formula f into the mixed solution. In the present invention, the drop velocity is preferably 1.0 to 4.0mL/min, and more preferably 2.0 to 3.0 mL/min.
In the invention, the temperature of the second condensation reaction is preferably 10-30 ℃, more preferably 15-25 ℃, and more preferably 20 ℃; the time is preferably 10 to 12 hours, and more preferably 10 to 11 hours.
In the present invention, the second condensation reaction is preferably judged to be complete by TLC detection.
After the second condensation reaction is finished, the invention preferably carries out post-treatment on the reaction product; the post-treatment preferably comprises vacuum filtration, pulping and drying which are carried out in sequence. In the present invention, the reduced pressure filtration is preferably performed by adding water to the solution obtained after the reaction and performing reduced pressure filtration to obtain a crude product. The amount of water added in the present invention is not particularly limited, and those skilled in the art will appreciate. In the present invention, the beating is preferably carried out by adding methylene chloride to the crude product. The amount of the methylene chloride added in the present invention is not particularly limited, and those known to those skilled in the art can be used. The invention has no special requirements on the condition parameters of the reduced pressure suction filtration, pulping, filtration and drying, and can adopt the conditions well known by the technical personnel in the field.
After an intermediate with a structure shown in a formula g is obtained, the intermediate with the structure shown in the formula g is subjected to ring closure reaction to obtain an intermediate with a structure shown in a formula h;
Figure BDA0003138726900000161
the intermediate with the structure shown in the formula h is obtained by mixing the intermediate with the structure shown in the formula g, the organic solvent IV and the acidic reagent to perform a ring closing reaction.
In the present invention, the organic solvent iv is preferably sulfolane and/or N-methylpyrrolidone; when the organic solvent IV is sulfolane and N-methyl pyrrolidone, the proportion of the organic solvent IV and the N-methyl pyrrolidone is not particularly required, and the organic solvent IV can be mixed in any proportion. In a particular embodiment of the invention, the organic solvent iv is in particular sulfolane.
In the present invention, the acidic agent is preferably p-toluenesulfonic acid and/or polyphosphoric acid; when the acidic reagent is p-toluenesulfonic acid and polyphosphoric acid, the ratio of the p-toluenesulfonic acid to the polyphosphoric acid is not particularly required, and the p-toluenesulfonic acid and polyphosphoric acid can be mixed in any ratio. In a particular embodiment of the invention, the acidic agent is in particular p-toluenesulfonic acid.
In the invention, the feeding ratio of the organic solvent IV to the intermediate with the structure shown in the formula g is preferably 10-12 mL/g, and more preferably 10-11 mL/g. In the invention, the molar ratio of the acidic reagent to the intermediate with the structure shown in the formula g is preferably 2.0-2.5: 1, more preferably 2.1 to 2.4: 1, more preferably 2.2 to 2.3: 1.
in the invention, the temperature of the ring closing reaction is preferably 150-180 ℃, more preferably 160-175 ℃, and more preferably 165-170 ℃; the time is preferably 3 to 4 hours, and more preferably 3 hours. In the present invention, the ring closure reaction is preferably carried out in a reflux condenser.
In the present invention, the ring closure reaction is preferably judged to be completed by TLC detection. The present invention does not require special means for such mixing, as would be known to one skilled in the art.
After the ring closing reaction is finished, the invention preferably carries out post-treatment on the reaction product; the post-treatment preferably comprises vacuum filtration, recrystallization and filtration drying which are sequentially carried out. In the present invention, the reduced pressure filtration is preferably performed by adding water to the solution obtained after the reaction and performing reduced pressure filtration to obtain a crude product. The amount of water added in the present invention is not particularly limited, and those skilled in the art will appreciate. In the present invention, the recrystallization is preferably performed by adding dioxane and water to the crude product. In the present invention, the volume ratio of dioxane to water is preferably 5: 1. the addition amount of the dioxane and the water is not required in the invention, and the addition amount is known by the skilled person. The present invention does not specifically limit the parameters of the vacuum filtration, recrystallization and filtration drying, and those known to those skilled in the art can be used.
After the intermediate with the structure shown in the formula h is obtained, the intermediate with the structure shown in the formula h is subjected to a second catalytic hydrogenation reaction to obtain the spirobisbenzoxazole diamine.
The intermediate with the structure shown in the formula h, the hydrogenation catalyst I and the organic solvent II are preferably mixed to perform a second catalytic hydrogenation reaction.
In the present invention, the condition parameters of the second catalytic hydrogenation reaction are the same as those of the first catalytic hydrogenation reaction, and are not described herein again.
