CN109535069B - Diamine monomer and preparation method thereof, and polyimide and preparation method thereof - Google Patents

Diamine monomer and preparation method thereof, and polyimide and preparation method thereof Download PDF

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CN109535069B
CN109535069B CN201811520199.5A CN201811520199A CN109535069B CN 109535069 B CN109535069 B CN 109535069B CN 201811520199 A CN201811520199 A CN 201811520199A CN 109535069 B CN109535069 B CN 109535069B
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diamine monomer
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trifluoromethyl
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陈春海
王书丽
王大明
周宏伟
赵晓刚
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Jilin University
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D213/73—Unsubstituted amino or imino radicals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
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    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties

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Abstract

The invention relates to the technical field of organic chemistry, in particular to a diamine monomer and a preparation method thereof, and polyimide and a preparation method thereof. The diamine monomer provided by the invention contains a spiro center (two rings share one atom), has a non-coplanar structure, increases the rigidity of a molecular chain, prevents a high-molecular main chain in polyimide prepared from the diamine monomer from freely rotating, and blocks effective accumulation among molecular chains, so that continuous micropores are formed in the polyimide, more cavities are formed, and the molecular structure is loose, so that the permeability, the solubility and the like of gas can be improved on the premise of keeping selectivity of a polyimide film prepared from the diamine monomer; in addition, the polyimide prepared from the diamine monomer provided by the invention has better solubility and light transmittance.

Description

Diamine monomer and preparation method thereof, and polyimide and preparation method thereof
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a diamine monomer and a preparation method thereof, and polyimide and a preparation method thereof.
Background
The gas membrane separation technology is a novel green separation technology, has the advantages of high separation efficiency, simple operation, low energy consumption, greenness, no pollution and the like, and is widely applied to the fields of medicine and food, biochemistry, energy environmental protection and the like. The high molecular polymer membrane has good separation performance, excellent mechanical property and physical and chemical properties, so that the high molecular polymer membrane becomes a common gas separation membrane material, and the gas separation membrane technology is an important component of numerous applications in the membrane separation technology and is a third generation gas separation technology after cryogenic separation and pressure swing adsorption. Compared with the traditional gas separation technology, the membrane separation has the advantages of low energy consumption, low investment, simple equipment and the likeO2/N2Separation, gas dehumidification, CO2Recovery, H2The separation and recovery and the like are all important applications.
Polyimide (PI) is a kind of high molecular polymer having an imide ring in its main chain, synthesized by Bogert and Renshaw in 1908, and developed by dupont in 1962, and then various PI products such as plastics, laminates, varnishes, adhesives, paints, and fiber impregnants were successively produced, and the polyimide film was applied to the research of gas separation membranes. With the continuous development and progress of social science and technology, people have higher and higher application standards of polyimide films in the field of gas membranes, and the key point of pursuit and attention is how to research a gas separation membrane with high separation efficiency and high mechanical performance. The main problems of the existing polyimide film are that the permeability of the polyimide film is low, and the solubility of the polyimide film is poor.
Disclosure of Invention
Aiming at the problems of the polyimide film, the diamine monomer is designed through a molecular structure, and the polyimide film obtained from the diamine monomer has the characteristics of high permeability and good solubility while ensuring good selectivity.
The invention provides a diamine monomer, which has a structure shown in a formula I:
Figure BDA0001903036760000011
r' is methyl or trifluoromethyl;
the R is selected from one of structures shown in a formula II;
Figure BDA0001903036760000021
preferably, the diamine monomer has a structure represented by formula III to formula VI:
Figure BDA0001903036760000022
the invention also provides a preparation method of the diamine monomer in the technical scheme,
when R' in the formula I is methyl, the preparation method of the diamine monomer comprises the following steps:
(1) carrying out microwave reaction on bisphenol A and methanesulfonic acid, discharging a microwave reaction product in an ice-water bath, and collecting a solid; heating and sublimating the solid to obtain a methyl diphenol compound;
(2) mixing the methyl diphenol compound obtained in the step (1), a catalyst and a solvent to obtain a phenol ionic liquid; carrying out substitution reaction on the phenol ionic liquid and a mononitro compound to obtain a dinitro compound; then, carrying out reduction reaction on the dinitro compound to obtain a diamine monomer with a structure R' shown in a formula I as methyl; the catalyst is potassium carbonate and/or cesium carbonate;
when R' in the formula I is trifluoromethyl, the preparation method of the diamine monomer comprises the following steps:
(a) heating bisphenol AF and trifluoroacetic acid for reaction, discharging the heated reaction product in an ice water bath, and obtaining a trifluoromethyl diphenol compound;
(b) mixing the trifluoromethyl diphenol compound obtained in the step (a), a catalyst and a solvent to obtain a phenol ionic liquid; carrying out substitution reaction on the phenol ionic liquid and a mononitro compound to obtain a dinitro compound; then, carrying out reduction reaction on the dinitro compound to obtain a diamine monomer with a structure R' shown in a formula I as trifluoromethyl; the catalyst is potassium carbonate and/or cesium carbonate.
Preferably, the molar ratio of the bisphenol A to the methanesulfonic acid in the step (1) is 1: 5-8.
Preferably, the frequency of the microwave reaction in the step (1) is 180-220 GHz, and the heating rate of the microwave reaction is 18-22 ℃/min.
Preferably, the molar ratio of the bisphenol AF to the trifluoroacetic acid in the step (a) is 1: 10-12.
Preferably, the heating reaction in the step (a) is carried out at the temperature of 180-220 ℃ for 15-20 h.
Preferably, the molar ratio of the phenolic ionic liquid to the mononitro compound in the step (2) or the step (b) is 1: 2-2.4; the mononitro compound comprises halogenated nitropyridine, halogenated methyl nitropyridine, halogenated nitroquinoline, halogenated methyl nitroquinoline, halogenated nitroisoquinoline or halogenated methyl nitroisoquinoline.
The invention also provides a preparation method of the polyimide, which comprises the following steps:
(i) under the protection of nitrogen, carrying out polycondensation reaction on a dianhydride monomer and a diamine monomer in a polar organic solvent to obtain a polyamic acid solution; the diamine monomer is the diamine monomer in the technical scheme or the diamine monomer prepared by the preparation method in the technical scheme;
(ii) and (ii) adding a catalyst and a dehydrating agent into the polyamic acid solution obtained in the step (i) to perform imidization reaction, thereby obtaining polyimide.
The invention also provides polyimide prepared by the method in the technical scheme.
The diamine monomer provided by the invention contains a 'spiro center' (two rings share one atom), has a non-coplanar structure, increases the rigidity of a molecular chain, prevents a high-molecular main chain in polyimide prepared from the diamine monomer from freely rotating, and blocks effective accumulation among the molecular chains, so that continuous micropores are formed in the polyimide, more cavities are formed, and the molecular structure is loose, so that the permeability of gas can be improved on the premise of keeping selectivity of a polyimide film prepared from the diamine monomer; in addition, the existence of flexible groups (ether bonds) in the diamine monomer increases the free volume and flexibility of a polymer molecular chain, so that a solvent is easy to permeate, the solubility of polyimide prepared from the diamine monomer is improved, and the optical transmittance of the polyimide is favorably improved. The results of the examples show that the polyimide prepared from the diamine monomer provided by the invention can be used in DMAC, DMF, NMP, DMSO, THF and CHCl3And 1,4-Dioxane are preferredThe solubility of the composition is good, and the visible light transmittance is good; in addition, the polyimide film prepared from the polyimide has the characteristic of high permeability while ensuring good selectivity in the field of gas separation.
