CN109912437B - Polyamine monomer and preparation method thereof, polyimide and preparation method thereof, and polyimide film - Google Patents
Polyamine monomer and preparation method thereof, polyimide and preparation method thereof, and polyimide film Download PDFInfo
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Abstract
The invention provides a polyamine monomer and a preparation method thereof, polyimide and a preparation method thereof, and a polyimide film, and belongs to the technical field of organic synthesis. The polyamine monomer provided by the invention has a structure shown in any one of formulas I to IV, has a microporous structure, a flexible group (ether bond) and a hydroxyl structure, and is further polymerized with a dianhydride monomer to obtain the polyimide. The polyimide film formed by the polyimide provided by the invention has better selective permeability and penetrability. In addition, the polyimide provided by the invention has better solubility.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a polyamine monomer and a preparation method thereof, polyimide and a preparation method thereof, and a polyimide film.
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 excellent physicochemical property, so the high molecular polymer membrane becomes a commonly used gas separation membrane material. 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 like, and has important application in the aspects of oxygen/nitrogen separation, gas dehumidification, carbon dioxide recovery, hydrogen separation recovery and the like.
Currently available gas separation membrane materials consist mainly of low-dispersion, solute-processable glassy polymers, which are inversely related, i.e. the permeability increases, the selectivity decreases, which is the so-called Trade-off effect. Therefore, the prepared polymer gas separation membrane with high permeability and high selectivity has very profound influence on improving the gas separation efficiency and expanding the application range.
Disclosure of Invention
The invention provides a polyamine monomer, and a polyimide film prepared from the polyamine monomer provided by the invention has better gas selectivity and permeability.
The invention provides a polyamine monomer, which has a structure shown in any one of a formula I to a formula IV:
the invention also provides a preparation method of the polyamine monomer in the technical scheme,
when the polyamine monomer has the structure shown in formula I or formula III, the preparation method comprises the following steps:
(1) heating, refluxing and cooling an acetone solution of hydrogen iodide and an acetic acid solution of catechol to obtain a supersaturated solution, and then carrying out hydrothermal treatment on the supersaturated solution to precipitate spiro tetraphenol; the spiro tetraphenol has a structure represented by formula V:
(2) carrying out substitution reaction on the spiro tetraphenol obtained in the step (1) and halogenated nitro methyl ether in the presence of a catalyst and an organic solvent to obtain a tetranitro methyl ether spiro compound; the halogenated nitrobenzyl ethers include 5-halo-2-nitrobenzyl ether or 2-halo-5-nitrobenzyl ether; the catalyst comprises one or two of potassium carbonate and cesium carbonate;
when the halogenated nitroanisole is 5-halo-2-nitroanisole, the tetranitroanisole spiro compound has a structure shown in formula VI; when the halogenated nitroanisole is 2-halo-5-nitroanisole, the tetranitroanisole spiro compound has a structure shown in formula VII:
(3) performing demethylation reaction on the tetranitrobenzyl ether spiro compound obtained in the step (2) and boron tribromide, and then quenching by adopting methanol to generate a tetranitrohydroxybenzene spiro compound; the tetranitrohydroxybenzene spiro-compound has a structure shown in a formula VIII or a formula IX:
(4) in the presence of sodium hydroxide, reducing the tetranitrohydroxybenzene spiro-compound obtained in the step (3) by adopting sodium arsenite to obtain a polyamine monomer with a structure shown as a formula I or a formula III;
when the polyamine monomer has the structure shown in formula II or formula IV, the preparation method comprises the following steps:
(a) heating, refluxing and cooling an acetone solution of hydrogen iodide, an acetic acid solution of catechol and an acetic acid solution of hydroxybenzene to obtain a supersaturated solution, and then carrying out hydrothermal treatment on the supersaturated solution to precipitate the spiro trisphenol; the spiro triphenol has a structure shown in a formula X:
(b) carrying out substitution reaction on the spiro-trisphenol obtained in the step (a) and halogenated nitroanisole in the presence of a catalyst and an organic solvent to obtain a trinitroanisole spiro-compound; the halogenated nitrobenzyl ethers include 5-halo-2-nitrobenzyl ether or 2-halo-5-nitrobenzyl ether; the catalyst comprises one or two of potassium carbonate and cesium carbonate;
when the halogenated nitroanisole is 5-halo-2-nitroanisole, the trinitroanisole spiro compound has a structure shown in formula XI; when the halogenated nitroanisole is 2-halo-5-nitroanisole, the trinitroanisole spiro compound has a structure represented by formula XII:
(c) carrying out demethylation reaction on the trinitroanisole spiro-compound obtained in the step (b) and boron tribromide, and then quenching by adopting methanol to generate a trinitrohydroxybenzene spiro-compound; the trinitrohydroxybenzene spiro-compound has a structure shown in a formula XIII or XIV:
(d) reducing the trinitrohydroxybenzene spiro-compound obtained in the step (c) by adopting sodium arsenite in the presence of sodium hydroxide to obtain a polyamine monomer with a structure shown as a formula II or a formula IV.