In the present invention, the second catalytic hydrogenation reaction is preferably judged to be completed by TLC detection. The present invention does not require special means for such mixing, as would be known to one skilled in the art.
After the second catalytic hydrogenation reaction is completed, the reaction product is preferably subjected to post-treatment, and the post-treatment process is the same as that of the first catalytic hydrogenation reaction, and is not described again.
The invention also provides application of the spirobisbenzoxazole prepared by the preparation method in the technical scheme or the spirobisbenzoxazole prepared by the preparation method in the technical scheme in preparation of polyimide.
The invention also provides polyimide, which has a structure shown in a formula II:
Figure BDA0003138726900000181
r is-H, -CH3or-OH;
and n is 40-60.
In the present invention, n is 40 to 60, more preferably 45 to 55, and still more preferably 45 to 50.
In the present invention, the polyimide is preferably a compound having a structure represented by formula II-1, formula II-2, formula II-3, formula II-4 or formula II-5;
Figure BDA0003138726900000182
Figure BDA0003138726900000191
in the present invention, the polyimide is further preferably a compound having a structure represented by the formula II-6, the formula II-7 or the formula II-8;
Figure BDA0003138726900000192
the invention also provides a preparation method of the polyimide, which comprises the following steps:
performing polycondensation reaction on spiro-bis-benzoxazole diamine and hexafluoro-dianhydride to obtain the polyimide;
the spirobisbenzoxazole diamine is the spirobisbenzoxazole diamine in the technical scheme or the spirobisbenzoxazole diamine prepared by the preparation method in the technical scheme.
In the present invention, the synthetic route of the polyimide is preferably:
Figure BDA0003138726900000201
in the present invention, the process of the polycondensation reaction preferably includes: mixing spirodiclobenzoxazole diamine, hexafluoro dianhydride and an organic solvent V to obtain a mixed solution; and mixing a catalyst with the mixed solution to perform a polycondensation reaction to obtain the catalyst.
The method comprises the step of mixing spirobisbenzoxazole diamine, hexafluoro dianhydride and an organic solvent V to obtain a mixed solution.
In the invention, the organic solvent V is preferably one or more of m-cresol, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylformamide; when the organic solvent v is two or more of the above specific choices, the specific ratio of the specific substances in the present invention is not particularly limited, and the organic solvent v may be mixed at any ratio. In a specific embodiment of the present invention, the organic solvent v is specifically m-cresol.
In the invention, the mole ratio of the spirobisbenzoxazole diamine to the hexafluorodianhydride is preferably 1.00-1.02: 1, more preferably 1.00 to 1.01: 1. in the invention, the solid content of the mixed solution is preferably 15-25%, more preferably 18-23%, and still more preferably 20-21%.
In the present invention, the mixing preferably includes heating and mixing the spirobisbenzoxazole diamine, the hexafluorodianhydride, and the organic solvent v. In the invention, the heating temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and more preferably 95-100 ℃; the time is preferably 0.5 to 1.0 hour, more preferably 0.6 to 0.9 hour, and still more preferably 0.7 to 0.8 hour.
In the present invention, the heating and mixing are preferably performed under stirring. In the invention, the rotation speed of the stirring is preferably 200-300 r/min, more preferably 220-280 r/min, and even more preferably 250-260 r/min. In the present invention, the heating and mixing are preferably performed under a nitrogen atmosphere.
After the mixed solution is obtained, the catalyst and the mixed solution are mixed to carry out polycondensation reaction to obtain the catalyst.
In the invention, the catalyst is preferably one or more of isoquinoline, pyridine and triethylamine; when the catalyst is two or more of the above specific choices, the specific ratio of the specific substances in the present invention is not particularly limited, and the specific substances may be mixed at any ratio. In a particular embodiment of the invention, the catalyst is in particular isoquinoline.
In the invention, the mass ratio of the catalyst to the organic solvent V is preferably 0.01-0.03: 1, more preferably 0.015 to 0.025:1, and still more preferably 0.018 to 0.020: 1.
In the present invention, the mixing is preferably performed by adding a catalyst to the mixed solution to cause a polycondensation reaction.
In the invention, the temperature of the polycondensation reaction is preferably 170-200 ℃, more preferably 175-195 ℃, and more preferably 180-190 ℃; the time is preferably 3 to 5 hours, and more preferably 3 to 4 hours. In the invention, the polycondensation reaction is preferably carried out under a stirring condition, and the rotation speed of the stirring is preferably 200 to 300r/min, more preferably 220 to 280r/min, and even more preferably 250 to 260 r/min. In the present invention, the polycondensation reaction is preferably carried out under a nitrogen atmosphere.