Drawings
FIG. 1 is a nuclear magnetic diagram of a diamine monomer prepared in example 3;
FIG. 2 is a nuclear magnetic diagram of a diamine monomer prepared in example 4;
FIG. 3 is an IR spectrum of a polyimide prepared in examples 9 to 14;
FIG. 4 is a DSC chart of the polyimide films prepared in examples 9 to 14;
FIG. 5 is a spectrum of a light transmittance test of polyimides prepared in examples 9 to 14;
FIG. 6 is a graph showing the thermogravimetric curves of the polyimide films prepared in examples 9 to 14;
FIG. 7 shows polyimide films O prepared in examples 9 to 142/N2Robeson's selectivity curve of (a);
FIG. 8 shows polyimide films CO prepared in examples 9 to 142/CH4Robeson's selectivity curve of (a).
Detailed Description
The invention provides a diamine monomer, which has a structure shown in a formula I:
Figure BDA0001903036760000051
r' is methyl or trifluoromethyl;
the R is selected from one of structures of a formula II;
Figure BDA0001903036760000052
in the present invention, the diamine monomer preferably has a structure represented by formula III to formula VI:
Figure BDA0001903036760000053
Figure BDA0001903036760000061
the invention provides a preparation method of a diamine monomer in the technical scheme, and in the invention, when R' in the formula I is methyl, the preparation method of the diamine monomer comprises the following steps:
(1) carrying out microwave reaction on bisphenol A and methanesulfonic acid, discharging a microwave reaction product in an ice-water bath, and collecting a solid; heating and sublimating the solid to obtain a methyl diphenol compound;
(2) mixing the methyl diphenol compound obtained in the step (1), a catalyst and a solvent to obtain a phenolic ionic liquid; carrying out substitution reaction on the phenol ionic liquid and a mononitro compound to obtain a dinitro compound; then, carrying out reduction reaction on the dinitro compound to obtain a diamine monomer with a structure R' shown in a formula I as methyl; the catalyst is potassium carbonate and/or cesium carbonate.
The bisphenol A and the methanesulfonic acid are subjected to microwave reaction, the microwave reaction product is discharged into an ice-water bath, and the solid is collected; heating and sublimating the solid to obtain the methyl diphenol compound.
In the present invention, the process for preparing the methyl diphenol compound from bisphenol A and methanesulfonic acid is represented by formula VII:
Figure BDA0001903036760000062
the invention carries out microwave reaction on bisphenol A and methanesulfonic acid to obtain a microwave reaction product. In the present invention, the molar ratio of bisphenol a to methanesulfonic acid is preferably 1:5 to 8, and more preferably 1:6 to 7. In the invention, the frequency of the microwave reaction is preferably 180-220 GHz, more preferably 200GHz, and the heating rate of the microwave reaction is preferably 18-22 ℃/min, more preferably 20 ℃/min. In the present invention, the microwave reaction is preferably carried out under the protection of nitrogen. In the present invention, it is preferable to stop the microwave reaction after the disappearance of the starting material spot is detected by TLC.
After the microwave reaction product is obtained, the microwave reaction product is discharged into an ice water bath, and preferably subjected to solid-liquid separation and drying to obtain a solid. In the present invention, the solid-liquid separation method is preferably suction filtration, and in the present invention, it is preferable that the solid obtained by the solid-liquid separation is dried to obtain a solid.
After obtaining the solid, the invention heats and sublimes the solid, and preferably collects the sublimed product to obtain the methyl diphenol compound. In the invention, the heating sublimation temperature is preferably 155-165 ℃, and the purity of the methyl diphenol compound is preferably improved by heating and sublimating the solid.
After the methyl diphenol compound is obtained, the methyl diphenol compound, a catalyst and a solvent are mixed to obtain the phenol ionic liquid; carrying out substitution reaction on the phenol ionic liquid and a mononitro compound to obtain a dinitro compound; then, the dinitro compound is subjected to reduction reaction to obtain the diamine monomer with the structure R' shown in the formula I as methyl.
In the invention, the preparation principle of the diamine monomer with the structure R' as methyl as shown in formula I is shown in formula VIII, and the mononitro compound 2-chloro-5-nitropyridine is taken as an example:
Figure BDA0001903036760000071
according to the invention, a methyl diphenol compound, a catalyst and a solvent are mixed to obtain the phenolic ionic liquid. In the present invention, the catalyst is potassium carbonate and/or cesium carbonate; the solvent preferably comprises trichloroethane. In the invention, the molar ratio of the methyl diphenol compound to the catalyst is preferably 1: 2-2.4, and more preferably 1: 2.1-2.3; the dosage ratio of the methyl diphenol compound to the solvent is preferably 1g: 2.7-3.3 mL, and more preferably 1g: 2.8-3.2 mL. In the invention, the mixing is preferably carried out under an ultrasonic treatment piece, and the frequency of the ultrasonic treatment is preferably 18-22 KHz, and is further preferably 20 KHz; the time of ultrasonic treatment is preferably 30-35 min.
After the phenol ionic liquid is obtained, the phenol ionic liquid and the mononitro compound are subjected to substitution reaction to obtain the dinitro compound.
In the present invention, the mononitro compound preferably includes a halogenated nitropyridine, a halogenated methylnitropyridine, a halogenated nitroquinoline, a halogenated methylnitroquinoline, a halogenated nitroisoquinoline, or a halogenated methylnitroisoquinoline; the molar ratio of the phenolic ionic liquid to the mononitro compound is preferably 1: 2-2.4, and more preferably 1: 2.1-2.3. In the invention, the substitution reaction is preferably carried out in an organic solvent, the organic solvent preferably comprises N, N-dimethylformamide, and the solid content of the substitution reaction system is preferably 15-20%. In the invention, the temperature of the substitution reaction is preferably 75-85 ℃, and more preferably 80 ℃; in the present invention, it is preferable to stop the substitution reaction after the disappearance of the starting material spot is detected by TLC.
The invention preferably discharges the substitution reaction product into sodium chloride solution with the mass fraction of 5%, solid-liquid separation and drying are carried out to obtain the dinitro compound crude product, the dinitro compound crude product is dissolved into N, N-dimethylformamide, the system is heated to the reflux temperature, deionized water is added, when the system is just separated out and is not dissolved, heating is stopped, cooling and suction filtration are carried out to obtain the dinitro compound. In the invention, the dosage ratio of the dinitro compound crude product to N, N-dimethylformamide is preferably 1g: 2-3 mL; the dosage ratio of the dinitro compound crude product to the deionized water is preferably 1g: 1-2 mL.
After obtaining the dinitro compound, the invention performs reduction reaction on the dinitro compound to obtain the diamine monomer with the structure R' as methyl as shown in the formula I.
In the present invention, the reduction reaction is preferably carried out in a 1,4-dioxane or absolute ethanol solvent; the solid content of the dinitro compound in the reaction system is preferably 15% to 20%. In the invention, the reduction reaction is preferably carried out in the presence of a catalyst, the catalyst preferably comprises caustic soda, and the mass ratio of the dinitro compound to the catalyst is preferably 1: 0.1-0.5.
According to the invention, preferably, a dinitro compound and a catalyst are heated in a solvent to reflux, then reducing agents of sodium arsenite and hydrazine hydrate are added into a reaction system, the reflux reaction is continued for 15-24 hours, and the reduction reaction product is obtained after TLC detection until the raw material point disappears. In the invention, the molar ratio of the dinitro compound to the sodium arsenite is preferably 1: 5-8; the molar ratio of the dinitro compound to the hydrazine hydrate is 1: 15-20.
Filtering the reduction reaction product while the reduction reaction product is hot to remove sodium arsenite, collecting filtrate, and concentrating the filtrate under reduced pressure to obtain a crude diamine monomer product; heating the diamine monomer crude product in a good solvent 1,4-dioxane until reflux, adding a poor solvent deionized water into a reflux system until precipitation and insolubilization are just carried out, stopping reflux, and carrying out solid-liquid separation and vacuum drying to obtain the diamine monomer with the structure of formula I, wherein R' is methyl.