After the polycondensation reaction is finished, the invention preferably carries out post-treatment on the reaction product; the post-treatment preferably comprises discharging, redissolving, precipitating, washing, suction filtering and drying which are sequentially carried out.
In the invention, the discharging mode is preferably that a crude product is obtained by mixing the reaction solution and ethanol, and then carrying out suction filtration and drying. In the present invention, the volume ratio of the reaction solution to ethanol is preferably 1: 10 to 20, and more preferably 1: 10 to 15. The invention has no special limitation on the suction filtration and drying, and can obtain a dry crude product.
After the crude product is obtained, the invention preferably redissolves the crude product. In the present invention, the redissolution is preferably performed by mixing the crude product with chloroform. In the present invention, the feed ratio of the crude product to chloroform is preferably 1: 10-20 g/mL, more preferably 1: 12-18 g/mL.
After the redissolution, the invention preferably mixes the redissolved solution with ethanol for precipitation to obtain a precipitate. In the present invention, the volume ratio of the solution to ethanol is preferably 1: 5-10, more preferably 1: 7 to 8.
After the precipitate is obtained, the present invention preferably washes the precipitate. In the present invention, the washing is preferably performed by washing the precipitate with ethanol. In the present invention, the number of washing is preferably 2 to 3.
After washing, the present invention preferably further comprises suction drying, which is not particularly required by the present invention and is well known to those skilled in the art.
The invention also provides the application of the polyimide prepared by the preparation method in the technical scheme or the polyimide prepared by the preparation method in the technical scheme in gas separation. In the invention, the application mode is preferably that polyimide is prepared to obtain a polyimide film, and the polyimide film is applied to gas separation.
In the invention, the preparation method of the polyimide film comprises the following steps: and mixing the polyimide and an organic solvent VI to form a film, thus obtaining the polyimide film.
In the invention, the organic solvent VI is preferably one or more of dichloromethane, chloroform, tetrahydrofuran and acetone; when the organic solvent vi is two or more of the above specific choices, the specific material ratio in the present invention is not particularly limited, and the organic solvent vi may be mixed at any ratio. In a specific embodiment of the present invention, the organic solvent vi is chloroform.
In the invention, the mass ratio of the polyimide to the organic solvent VI is preferably 0.02-0.053: 1, more preferably 0.025 to 0.05: 1, more preferably 0.031-0.04: 1.
in the present invention, the film forming process preferably includes: and mixing the polyimide and the organic solvent VI, and pouring the mixture into a mold to volatilize the solvent to obtain the polyimide film. In the invention, the volatilization temperature is preferably 20-30 ℃, more preferably 22-28 ℃, and more preferably 25-26 ℃.
In the present invention, the thickness of the polyimide film obtained is preferably 30 to 60 μm, more preferably 35 to 55 μm, and still more preferably 40 to 50 μm. In a particular embodiment of the invention, the mould is preferably a glass cylindrical mould, the diameter of the mould preferably being 8 cm.
In order to further illustrate the present invention, the spirobisbenzoxazole diamine and the preparation method and application thereof, the polyimide and the preparation method and application thereof provided by the present invention are described in detail below with reference to the drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Reacting 500g of bisphenol A with 50mL of methanesulfonic acid at 135 ℃ for 4.5h, after the reaction is determined by TLC detection, putting the reaction system into ice water, adding ethanol with the same volume for recrystallization, filtering and drying to obtain 315g of 3,3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1 '-spirobi [ indene ] -6,6' -diol, wherein the yield is 47%;
150g of 3,3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1 '-spirobi [ indene ] -6,6' -diol, 186g of benzyl chloride, 203g of potassium carbonate and 1500mL of acetonitrile are added into a reflux device, a first condensation reaction is carried out at a temperature of 80 ℃, and TLC detection determines that the reaction is finished. Adding the reacted solution into water, sequentially pulping, filtering and extracting with dichloromethane, carrying out rotary evaporation on the extracted material, then adding ethanol, filtering and drying to obtain 135g of 6,6 '-bis (benzyloxy) -3,3,3',3 '-tetramethyl-2, 2',3,3 '-tetrahydro-1, 1' -spirobi [ indene ] with the yield of 58%;
mixing 200mL of acetic acid, 127mL of concentrated nitric acid (the concentration is 14.5mol/L) and 80mL of concentrated sulfuric acid (the concentration is 18.4mol/L), and cooling to room temperature to obtain a mixed acid solution; adding 60g of 6,6 '-bis (benzyloxy) -3,3,3',3 '-tetramethyl-2, 2',3,3 '-tetrahydro-1, 1' -spirobi [ indene ] into 400mL of acetic acid to obtain an acetic acid solution; adding the acetic acid solution into the mixed acid solution, carrying out nitration reaction at 25 ℃, and determining the reaction completion by TLC detection. Adding the solution obtained after the reaction into water, and sequentially carrying out washing, dichloromethane extraction, rotary evaporation, petroleum ether precipitation, suction filtration and drying to obtain 55g of 6,6' -bis (benzyloxy) -3,3,3',3' -tetramethyl-5, 5' -dinitro-2, 2',3,3' -tetrahydro-1, 1' -spirobi [ indene ] with the yield of 79%;
55g of 6,6' -bis (benzyloxy) -3,3,3',3' -tetramethyl-5, 5' -dinitro-2, 2',3,3' -tetrahydro-1, 1' -spirobi [ indene ], 550mL of ethanol and 5.5g of palladium-carbon are added into an autoclave, nitrogen is firstly used for replacement for three times, then hydrogen is filled until the pressure is 1.0MPa, the temperature and the pressure are kept for 5h at 60 ℃, and TLC detection determines that the reaction is finished. Filtering the solution obtained after the reaction to recover the catalyst, and sequentially cooling, crystallizing, filtering and drying the obtained filtrate to obtain 32g of 5,5' -diamino-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1' -spirobi [ indene ] -6,6' -diol with the yield of 98%;
40g of 4-nitrobenzoic acid, 200mL of thionyl chloride and 10mLN, N-dimethylformamide are mixed, and the acylation and chlorination reactions are carried out at 80 ℃, and the completion of the reactions is determined by TLC detection. Performing rotary evaporation on the solution obtained after the reaction to remove redundant thionyl chloride, and repeatedly precipitating and rotary evaporating the material obtained after the rotary evaporation by using tetrahydrofuran to obtain a tetrahydrofuran (100mL) solution of 4-nitrobenzoyl chloride (40g), wherein the yield is 90%;
30g of 5,5' -diamino-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1' -spirobi [ indene ] -6,6' -diol, 200mL of tetrahydrofuran and 20g of triethylamine are mixed, the mixture is cooled to 10 ℃, a tetrahydrofuran (100mL) solution of 4-nitrobenzoyl chloride (39g) is added dropwise at the speed of 2.0mL/min, a second condensation reaction is carried out at the temperature of 25 ℃, and after 12 hours of reaction, TLC detection determines that the reaction is finished. Adding water into the solution obtained by the reaction, and performing vacuum filtration to obtain a crude product; adding dichloromethane into the crude product, and sequentially pulping, filtering and drying to obtain 26g N, N '- (6,6' -dihydroxy-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1 '-spirobi [ indene ] -5,5' -diyl) bis (4-nitrobenzamide) with the yield of 47%;
24g N, N '- (6,6' -dihydroxy-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1 '-spirobi [ indene ] -5,5' -diyl) bis (4-nitrobenzamide), 16g of p-toluenesulfonic acid and 240mL of sulfolane are added into a reflux condenser, and reacted for 3 hours at the temperature of 170 ℃, and TLC detection confirms that the reaction is completed. Adding water into the solution obtained by the reaction, and obtaining a crude product through reduced pressure suction filtration; recrystallizing the obtained crude product in a dioxane/water (volume ratio of 5: 1) system, filtering and drying to obtain 17g of 5,5,5',5' -tetramethyl-2, 2 '-bis (4-nitrophenyl) -5,5',6,6 '-tetrahydro-7, 7' -spirobis [ indenooxazole ], wherein the yield is 76%;
15g of 5,5,5',5' -tetramethyl-2, 2 '-bis (4-nitrophenyl) -5,5',6,6 '-tetrahydro-7, 7' -spiro [ indenooxazole ], 150mL of ethanol and 1.5g of palladium-carbon are added into an autoclave, the autoclave is replaced by nitrogen for three times, then hydrogen is filled until the pressure is 1.0MPa, the temperature and the pressure are kept at 60 ℃ for 5h, and the reaction is determined to be completed by TLC detection. Filtering the solution obtained after the reaction to recover the catalyst, and sequentially cooling, crystallizing, filtering and drying the obtained filtrate to obtain 12.5g of 4,4' - (5,5,5',5' -tetramethyl-5, 5',6,6' -tetrahydro-7, 7' -spirobi [ indenooxazole ] -2,2' -diyl) diphenylamine (formula I-6), wherein the yield is 93%;
10.00g of 4,4' - (5,5,5',5' -tetramethyl-5, 5',6,6' -tetrahydro-7, 7' -spirobis [ indenooxazole ] -2,2' -diyl) diphenylamine, 8.22 g of hexafluoro dianhydride and 72.88g of m-cresol were heated to 100 ℃ under nitrogen protection and stirred at 250r/min for 1 hour; after complete dissolution, 1.09g of isoquinoline is added, the mixture is heated to 180 ℃, and the reaction is carried out for 4 hours at the rotating speed of 250 r/min; after the reaction is finished, pouring the solution obtained after the reaction into 1L of ethanol, and performing suction filtration and drying to obtain a crude product; dissolving the crude product in 500mL of chloroform, re-precipitating in 1L of ethanol after dissolving, and performing suction filtration to obtain a precipitate; the precipitate was washed with ethanol 2 to 3 times, and dried to obtain 16.8g of polyimide (formula II-6) with a yield of 92.2%.