In the present invention, when R' in the formula I is trifluoromethyl, the preparation method of the diamine monomer comprises the following steps:
(a) heating bisphenol AF and trifluoroacetic acid for reaction, discharging the heated reaction product in an ice water bath, and obtaining a trifluoromethyl diphenol compound;
(b) mixing the trifluoromethyl diphenol compound obtained in the step (a), a catalyst and a solvent to obtain a phenol ionic liquid; carrying out substitution reaction on the phenol ionic liquid and a mononitro compound to obtain a dinitro compound; then, carrying out reduction reaction on the dinitro compound to obtain a diamine monomer with a structure R' shown in a formula I as trifluoromethyl; the catalyst is potassium carbonate and/or cesium carbonate.
The invention carries out heating reaction on bisphenol AF and trifluoroacetic acid, discharges the heated reaction product into an ice water bath, and preferably obtains the trifluoromethyl diphenol compound through solid-liquid separation and drying.
In the present invention, the preparation method of the trifluoromethyl diphenol compound is shown as formula IX:
Figure BDA0001903036760000091
the bisphenol AF and trifluoroacetic acid are heated to react to obtain a heated reaction product. In the invention, the molar ratio of the bisphenol AF to the trifluoroacetic acid is preferably 1: 10-12; the temperature of the heating reaction is preferably 180-220 ℃, and further preferably 200 ℃; the heating reaction time is preferably 14-16 h, and more preferably 15 h.
After obtaining the heating reaction product, discharging the heating reaction product into an ice water bath, preferably carrying out solid-liquid separation and drying to obtain the trifluoromethyl diphenol compound. In the present invention, the solid-liquid separation is preferably performed by suction filtration, and in the present invention, the solid obtained by the solid-liquid separation is preferably dried to obtain the trifluoromethylbiphenol compound.
After obtaining the trifluoromethyl diphenol compound, mixing the trifluoromethyl diphenol compound, a catalyst and a solvent, preferably performing ultrasonic treatment to obtain a phenol ionic liquid; carrying out substitution reaction on the phenol ionic liquid and a mononitro compound to obtain a dinitro compound; then, the dinitro compound is subjected to reduction reaction to obtain the diamine monomer with the structure R' shown in the formula I as trifluoromethyl.
In the invention, the preparation method of the diamine monomer with the structure R' shown in the formula I as trifluoromethyl is shown in the formula X, and the mononitro compound is 2-bromo-5-nitroquinoline as an example:
Figure BDA0001903036760000092
according to the invention, the phenol ionic liquid is obtained by mixing the trifluoromethyl diphenol compound, the catalyst and the solvent, preferably by ultrasonic treatment. In the invention, the catalyst is potassium carbonate and/or cesium carbonate, and the molar ratio of the methyl diphenol compound to the catalyst is preferably 1: 2-2.4, and more preferably 1: 2.1-2.3. In the present invention, the solvent preferably includes trichloroethane, and the use amount ratio of the trifluoromethyl diphenol compound to the solvent is preferably 1g: 2.7-3.3 mL, and more preferably 1g: 2.8-3.2 mL. In the invention, the frequency of ultrasonic treatment is preferably 18-22 KHz, and is further preferably 20 KHz; the time of ultrasonic treatment is preferably 30-35 min.
After the phenol ionic liquid is obtained, the phenol ionic liquid and the mononitro compound are subjected to substitution reaction to obtain the dinitro compound.
In the present invention, the mononitro compound preferably includes a halogenated nitropyridine, a halogenated methylnitropyridine, a halogenated nitroquinoline, a halogenated methylnitroquinoline, a halogenated nitroisoquinoline, or a halogenated methylnitroisoquinoline; the molar ratio of the phenolic ionic liquid to the mononitro compound is preferably 1: 2-2.4, and more preferably 1: 2.1-2.3. In the invention, the solid content of the substitution reaction system is preferably 15-20%. In the invention, the temperature of the substitution reaction is preferably 75-85 ℃, and more preferably 80 ℃; in the present invention, it is preferable to stop the substitution reaction after the disappearance of the starting material spot is detected by TLC.
The invention preferably discharges the substitution reaction product into sodium chloride solution with the mass fraction of 5%, solid-liquid separation and drying are carried out to obtain the dinitro compound crude product, the dinitro compound crude product is dissolved into N, N-dimethylformamide, the system is heated to the reflux temperature, deionized water is added, when the system is just separated out and is not dissolved, heating is stopped, and the dinitro compound is obtained by cooling and suction filtration. In the invention, the dosage ratio of the dinitro compound crude product to the N, N-dimethylformamide is preferably 1: 2-3; the dosage ratio of the dinitro compound crude product to the deionized water is preferably 1: 1-2.
After obtaining the dinitro compound, the invention performs reduction reaction on the dinitro compound to obtain the diamine monomer with the structure R' as methyl as shown in the formula I.
In the present invention, the reduction reaction is preferably carried out in a 1,4-dioxane or absolute ethanol solvent; the solid content of the dinitro compound in the reaction system is preferably 15% to 20%. In the invention, the reduction reaction is preferably carried out in the presence of a catalyst, the catalyst preferably comprises caustic soda, and the mass ratio of the dinitro compound to the catalyst is preferably 1: 0.1-0.5.
According to the invention, preferably, a dinitro compound and a catalyst are heated in a solvent to reflux, then reducing agents of sodium arsenite and hydrazine hydrate are added into a reaction system, the reflux reaction is continued for 15-24 hours, and the reduction reaction product is obtained after TLC detection until the raw material point disappears. In the invention, the molar ratio of the dinitro compound to the sodium arsenite is preferably 1: 5-8; the molar ratio of the dinitro compound to the hydrazine hydrate is 1: 15-20.
Filtering the reduction reaction product while the reduction reaction product is hot to remove sodium arsenite, collecting filtrate, and concentrating the filtrate under reduced pressure to obtain a crude diamine monomer product; the invention heats a diamine monomer crude product in a good solvent 1,4-dioxane until reflux, then adds a poor solvent deionized water into a reflux system until precipitation and insolubilization are just carried out, stops reflux, and obtains a diamine monomer with a structure R' shown in a formula I being trifluoromethyl through solid-liquid separation and vacuum drying.
The invention also provides a preparation method of the polyimide, which comprises the following steps:
(i) under the protection of nitrogen, carrying out polycondensation reaction on a dianhydride monomer and a diamine monomer in a polar organic solvent to obtain a polyamic acid solution; the diamine monomer is the diamine monomer in the technical scheme or the diamine monomer prepared by the preparation method in the technical scheme;
(ii) and (ii) adding a catalyst and a dehydrating agent into the polyamic acid solution obtained in the step (i) to perform imidization reaction, thereby obtaining polyimide.
In the invention, under the protection of nitrogen, dianhydride monomer and diamine monomer are subjected to polycondensation reaction in a polar organic solvent to obtain the polyamic acid solution.
In the invention, the diamine monomer is the diamine monomer described in the above technical scheme or the diamine monomer prepared by the preparation method described in the above technical scheme. In the present invention, the dianhydride monomer preferably comprises 4,4 ' - (hexafluoroisopropylidene) diphthalic anhydride, 3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride, or 4,4 ' - (4,4 ' -diphenoloxypropyl) -dibenzoic anhydride, and preferably has the structure shown in formula XI:
Figure BDA0001903036760000111
wherein AR preferably has a structure represented by formula 1, formula 2, or formula 3:
Figure BDA0001903036760000112
in the present invention, the molar ratio of the dianhydride monomer to the diamine monomer is preferably 1:0.8 to 1.2, and more preferably 2 to 3:2 to 3. In the present invention, the sum of the solid contents of the dianhydride monomer and the diamine monomer in the polar organic solvent is preferably 28% to 32%, and more preferably 20%. The invention preferably carries out the polycondensation reaction at room temperature, and the time of the polycondensation reaction is preferably 3-24 h.