Example 2
5,5' -diamino-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1' -spirobi [ indene ] -6,6' -diol prepared by the method of example 1;
39g of 2-methyl-4-nitrobenzoic acid, 200mL of thionyl chloride and 10mL of N, N-dimethylformamide are mixed, and then the acylation chlorination reaction is carried out at 80 ℃, and the reaction is determined to be completed by TLC detection. Performing rotary evaporation on the solution obtained after the reaction to remove redundant thionyl chloride, and repeatedly precipitating and rotary evaporating the material obtained after the rotary evaporation by using tetrahydrofuran to obtain 39g of 2-methyl-4-nitrobenzoyl chloride, wherein the yield is 90%;
mixing 30g of 5,5' -diamino-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1' -spirobi [ indene ] -6,6' -diol, 300mL of tetrahydrofuran and 20g of triethylamine, cooling to 10 +/-1 ℃, dropwise adding a tetrahydrofuran (100mL) solution of 2-methyl-4-nitrobenzoyl chloride (39g), completing dropwise adding within 0.5-1 h, carrying out a second condensation reaction at the temperature of 25 ℃, and after reacting for 12h, determining that the reaction is completed by TLC detection. Adding water into the solution obtained by the reaction, and performing vacuum filtration to obtain a crude product; adding dichloromethane into the crude product, and sequentially pulping, filtering and drying to obtain 30g N, N '- (6,6' -dihydroxy-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1 '-spirobi [ indene ] -5,5' -diyl) bis (2-methyl-4-nitrobenzamide) with the yield of 47%;
30g N, N '- (6,6' -dihydroxy-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1 '-spirobi [ indene ] -5,5' -diyl) bis (2-methyl-4-nitrobenzamide), 19g of p-toluenesulfonic acid and 300mL of sulfolane were added to a reflux condenser, reacted at 170 ℃ for 3 hours, and the reaction was determined to be complete by TLC detection. Adding water into the solution obtained by the reaction, and obtaining a crude product through reduced pressure suction filtration; recrystallizing the obtained crude product in a dioxane/water (volume ratio of 5: 1) system, filtering and drying to obtain 22g of 5,5,5',5' -tetramethyl-2, 2 '-bis (2-methyl-4-nitrophenyl) -5,5',6,6 '-tetrahydro-7, 7' -spirobis [ indenooxazole ], wherein the yield is 77.9%;
adding 21g of 5,5,5',5' -tetramethyl-2, 2 '-bis (2-methyl-4-nitrophenyl) -5,5',6,6 '-tetrahydro-7, 7' -spirobis [ indenooxazole ], 210mL of ethanol and 2.1g of palladium-carbon into an autoclave, replacing three times with nitrogen, then filling hydrogen to the pressure of 0.9-1.0 MPa, preserving heat and maintaining pressure for 5 hours at the temperature of 50-60 ℃, and determining that the reaction is finished by TLC detection. Filtering the solution obtained after the reaction to recover the catalyst, and sequentially cooling, crystallizing, filtering and drying the obtained filtrate to obtain 18g of 4,4' - (5,5,5',5' -tetramethyl-5, 5',6,6' -tetrahydro-7, 7' -spirobi [ indenooxazole ] -2,2' -diyl) bis (3-methylaniline) (formula I-7) with the yield of 94.1%;
10.00g of 4,4' - (5,5,5',5' -tetramethyl-5, 5',6,6' -tetrahydro-7, 7' -spirobis [ indenooxazole ] -2,2' -diyl) bis (3-methylaniline), 7.81g of hexafluorodianhydride and 71.24g of m-cresol were heated to 100 ℃ under nitrogen and stirred at 250r/min for 1 hour; after complete dissolution, 1.07g of isoquinoline is added, the mixture is heated to 180 ℃, and the reaction is carried out for 4 hours at the rotating speed of 250 r/min; after the reaction is finished, pouring the solution obtained after the reaction into 1L of ethanol, and performing suction filtration and drying to obtain a crude product; dissolving the crude product in 500mL of chloroform, re-precipitating in 1L of ethanol after dissolving, and performing suction filtration to obtain a precipitate; washing the precipitate with ethanol for 2-3 times, and drying to obtain 15.5g of polyimide (formula II-7), wherein the yield is 87%;
example 3