In the present invention, the kind of the polar organic solvent preferably includes N, N '-dimethylformamide or N, N' -dimethylacetamide.
After the polyamic acid solution is obtained, a catalyst and a dehydrating agent are added into the polyamic acid solution to carry out imidization reaction, so as to obtain the polyimide.
In the present invention, the catalyst preferably comprises pyridine or isoquinoline; the dehydrating agent preferably comprises acetic anhydride or isoquinoline, and the present invention preferably adds pyridine and acetic anhydride to the polyamic acid solution, or adds isoquinoline to the polyamic acid solution. In the invention, when pyridine and acetic anhydride are preferably added, the volume ratio of the acetic anhydride to the pyridine is preferably 2:1, and the using ratio of the acetic anhydride to the diamine monomer is preferably 4mL: 1-3 mmol; in the invention, when isoquinoline is preferably added, the dosage ratio of isoquinoline to diamine monomer is preferably 0.2-0.3 mL: 1-2 mmol. In the invention, the temperature of the imidization reaction is preferably 55-65 ℃, and more preferably 60 ℃; the time of the imidization reaction is preferably 24-25 h. In the imidization reaction process, the polyamic acid solution generates cyclization dehydration reaction to generate polyimide.
In the invention, preferably, the imidization reaction product is cooled and poured into deionized water, and then filtering, filter cake alcohol washing and vacuum drying treatment are sequentially carried out to obtain the polyimide. The present invention is not particularly limited to the specific embodiments of the filtration, alcohol washing of the filter cake and vacuum drying under reduced pressure, and may be carried out by methods commonly used by those skilled in the art. In the present invention, the temperature of the vacuum drying treatment is preferably 80 ℃; the time of the vacuum drying treatment is preferably 12 h.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1: preparation of methyldiphenol compounds
Adding 10mmol of bisphenol A and 50mmol of methanesulfonic acid into a 250mL three-neck flask provided with a mechanical stirring device, reacting at room temperature for half an hour under the protection of nitrogen gas, heating to the melting temperature of the system above 180 ℃ at the heating rate of 20 ℃/min by using a microwave with the frequency of 200GHz, stopping the reaction when a raw material point disappears by TLC (thin layer chromatography), discharging the system after the reaction is finished, performing suction filtration and drying in an ice water bath to obtain a crude product, placing the crude product in a vacuum tube furnace, heating and sublimating the crude product, collecting a sublimed product to obtain a methyl diphenol compound, and performing vacuum drying at 100 ℃ for 12 hours to obtain 1.5980g of the methyl diphenol compound, wherein the obtained product has the following structure:
Figure BDA0001903036760000131
example 2: preparation of trifluoromethyl diphenol compound
Adding 10mmol of bisphenol AF and 100mmol of trifluoroacetic acid into a tetrafluoro reaction vessel provided with a mechanical stirring device, fully stirring and dissolving at room temperature, placing the tetrafluoro reaction vessel provided with reaction raw materials into a high-temperature reaction kettle, adjusting the heating temperature of a system to be 200 ℃, carrying out a melting reaction for 15 hours, and stopping the reaction; discharging the system after the reaction, placing the system in an ice water bath, carrying out suction filtration and drying to obtain a crude product, fully dissolving the obtained crude product in a good solvent 1,4-dioxane, adding a poor solvent deionized water until the crude product is just separated out and is stirred to separate out insoluble, carrying out suction filtration and drying to obtain a trifluoromethyl diphenol compound, wherein the obtained product has the following structure:
Figure BDA0001903036760000132
example 3: preparation of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxopyridyldiamine
The first step of reaction: adding 20mmol of methyl diphenol compound and 44mmol of potassium carbonate into a 250mL three-neck flask provided with a mechanical stirring device, reacting the system for half an hour by adopting a20 KHz ultrasonic method to obtain phenol ionic liquid, adding 44mmol of 2-chloro-5-nitropyridine to ensure that the total solid content of the reaction system is 15%, stirring, heating the system to 80 ℃, detecting by TLC (thin layer chromatography) until a raw material point disappears to obtain the end of the reaction, cooling the system, discharging the cooled system, leaching and drying the cooled system with 5% NaCl saline to obtain a crude product, dissolving the crude product in N, N-dimethylformamide, heating the system to a reflux temperature, adding deionized water until the system is just separated out and insoluble, stopping heating, cooling and leaching to obtain the dinitro compound.
The second step of reaction: adding 8mmol of dinitro compound obtained in the first step of reaction into a 250mL three-necked flask provided with a mechanical stirring device, adding 68mL of 1,4-dioxane, enabling the solid content of the system to be 15% of the total solid content of the reaction system, adding 1.3291g of catalyst caustic soda, stirring and heating the system to reflux, reacting the system for half an hour, adding 40mmol of reducing agent sodium arsenite, refluxing for 24 hours, detecting by TLC until the raw material point disappears, namely ending the reaction, filtering while hot (preventing the temperature cooling product from being separated out) to remove the reducing agent sodium arsenite, collecting filtrate, heating to reflux, introducing 4 hours of hydrogen, catalytically hydrogenating the filtrate, concentrating the filtrate to obtain a crude product, vacuum drying at 100 ℃ for 12 hours, dissolving the crude product in good solvent 1,4-dioxane, heating to the reflux temperature of the reaction solution to 110 ℃, slowly adding poor solvent deionized water into the reflux reaction solution, until just precipitated and did not dissolve, the heating was turned off and dried at 100 ℃ in vacuo for 12h to give 3.9702g of diamine monomer, the product having the following structure:
Figure BDA0001903036760000141
the diamine monomer prepared in example 3 was subjected to nuclear magnetic resonance test, and the results are shown in FIG. 1. it can be seen from FIG. 1 that the substance prepared according to the present invention has the above structure.
Example 4: preparation of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxo-3-methylpyridine diamine
The first step of reaction: adding 10mmol of methyl diphenol compound and 24mmol of potassium carbonate into a 250mL three-neck flask provided with a mechanical stirring device, reacting the system for half an hour by adopting an ultrasonic method to obtain phenol ionic liquid, adding 24mmol of 2-chloro-3-methyl-5-nitropyridine to ensure that the total solid content of the reaction system is 20%, stirring, heating the system to 100 ℃, detecting by TLC (thin layer chromatography) until a raw material point disappears to obtain the end of the reaction, cooling the system, discharging, performing suction filtration and drying on the cooled system and deionized water to obtain a crude product, dissolving the crude product in N, N-dimethylformamide, heating the system to a reflux temperature, adding deionized water until the system is just separated out and insoluble, closing the heating, cooling and suction filtration to obtain 6.7903g of the dinitro compound.
The second step of reaction: adding 17mmol of dinitro compound obtained in the first step of reaction into a 250mL three-necked flask provided with a mechanical stirring device, adding 86mL of 1,4-dioxane, enabling the solid content of the system to be 15% of the total solid content of the reaction system, adding 4.9354g of catalyst caustic soda, stirring and heating the system to reflux, reacting the system for half an hour, adding 85mmol of reducing agent sodium arsenite, refluxing for 20 hours, detecting by TLC until the raw material point disappears, namely finishing the reaction, filtering while hot (preventing the temperature cooling product from being separated out) to remove the reducing agent sodium arsenite, collecting the filtrate, heating to reflux, introducing 6 hours of hydrogen, catalytically hydrogenating the filtrate, concentrating the filtrate to obtain a crude product, vacuum drying at 100 ℃ for 12 hours, dissolving the crude product in good solvent 1,4-dioxane, heating to the reflux temperature of the reaction solution to 110 ℃, slowly adding poor solvent deionized water into the reflux reaction solution, until just precipitated and did not dissolve, the heating was turned off and dried at 100 ℃ in vacuo for 12h to give 8.0632g of diamine monomer, the product having the following structure:
Figure BDA0001903036760000151
the diamine monomer prepared in example 4 was subjected to nuclear magnetic resonance test, and the results are shown in FIG. 2, and it can be seen from FIG. 2 that the substance prepared according to the present invention has the above structure.
Example 5: preparation of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxo-quinolinediamine
The first step of reaction: adding 10mmol of methyl diphenol compound and 24mmol of potassium carbonate into a 250mL three-neck flask provided with a mechanical stirring device, reacting the system for half an hour by adopting an ultrasonic method with the frequency of 20KHz to obtain phenol ionic liquid, adding 24mmol of 2-chloro-5-nitroquinoline to ensure that the total solid content of the reaction system is 20%, stirring, heating the system to 100 ℃, detecting by TLC (thin layer chromatography) until a raw material point disappears to obtain the end of the reaction, cooling the system, discharging, performing suction filtration and drying on the cooled system and deionized water to obtain a crude product, dissolving the crude product in N, N-dimethylformamide, heating the system to a reflux temperature, adding deionized water until the system is just separated out and insoluble, closing the heating, cooling and performing suction filtration to obtain 6.0003g of the dinitro compound.
The second step of reaction: adding 10mmol of dinitro compound obtained in the first step of reaction into a 250mL three-necked flask provided with a mechanical stirring device, adding 59mL of 1,4-dioxane, enabling the solid content of the system to be 10% of the total solid content of the reaction system, adding 3.2636g of catalyst caustic soda, stirring and heating the system to reflux, reacting the system for half an hour, adding 80mmol of reducing agent sodium arsenite, refluxing for 15 hours, detecting by TLC until the raw material point disappears, namely finishing the reaction, filtering while hot (preventing the temperature cooling product from being separated out) to remove the reducing agent sodium arsenite, collecting the filtrate, heating to reflux, introducing 5 hours of hydrogen, catalytically hydrogenating the filtrate, concentrating the filtrate to obtain a crude product, vacuum drying at 100 ℃ for 12 hours, dissolving the crude product in good solvent 1,4-dioxane, heating to the reflux temperature of the reaction solution to 110 ℃, slowly adding poor solvent deionized water into the reflux reaction solution, until just precipitated and did not dissolve, the heating was turned off and dried at 100 ℃ in vacuo for 12h to give 5.0967g of diamine monomer, the product having the following structure:
Figure BDA0001903036760000152
example 6: preparation of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxo-isoquinolinediamine
The first step of reaction: adding 10mmol of methyl diphenol compound and 24mmol of potassium carbonate into a 250mL three-neck flask provided with a mechanical stirring device, reacting the system for half an hour by adopting an ultrasonic method to obtain phenol ionic liquid, adding 24mmol of 2-chloro-5-nitroisoquinoline to ensure that the total solid content of the reaction system is 20%, stirring, heating the system to 100 ℃, detecting by TLC (thin layer chromatography) until a raw material point disappears to obtain the end of the reaction, cooling the system, discharging the cooled system, performing suction filtration on the cooled system and deionized water, drying to obtain a crude product, dissolving the crude product in N, N-dimethylformamide, heating the system to a reflux temperature, adding deionized water until the system is just separated out and insoluble, closing the heating, cooling and suction filtration to obtain 5.6503g of the dinitro compound.
The second step of reaction: adding 10mmol of dinitro compound obtained in the first step of reaction into a 250mL three-necked flask provided with a mechanical stirring device, adding 59mL of 1,4-dioxane, enabling the solid content of the system to be 10% of the total solid content of the reaction system, adding 3.2636g of catalyst caustic soda, stirring and heating the system to reflux, reacting the system for half an hour, adding 80mmol of reducing agent sodium arsenite, refluxing for 22 hours, detecting by TLC until the raw material point disappears, namely finishing the reaction, filtering while hot (preventing the temperature cooling product from being separated out) to remove the reducing agent sodium arsenite, collecting the filtrate, heating to reflux, introducing 5 hours of hydrogen, catalytically hydrogenating the filtrate, concentrating the filtrate to obtain a crude product, vacuum drying at 100 ℃ for 12 hours, dissolving the crude product in good solvent 1,4-dioxane, heating to the reflux temperature of the reaction solution to 110 ℃, slowly adding poor solvent deionized water into the reflux reaction solution, until just precipitated and did not dissolve, the heating was turned off and dried at 100 ℃ in vacuo for 12h to give 5.3109g of diamine monomer, the product having the following structure:
Figure BDA0001903036760000161
example 7: preparation of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxotrifluoromethylpyridine diamine
The first step of reaction: adding 20mmol of trifluoromethyl diphenol compound and 46mmol of potassium carbonate into a 250mL three-neck flask provided with a mechanical stirring device, reacting the system for half an hour by adopting a20 KHz ultrasonic method to obtain phenol ionic liquid, adding 46mmol of 2-chloro-5-nitropyridine to ensure that the total solid content of the reaction system is 15%, stirring, heating the system to 100 ℃, detecting by TLC (thin layer chromatography) until a raw material point disappears to obtain the end of the reaction, cooling the system, discharging the cooled system, leaching and drying the cooled system with 5% NaCl saline to obtain a crude product, dissolving the crude product in N, N-dimethylformamide, heating the system to a reflux temperature, adding deionized water until the system just precipitates and does not dissolve, stopping heating, cooling and leaching to obtain a dinitro compound.
The second step of reaction: adding 8mmol of dinitro compound obtained in the first step of reaction into a 250mL three-necked flask provided with a mechanical stirring device, adding 64mL of 1,4-dioxane, enabling the solid content of the system to be 20% of the total solid content of the reaction system, adding 1.3291g of catalyst caustic soda, stirring and heating the system to reflux, reacting the system for half an hour, adding 40mmol of reducing agent sodium arsenite, refluxing for 24 hours, detecting by TLC until the raw material point disappears, namely ending the reaction, filtering while hot (preventing the temperature cooling product from being separated out) to remove the reducing agent sodium arsenite, collecting filtrate, heating to reflux, introducing 4 hours of hydrogen, catalytically hydrogenating the filtrate, concentrating the filtrate to obtain a crude product, vacuum drying at 100 ℃ for 12 hours, dissolving the crude product in good solvent 1,4-dioxane, heating to the reflux temperature of the reaction solution to 110 ℃, slowly adding NaCl brine with 5% of poor solvent into the refluxing reaction solution, until just precipitated and did not dissolve, the heating was turned off and dried at 100 ℃ in vacuo for 12h to give 3.0602g of diamine monomer, the product having the following structure:
Figure BDA0001903036760000171
example 8: preparation of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindene) -6,6 ' -dioxo-3-methyltrifluoromethylpyridinediamine
The first step of reaction: adding 10mmol of trifluoromethyl diphenol compound and 28mmol of potassium carbonate into a 250mL three-neck flask provided with a mechanical stirring device, reacting the system for half an hour by adopting an ultrasonic method to obtain phenol ionic liquid, adding 28mmol of 2-chloro-3-methyl-5-nitropyridine to ensure that the total solid content of the reaction system is 22%, stirring, heating the system to 120 ℃, detecting by TLC (thin layer chromatography) until a raw material point disappears to obtain the end of the reaction, cooling the system, discharging, performing suction filtration and drying on the cooled system and deionized water to obtain a crude product, dissolving the crude product in N, N-dimethylformamide, heating the system to a reflux temperature, adding deionized water until the system is just separated out and insoluble, closing the heating, cooling and suction filtration to obtain 6.4303g of the dinitro compound.