5,5' -diamino-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1' -spirobi [ indene ] -6,6' -diol prepared by the method of example 1;
39g of 3-methyl-4-nitrobenzoic acid, 200mL of thionyl chloride and 10mL of N, N-dimethylformamide are mixed, and then the acylation chlorination reaction is carried out at 80 ℃, and the reaction is determined to be completed by TLC detection. Performing rotary evaporation on the solution obtained after the reaction to remove redundant thionyl chloride, and repeatedly precipitating and rotary evaporating the material obtained after the rotary evaporation by using tetrahydrofuran to obtain 39g of 3-methyl-4-nitrobenzoyl chloride, wherein the yield is 91%;
30g of 5,5' -diamino-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1' -spirobi [ indene ] -6,6' -diol, 300mL of tetrahydrofuran and 20g of triethylamine are mixed, the mixture is cooled to 10 ℃, a tetrahydrofuran (100mL) solution of 3-methyl-4-nitrobenzoyl chloride (39g) is added dropwise, the dropwise addition is completed within 1h, a second condensation reaction is carried out at the temperature of 25 ℃, and after the reaction is carried out for 12h, the reaction is determined to be completed by TLC detection. Adding water into the solution obtained by the reaction, and performing vacuum filtration to obtain a crude product; adding dichloromethane into the crude product, and sequentially pulping, filtering and drying to obtain 30g N, N '- (6,6' -dihydroxy-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1 '-spirobi [ indene ] -5,5' -diyl) bis (3-methyl-4-nitrobenzamide) with the yield of 47%;
30g N, N '- (6,6' -dihydroxy-3, 3,3',3' -tetramethyl-2, 2',3,3' -tetrahydro-1, 1 '-spirobi [ indene ] -5,5' -diyl) bis (3-methyl-4-nitrobenzamide), 19g of p-toluenesulfonic acid and 300mL of sulfolane were added to a reflux condenser, reacted at 170 ℃ for 3 hours, and the reaction was determined to be complete by TLC detection. Adding water into the solution obtained by the reaction, and obtaining a crude product through reduced pressure suction filtration; recrystallizing the obtained crude product in a dioxane/water (volume ratio of 5: 1) system, filtering and drying to obtain 22g of 5,5,5',5' -tetramethyl-2, 2 '-bis (3-methyl-4-nitrophenyl) -5,5',6,6 '-tetrahydro-7, 7' -spirobis [ indenooxazole ], wherein the yield is 78.1%;
21g of 5,5,5',5' -tetramethyl-2, 2 '-bis (3-methyl-4-nitrophenyl) -5,5',6,6 '-tetrahydro-7, 7' -spirobis [ indenooxazole ], 210mL of ethanol and 2.1g of palladium-carbon are added into an autoclave, the autoclave is replaced by nitrogen for three times, then hydrogen is filled until the pressure is 1.0MPa, the temperature and the pressure are kept for 5 hours at 60 ℃, and the reaction is determined to be completed by TLC detection. Filtering the solution obtained after the reaction to recover the catalyst, and sequentially cooling, crystallizing, filtering and drying the obtained filtrate to obtain 18g of 4,4' - (5,5,5',5' -tetramethyl-5, 5',6,6' -tetrahydro-7, 7' -spirobi [ indenooxazole ] -2,2' -diyl) bis (2-methylaniline) (formula I-10) with the yield of 94.0%;
10.00g of 4,4' - (5,5,5',5' -tetramethyl-5, 5',6,6' -tetrahydro-7, 7' -spirobis [ indenooxazole ] -2,2' -diyl) bis (2-methylaniline), 7.81g of hexafluorodianhydride and 71.24g of m-cresol were heated to 100 ℃ under nitrogen and stirred at 250r/min for 1 hour; after complete dissolution, 1.07g of isoquinoline is added, the mixture is heated to 180 ℃, and the reaction is carried out for 4 hours at the rotating speed of 250 r/min; after the reaction is finished, pouring the solution obtained after the reaction into 1L of ethanol, and performing suction filtration and drying to obtain a crude product; dissolving the crude product in 500mL of chloroform, re-precipitating in 1L of ethanol after dissolving, and performing suction filtration to obtain a precipitate; the precipitate was washed with ethanol 2 to 3 times and dried to obtain 16.1g of polyimide (formula II-8) with a yield of 90.4%.