The second step of reaction: adding 17mmol of dinitro compound obtained in the first step of reaction into a 250mL three-necked flask provided with a mechanical stirring device, adding 80mL of 1,4-dioxane, enabling the solid content of the system to be 20% of the total solid content of the reaction system, adding 4.9354g of catalyst caustic soda, stirring and heating the system to reflux, reacting the system for half an hour, adding 85mmol of reducing agent sodium arsenite, refluxing for 20 hours, detecting by TLC until the raw material point disappears, namely finishing the reaction, filtering while hot (preventing the temperature cooling product from being separated out) to remove the reducing agent sodium arsenite, collecting the filtrate, heating to reflux, introducing 6 hours of hydrogen, catalytically hydrogenating the filtrate, concentrating the filtrate to obtain a crude product, vacuum drying at 100 ℃ for 12 hours, dissolving the crude product in good solvent 1,4-dioxane, heating to the reflux temperature of the reaction solution to 110 ℃, slowly adding poor solvent deionized water into the reflux reaction solution, until just precipitated and did not dissolve, the heating was turned off and dried at 100 ℃ in vacuo for 12h to give 7.0098g of diamine monomer, the product having the following structure:
Figure BDA0001903036760000181
example 9: the polyimide is prepared from 4,4 '- (2, 2', 3 '-tetrahydro-1, 1' -spirobiindane) -6,6 '-dioxopyridyldiamine and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride by the following specific steps:
adding 2.2mmol of 4,4 '- (2, 2', 3 '-tetrahydro-1, 1' -spirobiindane) -6,6 '-dioxopyridyldiamine and 13mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.2mmol of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 2mL of pyridine and 4mL of acetic anhydride into the reaction system, heating the reaction system to 60 ℃, maintaining the temperature for 24h, closing and heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, refluxing and washing with ethanol for 3 times, drying at 80 ℃ in a vacuum oven to obtain 1.7309g of target polyimide polymer PI-1, the resulting product has the following structure:
Figure BDA0001903036760000182
example 10: the polyimide is prepared from 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxopyridine diamine and 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride by the following specific steps:
adding 2.0mmol of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxopyridyldiamine and 10mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.0mmol of 3,3 ', 4,4 ' -diphenylether tetraacid dianhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 2mL of pyridine and 4mL of polyamic acid into the reaction system, heating the acetic anhydride system to 60 ℃, maintaining the temperature for reaction for 24h, closing and heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, refluxing and washing with ethanol for 3 times, drying at 80 ℃ in a vacuum oven to obtain 1.3006g of target polyimide polymer PI-2, the resulting product has the following structure:
Figure BDA0001903036760000191
example 11: the polyimide is prepared from 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxopyridine diamine and 4,4 ' - (4,4 ' -diphenol oxy propyl) -dibenzoic anhydride by the following specific steps:
adding 2.0mmol of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindene) -6,6 ' -dioxopyridyldiamine and 12mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.0mmol of 4,4 ' - (4,4 ' -diphenoloxy propyl) -dibenzoic acid anhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 2mL of pyridine and 4mL of acetic anhydride into the reaction system, heating the reaction system to 60 ℃, keeping the temperature for 24h, closing the heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, carrying out ethanol reflux washing for 3 times, drying in a vacuum oven at 80 ℃, 1.8306g of the target polyimide polymer PI-3 were obtained, giving a product having the following structure:
Figure BDA0001903036760000192
example 12: the polyimide is prepared from 4,4 '- (2, 2', 3 '-tetrahydro-1, 1' -spirobiindane) -6,6 '-dioxo-3-methylpyridine diamine and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride by the following specific steps:
adding 3.0mmol of 4,4 '- (2, 2', 3 '-tetrahydro-1, 1' -spirobiindane) -6,6 '-dioxo-3-methylpyridine and 18mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.0mmol of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride after diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 2mL of pyridine and 4mL of acetic anhydride into the reaction system, heating the reaction system to 80 ℃, keeping the temperature for 24h, closing the heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, carrying out ethanol reflux washing for 3 times, drying in a vacuum oven at 80 ℃, 2.7306g of the target polyimide polymer PI-4 were obtained, giving a product having the following structure:
Figure BDA0001903036760000201
example 13: the polyimide is prepared from 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxo-3-methylpyridine diamine and 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride by the following specific steps:
adding 3.0mmol of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindene) -6,6 ' -dioxo-3-methylpyridine diamine and 18mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 3.0mmol of 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 3mL of pyridine and 6mL of acetic anhydride into the reaction system, heating the reaction system to 80 ℃, keeping the temperature for 24h, cooling the system to room temperature, discharging the material into 200mL of deionized water, carrying out ethanol reflux washing for 3 times, drying in a vacuum oven at 80 ℃, 2.3106g of the target polyimide polymer PI-5 were obtained, giving a product having the following structure:
example 14: the polyimide is prepared from 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindene) -6,6 ' -dioxo-3-methylpyridine diamine and 4,4 ' - (4,4 ' -diphenoloxy propyl) -dibenzoic anhydride by the following specific steps:
adding 3.0mmol of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindene) -6,6 ' -dioxo-3-methylpyridine diamine and 19mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 3.0mmol of 4,4 ' - (4,4 ' -diphenoloxy propyl) -dibenzoic anhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 3mL of pyridine and 6mL of acetic anhydride into the reaction system, heating the reaction system to 80 ℃, keeping the temperature for reacting for 24h, closing the heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, refluxing and washing with ethanol for 3 times, drying in a vacuum oven at 80 ℃ to obtain 3.0209g of target polyimide polymer PI-6, wherein the structure of the obtained product is as follows:
Figure BDA0001903036760000203
example 15: the polyimide is prepared from 4,4 '- (2, 2', 3 '-tetrahydro-1, 1' -spirobisindane) -6,6 '-dioxoquinoline diamine and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride by the following specific steps:
adding 2.2mmol of 4,4 '- (2, 2', 3 '-tetrahydro-1, 1' -spirobisindane) -6,6 '-dioxoquinoline diamine and 13mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.2mmol of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 2mL of pyridine and 4mL of acetic anhydride into the reaction system, heating the system to 60 ℃, maintaining the temperature for reaction for 24h, closing and heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, refluxing and washing with ethanol for 3 times, drying at 80 ℃ in a vacuum oven to obtain 1.9329g of target polyimide polymer, the resulting product has the following structure:
Figure BDA0001903036760000211
example 16: the polyimide is prepared from 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxoquinoline diamine and 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride by the following specific steps:
adding 2.0mmol of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindenyl) -6,6 ' -dioxyquinoline diamine and 10mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.0mmol of 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 2mL of pyridine and 4mL of polyamic acid into the reaction system, heating the acetic anhydride system to 60 ℃, maintaining the temperature for reaction for 24h, closing and heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, refluxing and washing with ethanol for 3 times, drying at 80 ℃ in a vacuum oven to obtain 1.4016g of target polyimide polymer, the resulting product has the following structure:
Figure BDA0001903036760000212
example 17: the polyimide is prepared from 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxoquinoline diamine and 4,4 ' - (4,4 ' -diphenol oxy propyl) -dibenzoic anhydride by the following specific steps:
adding 2.0mmol of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindene) -6,6 ' -dioxoquinoline diamine and 12mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.0mmol of 4,4 ' - (4,4 ' -diphenoloxy propyl) -dibenzoic acid anhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 2mL of pyridine and 4mL of acetic anhydride into the reaction system, heating the reaction system to 60 ℃, keeping the temperature for 24h, closing the heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, carrying out ethanol reflux washing for 3 times, drying in a vacuum oven at 80 ℃, 1.9006g of the objective polyimide polymer was obtained, giving a product having the following structure:
Figure BDA0001903036760000221
example 18: the polyimide is prepared from 4,4 '- (2, 2', 3 '-tetrahydro-1, 1' -spirobisindane) -6,6 '-dioxo-isoquinoline diamine and 4, 4' - (hexafluoroisopropylene) diphthalic anhydride by the following specific steps:
adding 2.2mmol of 4,4 '- (2, 2', 3 '-tetrahydro-1, 1' -spirobisindane) -6,6 '-dioxoquinoline diamine and 13mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.2mmol of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 2mL of pyridine and 4mL of acetic anhydride into the reaction system, heating the system to 60 ℃, maintaining the temperature for reaction for 24h, closing and heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, refluxing and washing with ethanol for 3 times, drying at 80 ℃ in a vacuum oven to obtain 1.6904g of target polyimide polymer, the resulting product has the following structure:
Figure BDA0001903036760000222
example 19: the polyimide is prepared from 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxo-isoquinoline diamine and 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride by the following specific process:
adding 2.0mmol of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxoquinoline diamine and 10mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.0mmol of 3,3 ', 4,4 ' -diphenylether tetracarboxylic dianhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 2mL of pyridine and 4mL into the reaction system, heating the acetic anhydride system to 60 ℃, maintaining the temperature for reaction for 24h, closing and heating, cooling the system to room temperature, discharging into 200mL of deionized water, refluxing and washing with ethanol for 3 times, drying at 80 ℃ in a vacuum oven to obtain 1.0126g of target polyimide polymer, the resulting product has the following structure:
Figure BDA0001903036760000231
example 20: the polyimide is prepared from 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxo-isoquinoline diamine and 4,4 ' - (4,4 ' -diphenoloxy propyl) -dibenzoic anhydride by the following specific steps:
adding 2.0mmol of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindene) -6,6 ' -dioxoquinoline diamine and 12mL of N, N-dimethylacetamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.0mmol of 4,4 ' - (4,4 ' -diphenoloxy propyl) -dibenzoic acid anhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 2mL of pyridine and 4mL of acetic anhydride into the reaction system, heating the reaction system to 60 ℃, keeping the temperature for 24h, closing the heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, carrying out ethanol reflux washing for 3 times, drying in a vacuum oven at 80 ℃, 1.7006g of the objective polyimide polymer was obtained, giving a product having the following structure:
Figure BDA0001903036760000232
example 21: the specific process for preparing polyimide by using 4,4 '- (2, 2', 3 '-tetrahydro-1, 1' -spirobiindane) -6,6 '-dioxo trifluoromethyl pyridine diamine and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is as follows
Adding 2.2mmol of 4,4 '- (2, 2', 3 '-tetrahydro-1, 1' -spirobisindene) -6,6 '-dioxy trifluoromethyl pyridine diamine and 16mL of N, N-dimethylformamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.2mmol of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, dropwise adding 0.35mL of isoquinoline into the reaction system, heating the system to 120 ℃, keeping the temperature for reacting for 24h, closing the heating, cooling the system to room temperature, discharging the material into 200mL deionized water, refluxing and washing with ethanol for 3 times, drying at 80 ℃ in a vacuum oven to obtain 1.6399g of target polyimide, the resulting product has the following structure:
Figure BDA0001903036760000241
example 22: the polyimide is prepared from 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindane) -6,6 ' -dioxy trifluoromethyl quinoline diamine and 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride by the following specific steps:
adding 2.0mmol of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindene) -6,6 ' -dioxy trifluoromethyl quinoline diamine and 10mL of N, N-dimethylformamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer and a condenser under the protection of nitrogen to ensure that the solid content of the system is 15%, adding 2.0mmol of 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, adding 0.2mL of isoquinoline into the reaction system, heating the reaction system to 160 ℃, keeping the temperature for reacting for 24h, closing the heating, cooling the system to room temperature, discharging the material into 200mL of deionized water, refluxing and washing 3 times with ethanol, drying at 80 ℃ in a vacuum oven to obtain 1.7916g of target polyimide polymer, the resulting product has the following structure:
Figure BDA0001903036760000242
example 23: the polyimide is prepared from 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindene) -6,6 ' -dioxy trifluoromethyl-3-methylquinoline diamine and 4,4 ' - (4,4 ' -diphenol oxygen propyl) -dibenzoic anhydride by the following specific steps:
adding 2.0mmol of 4,4 ' - (2,2 ', 3 ' -tetrahydro-1, 1 ' -spirobisindene) -6,6 ' -dioxy trifluoromethyl-3-methylquinoline diamine and 10mL of N, N-dimethylformamide into a 50mL three-necked flask provided with a nitrogen inlet and a nitrogen outlet, a magnetic stirrer, a thermometer, a condenser and a water device under the protection of nitrogen, ensuring that the solid content of the system is 15%, adding 2.0mmol of 4,4 ' - (4,4 ' -diphenoloxy propyl) -dibenzoic anhydride after the diamine is completely dissolved, reacting for 24h at room temperature to form viscous polyamic acid, adding 2mL of pyridine, 4mL of acetic anhydride and 5mL of toluene into the reaction system, heating the reaction system to 180 ℃, maintaining the temperature, reacting for 24h, closing and heating, cooling the reaction system to room temperature, discharging the material into 200mL deionized water, refluxing and washing with ethanol for 3 times, and drying in a vacuum oven at 80 ℃ to obtain 2.2016g of target polyimide polymer, wherein the obtained product has the following structure:
Figure BDA0001903036760000251
performance testing
The polyimides prepared in examples 9 to 14 were subjected to an infrared spectrum test, and the test results are shown in fig. 3. In the present invention, the polyimides synthesized in examples 9 to 14 are represented by PI-1, PI-2, PI-3, PI-4, PI-5 and PI-6 in this order. As can be seen from FIG. 3, the infrared spectrum provided by the present invention has characteristic peaks of polyimide, which proves that the target polymer is successfully synthesized.
DSC tests of the polyimides prepared in examples 9 to 14 showed that the glass transition temperature of the polyimide of the present invention is 230 ℃ or higher and the thermal stability is good as shown in FIG. 4.
The light transmittance of the polyimides prepared in examples 9 to 14 under ultraviolet light was measured, and the measurement results are shown in fig. 5, and it can be seen from fig. 5 that the polyimides provided by the present invention have high transmittance in the visible light range, and the average transmittance in the visible light range reaches 85%. In the invention, the light transmittance is tested by adopting an ultraviolet wave-front test, and specifically comprises the following steps: the method is characterized by adopting a UV2550 type ultraviolet-visible spectrophotometer of Nippon Jinshima company to measure, wherein the scanning range is 200-800 nm.
The thermal weight loss performance of the polyimides prepared in examples 9 to 14 was tested, and the test results are shown in fig. 6, and it can be seen from fig. 6 that the polyimide provided by the present invention has good thermal stability, and the 5% thermal weight loss temperature is 480 ℃ or higher under nitrogen atmosphere. The method adopts a TA2050 thermogravimetric analyzer to measure in the nitrogen atmosphere, the temperature rise range is 100-800 ℃, and the flow of atmosphere gas is 10 ml/min.
The gas selectivity of the polyimides prepared in examples 9 to 14 was tested, and the test results are shown in fig. 7 and 8, and it can be seen from fig. 7 and 8 that the present invention has a good effect of separating oxygen and nitrogen, and a good effect of separating carbon dioxide and methane.
Solubility test
The solubility of the polyimides prepared in examples 9 to 14 was tested by the following method: the polyimide was dissolved in DMAC, DMF, NMP, DMSO, THF, CHCl, respectively3And 1,4-Dioxane, the concentration of polyimide in different solvents was 10 mg/mL. Polyimide was tested for solubility in different solvents, + +: fully dissolving at room temperature; +: heating for complete dissolution; + -: partial dissolution; - -: heating for insolubilization. The test results are shown in table 1.