Application example
The polyimide obtained in example 1 to 3 was used as a raw material to prepare a polyimide film:
0.15g of polyimide was dissolved in 4.85g of chloroform, and after completely dissolving, the solution was cast on a glass cylindrical mold, and the organic solvent was evaporated at room temperature to obtain a polyimide film having a thickness of 44 μm.
Performance testing
Test example 1
The nuclear magnetic hydrogen spectrum detection is performed on the spirobisbenzoxazole diamines obtained in examples 1 to 3, and the test results are shown in fig. 1.
Test example 2
Relative molecular weight (M) of the polyimides obtained in examples 1 to 3nAnd Mw) And molecular weight (PDI) distribution test, test method: by gel permeation chromatography with polystyrene as external standard and THF as eluent; the test results are shown in table 1.
TABLE 1 results of molecular weight test of polyimides obtained in examples 1 to 3
Mn/×104gmol-1 Mw/×104gmol-1 PDI
Example 1 3.1 5.1 1.65
Example 2 3.4 5.6 1.65
Example 3 3.3 5.8 1.76
As can be seen from Table 1, the polyimide obtained by the present invention has a higher molecular weight and a lower molecular weight distribution.
Test example 3
The polyimide obtained in examples 1 to 3 was subjected to a solubility test, and the test results are shown in Table 2.
TABLE 2 polyimide solubility test results obtained in examples 1 to 3
Figure BDA0003138726900000271
Note: + represents a solubility of 10mg/mL or more; + represents a solubility of not less than 5 mg/mL; NMP: n-methyl pyrrolidone; DMAc: n, N-dimethylacetamide; DMF: n, N-dimethylformamide; DMSO, DMSO: dimethyl sulfoxide; THF: tetrahydrofuran; CH (CH)2Cl2Dichloromethane; CHCl3: chloroform; m-cresol is m-cresol.
As can be seen from Table 2, the polyimide obtained by the present invention has good solubility in both high boiling point solvents and low boiling point solvents, ensuring good subsequent processability.
Test example 4
The polyimide film prepared by using the polyimide obtained in examples 1 to 3 as a raw material was subjected to infrared spectroscopy, and the test results are shown in fig. 2. As can be seen from FIG. 2, the polyimide films obtained in examples 1 to 3 were 1770cm in thickness-1(symmetrical stretching peak of imide carbonyl group), 1700cm-1(asymmetric stretching peak of imide carbonyl group), 2800-3000 cm-1(-CH2-) respectively shows characteristic absorption peaks of methylene on typical imide and indane, which shows that the spiro-bis-benzoxazolyl polyimide film with the structure shown in the invention is successfully prepared.
Test example 5
The polyimide film is prepared by adopting the polyimide obtained in the embodiment 1-3 as a raw material, and the polyimide film is subjected to a thermal stability test, wherein the test method comprises the following steps: the temperature is raised from room temperature to 800 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere by adopting a TGA550 thermogravimetric analyzer. The test results are shown in fig. 3 and table 3.
Test example 6
The polyimide film is prepared by adopting the polyimide obtained in the embodiment 1-3 as a raw material, and the polyimide film is subjected to a glass transition temperature test, wherein the test method comprises the following steps: the obtained polymer film was measured by DSC250 differential scanning calorimeter, and the temperature was raised from 40 ℃ to 400 ℃ at a temperature rising rate of 10 ℃/min under a nitrogen atmosphere, and the measurement results are shown in FIG. 4 and Table 3.
Test example 7
The polyimide film is prepared by adopting the polyimide obtained in the embodiment 1-3 as a raw material, and the polyimide film is subjected to a mechanical tensile test, wherein the test method comprises the following steps: a5 x 1cm rectangular film sample was prepared with a draw rate of 5 mm/min. The test results are shown in fig. 5 and table 3.
TABLE 3 results of thermogravimetric tests of polyimide films obtained in examples 1 to 3
Tg/℃ Td5％/℃ Rw/％ σ/MPa E/GPa ε/％
Example 1 >400 500 58 91 2.1 10.4
Example 2 >400 497 61 95 2.2 9.5
Example 3 >400 505 60 100 2.2 8.6
Note: tg denotes the glass transition temperature, Td5％Denotes the 5% thermogravimetric temperature, RwThe heat retention at 800 ℃ is shown, σ is the tensile strength, E is the tensile modulus, and ε is the elongation at break.