TABLE 1 solubility of polyimides prepared in examples 9 to 14
Solvent/sample Example 9 Example 10 Example 11 Example 12 Example 13 Example 14
DMAC ++ ++ ++ ++ ++ ++
DMF ++ ++ ++ ++ ++ ++
NMP ++ ++ ++ ++ ++ ++
DMSO + + + + + +
THF ++ ++ ++ ++ ++ ++
CHCl3 ++ ++ ++ ++ ++ ++
1,4-Dioxane ++ ++ ++ ++ ++ ++
As can be seen from the test results in Table 1, the polyimide prepared from the diamine monomer provided by the invention has better solubility. The diamine monomer provided by the invention introduces groups such as aliphatic structures, ether bonds and the like, so that the polyimide prepared from the diamine monomer has good solubility in most polar solvents.
Gas separation test
The polyimide film prepared from the polyimide prepared in the embodiment 9-14 of the invention is prepared by the following specific preparation method:
dissolving polyimide in N, N-dimethylacetamide at a solid content of 15%, filtering through a 0.45-micron Teflon filter to remove insoluble substances to obtain a uniform polyimide solution, uniformly coating the solution on a clean 9cm × 9cm glass plate, placing the glass plate in an oven, raising the temperature by adopting a program, sequentially treating the glass plate at 60 ℃/4h, 90 ℃/12h, 120 ℃/4h and 150 ℃/4h, and naturally cooling to obtain the transparent polyimide film.
The polyimide films prepared in examples 9 to 14 were subjected to a gas separation test, and the test results are shown in table 2, and the test method was:
the polyimide prepared by the invention adopts a self-made gas permeameter in the aspect of gas separation, and the specific method is as follows: the gas permeation properties of the polymer films were tested by a pressure differential method (constant volume pressure method). In the testing process, the testing film is sealed in a testing pool by epoxy resin, the upstream pressure is set to be 2atm, the downstream is vacuumized, after the downstream pressure is stabilized for a period of time, the testing is carried out at 35 ℃, the separation effect of the polymer film on gas is represented by a gas permeability coefficient, and the gas separation coefficient represents the selectivity of ideal gas.
TABLE 2 gas separation Performance of polyimide films of examples 9 to 14
Figure BDA0001903036760000271
As can be seen from Table 2, the polyimide film prepared from the polyimide provided by the invention has good gas separation performance, and has a permeability coefficient to nitrogen of 1.92-3.59 Barrer, a permeability coefficient to methane of 1.42-12.72 Barrer, a permeability coefficient to oxygen of 2.33-16.9 Barrer and a permeability coefficient to carbon dioxide of 48-63.18 Barrer. Therefore, the polyimide film prepared from the polyimide provided by the invention has high gas permeability.
The polyimide film provided by the invention has a gas separation coefficient of 17.4-25.7 for a mixed gas of carbon dioxide and nitrogen, a gas separation coefficient of 16.2-36.9 for a mixed gas of carbon dioxide and methane, and a gas separation coefficient of 4.4-6.9 for a mixed gas of oxygen and nitrogen, and the calculation method of the gas separation coefficient is αA/B＝PA/PB，PAAnd PBThe permeability coefficients of the two gases A and B are respectively. Therefore, the polyimide film prepared from the polyimide provided by the invention has high selectivity to gas, namely, after the polyimide film is prepared from the polyimide provided by the invention, the polyimide film has the characteristic of high permeability while ensuring good selectivity.
In conclusion, the polyimide prepared from the diamine monomer provided by the invention is prepared by adding DMAC, DMF, NMP, DMSO, THF and CHCl3And 1,4-Dioxane, and is made by the present inventionThe polyimide film prepared from the polyimide has the characteristics of high permeability while ensuring good selectivity in the field of gas separation.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A diamine monomer having the structure of formula I:
Figure FDA0002424797920000011
r' is methyl or trifluoromethyl;
the R is selected from one of structures shown in a formula II;
Figure FDA0002424797920000012
2. the diamine monomer of claim 1, wherein the diamine monomer has a structure of formula III to formula VI:
Figure FDA0002424797920000013
Figure FDA0002424797920000021
3. the process for producing a diamine monomer according to claim 1 or 2,
when R' in the formula I is methyl, the preparation method of the diamine monomer comprises the following steps:
(1) carrying out microwave reaction on bisphenol A and methanesulfonic acid, discharging a microwave reaction product in an ice-water bath, and collecting a solid; heating and sublimating the solid to obtain a methyl diphenol compound;
the structural formula of the methyl diphenol compound is as follows:
Figure FDA0002424797920000022
(2) mixing the methyl diphenol compound obtained in the step (1), a catalyst and a solvent to obtain methyl diphenol ionic liquid; carrying out substitution reaction on the methyl diphenol ionic liquid and the mononitro compound to obtain a dinitro compound with R' being methyl; then, carrying out reduction reaction on the dinitro compound with the R 'being methyl to obtain a diamine monomer with the structure R' being methyl as shown in the formula I; the catalyst is potassium carbonate and/or cesium carbonate;
when R' in the formula I is trifluoromethyl, the preparation method of the diamine monomer comprises the following steps:
(a) heating bisphenol AF and trifluoroacetic acid for reaction, discharging the heated reaction product in an ice water bath, and obtaining a trifluoromethyl diphenol compound;
the structural formula of the trifluoromethyl diphenol compound is as follows:
Figure FDA0002424797920000031
(b) mixing the trifluoromethyl diphenol compound obtained in the step (a), a catalyst and a solvent to obtain trifluoromethyl diphenol ionic liquid; carrying out substitution reaction on the trifluoromethyl diphenol ionic liquid and a mononitro compound to obtain a dinitro compound with R' being trifluoromethyl; then, carrying out reduction reaction on the dinitro compound with R 'as trifluoromethyl to obtain a diamine monomer with a structure R' as trifluoromethyl shown in the formula I; the catalyst is potassium carbonate and/or cesium carbonate;
the mononitro compound in the step (2) and the step (b) is independently halogenated nitropyridine, halogenated methylnitropyridine, halogenated nitroquinoline, halogenated methylnitroquinoline or halogenated nitroisoquinoline.
4. The method according to claim 3, wherein the molar ratio of bisphenol A to methanesulfonic acid in step (1) is 1:5 to 8.
5. The preparation method according to claim 3 or 4, wherein the frequency of the microwave reaction in the step (1) is 180 to 220GHz, and the heating rate of the microwave reaction is 18 to 22 ℃/min.
6. The method according to claim 3, wherein the molar ratio of bisphenol AF to trifluoroacetic acid in step (a) is 1: 10-12.
7. The preparation method according to claim 3 or 6, wherein the heating reaction in the step (a) is carried out at a temperature of 180 to 220 ℃ for 15 to 20 hours.
8. The preparation method according to claim 3, wherein the molar ratio of the methyldiphenol ionic liquid to the mononitro compound in the step (2) is 1: 2-2.4; the molar ratio of the trifluoromethyl diphenol ionic liquid to the mononitro compound in the step (b) is 1: 2-2.4.
9. A preparation method of polyimide comprises the following steps:
(i) under the protection of nitrogen, carrying out polycondensation reaction on a dianhydride monomer and a diamine monomer in a polar organic solvent to obtain a polyamic acid solution; the diamine monomer is the diamine monomer according to claim 1 or 2;
(ii) and (ii) adding a catalyst and a dehydrating agent into the polyamic acid solution obtained in the step (i) to perform imidization reaction, thereby obtaining polyimide.
10. A polyimide prepared by the process of claim 9.
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