As can be seen by combining FIGS. 3 to 5 and Table 3, the polyimide film prepared by the present invention has a high glass transition temperature, i.e., no significant glass transition step is detected within 400 ℃. Under the nitrogen atmosphere, the initial decomposition temperature is more than 450 ℃, and the 5% thermal weight loss temperature is near 500 ℃; the heat retention rate at 800 ℃ was close to 60%. Meanwhile, the tensile strength of the polyimide film provided by the invention is 91-100 MPa, the tensile modulus is 2.1-2.2 GPa, and the elongation at break is 8.6-10.4%, so that the actual production requirement can be met.
Test example 7
The polyimide film prepared by using the polyimide obtained in the embodiment 1-3 as a raw material is subjected to a gas permeability test, and the test method comprises the following steps: testing CO at 35 deg.C and 1atm upstream pressure by variable pressure infiltration2，O2，N2And CH4The desired selectivity for a pair of gases is determined by the ratio of the respective permeabilities. The test results are shown in table 4.
TABLE 4 gas permeability test results of polyimide films obtained in examples 1 to 3
Figure BDA0003138726900000291
As can be seen from Table 4, the polyimide film prepared by the present invention has high gas permeability and excellent gas selectivity. Compared with the gas separation membrane of Matrimid5218 polyimide sold in the market, the gas permeability is obviously improved, and good gas selectivity is ensured.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.

Claims (10)

1. A spirobisbenzoxazole diamine having the structure shown in formula I:
Figure FDA0003138726890000011
wherein R is-H, -CH3or-OH.
2. A spirobisbenzoxazole diamine as claimed in claim 1, characterized in that said spirobisbenzoxazole diamine is a compound having a structure represented by formula I-1, formula I-2, formula I-3, formula I-4 or formula I-5;
Figure FDA0003138726890000012
。
3. a spirobisbenzoxazole diamine as claimed in claim 1 or 2, characterized in that said spirobisbenzoxazole diamine is a compound having a structure represented by formula i-6, formula i-7, formula i-8, formula i-9 or formula i-10;
Figure FDA0003138726890000021
4. a process for the preparation of a spirobisbenzoxazole diamine as claimed in any one of claims 1 to 3, characterized in that it comprises the following steps:
carrying out rearrangement reaction on bisphenol A and methanesulfonic acid to obtain an intermediate with a structure shown in a formula a;
carrying out a first condensation reaction on the intermediate with the structure shown in the formula a and benzyl chloride to obtain an intermediate with the structure shown in the formula b;
carrying out nitration reaction on the intermediate with the structure shown in the formula b to obtain an intermediate with the structure shown in the formula c;
carrying out a first catalytic hydrogenation reaction on the intermediate with the structure shown in the formula c to obtain an intermediate with the structure shown in the formula d;
carrying out acyl chlorination on a monomer with a structure shown as a formula e to obtain an intermediate with a structure shown as a formula f;
carrying out a second condensation reaction on the intermediate with the structure shown in the formula f and the intermediate with the structure shown in the formula d to obtain an intermediate with the structure shown in the formula g;
carrying out ring closing reaction on the intermediate with the structure shown in the formula g to obtain an intermediate with the structure shown in the formula h;
carrying out a second catalytic hydrogenation reaction on the intermediate with the structure shown in the formula h to obtain the spirobisbenzoxazole diamine;
Figure FDA0003138726890000031
5. use of the spirobisbenzoxazole diamine according to any one of claims 1 to 3 or the spirobisbenzoxazole diamine obtained by the process according to claim 4 for the preparation of polyimides.
6. A polyimide having a structure represented by formula II:
Figure FDA0003138726890000032
r is-H, -CH3or-OH;
and n is 40-60.
7. The polyimide of claim 6, wherein the polyimide is a compound having a structure represented by formula ii-1, formula ii-2, formula ii-3, formula ii-4, or formula ii-5;
Figure FDA0003138726890000041
。
8. the polyimide according to claim 6 or 7, wherein the polyimide is a compound having a structure represented by formula ii-6, formula ii-7, or formula ii-8;
Figure FDA0003138726890000042
Figure FDA0003138726890000051
9. a process for producing a polyimide as claimed in any one of claims 6 to 8, which comprises the steps of:
performing polycondensation reaction on spiro-bis-benzoxazole diamine and hexafluoro-dianhydride to obtain the polyimide;
the spirobisbenzoxazole diamine is spirobisbenzoxazole diamine according to any one of claims 1 to 3 or spirobisbenzoxazole diamine prepared by the preparation method according to claim 4.
10. Use of the polyimide according to any one of claims 6 to 8 or the polyimide produced by the production method according to claim 9 for gas separation.
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