Preferably, the molar ratio of hydrogen iodide to catechol in the step (1) is 1: 2-5; the temperature of the hydrothermal treatment in the step (1) is 200-240 ℃, and the pressure is 1 MPa-0.5 GPa.
Preferably, the molar ratio of hydrogen iodide, catechol and hydroxybenzene in the step (a) is 1: 1-4; the temperature of the hydrothermal treatment in the step (a) is 200-240 ℃, and the pressure is 1 MPa-0.5 GPa.
Preferably, the molar ratio of the spirocyclic tetraphenol to the halogenated nitrobenzyl ether in the step (2) is 1: 5-9; the temperature of the substitution reaction in the step (2) is 150-200 ℃, and the time is 8-10 h;
the molar ratio of the spiro trisphenol to the halogenated nitrobenzyl ether in the step (b) is 1: 5-9; the temperature of the substitution reaction in the step (b) is 150-200 ℃, and the time is 8-10 h.
Preferably, the molar ratio of the tetranitrobenzyl ether spiro-compound to the boron tribromide to the methanol in the step (3) is 1: 6-9: 10-14; the temperature of the substitution reaction in the step (3) is-5 to-10 ℃, and the time is 3 to 6 hours;
the molar ratio of the trinitroanisole spiro-compound to the boron tribromide to the methanol in the step (c) is 1: 6-9: 10-14; the temperature of the substitution reaction in the step (c) is-5 to-10 ℃, and the time is 1 to 2 hours.
Preferably, the molar ratio of the tetranitrohydroxybenzene spiro-compound to the sodium arsenite in the step (4) is 1: 5-8; the temperature of reduction in the step (4) is 100-120 ℃, and the time is 8-10 h;
the molar ratio of the trinitrohydroxybenzene spiro-compound to the sodium arsenite in the step (d) is 1: 5-8; the temperature of the reduction in the step (d) is 100-130 ℃, and the time is 8-10 h.
The invention provides polyimide, which has a structure shown in a formula XV:
wherein one of the four R substituents is H and the remaining three R substituents are
Or all four R substituents are
Wherein AR has a structure according to any one of formulas 1 to 3:
the invention provides a preparation method of polyimide in the technical scheme, which comprises the following steps:
(i) under the protection of nitrogen, carrying out polycondensation reaction on a dianhydride monomer and a polyamine monomer in a polar organic solvent to obtain a polyamic acid solution; the polyamine monomer is the polyamine monomer in the technical scheme or the polyamine 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 a polyimide film, which is characterized by comprising the polyimide in the technical scheme or the polyimide prepared by the method in the technical scheme; the thickness of the polyimide film is 60-70 um.
The invention provides a polyamine monomer which has a structure shown in any one of a formula I to a formula IV. The polyamine monomer provided by the invention has a spiro microporous structure and a flexible group (ether bond), and the hyperbranched polyimide polymer is obtained by further polymerizing the polyamine monomer provided by the invention with a dianhydride monomer. The polyamine monomer provided by the invention contains a plurality of amino groups, which is beneficial to forming hyperbranched polyimide by polymerizing with dianhydride monomer, and the hyperbranched polyimide polymer provided by the invention has a microporous structure, so that small gas molecules can easily permeate into the microporous structure, and the selective permeability of a membrane is increased; in addition, the polyamine monomer provided by the invention contains a plurality of amino groups, so that the formed hyperbranched polymer and the polymer have larger gaps and larger permeability coefficient. In addition, the flexible group (ether bond) and the hydroxyl group in the polyimide provided by the invention act together, so that the interaction between a polyamine monomer and solvent molecules is increased, the free volume and flexibility of a polymer molecular chain are increased, the solvent is easy to permeate, and the problem of poor solubility caused by a rigid chain in the traditional gas separation membrane is solved. The embodiment result shows that the polyimide film prepared by the polyimide has the characteristic of high permeability while ensuring good selectivity in the field of gas separation; the polyimide prepared from the polyamine monomer provided by the invention can be applied to DMAC, DMF, NMP, DMSO, THF and CHCl3Has better solubility.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a polyamine monomer prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a polyimide prepared in application examples 1 to 5 of the present invention;
FIG. 3 is a diagram showing the distribution of pore diameters of polyimides produced in application examples 1 to 3 of the present invention.
Detailed Description
The invention provides a polyamine monomer, which has a structure shown in any one of a formula I to a formula IV:
the invention also provides a preparation method of the polyamine monomer in the technical scheme,
when the polyamine monomer has the structure shown in formula I or formula III, the preparation method comprises the following steps:
(1) heating, refluxing and cooling an acetone solution of hydrogen iodide and an acetic acid solution of catechol to obtain a supersaturated solution, and then carrying out hydrothermal treatment on the supersaturated solution to precipitate spiro tetraphenol; the spiro tetraphenol has a structure represented by formula V:
(2) carrying out substitution reaction on the spiro tetraphenol obtained in the step (1) and halogenated nitro methyl ether in the presence of a catalyst and an organic solvent to obtain a tetranitro methyl ether spiro compound; the halogenated nitrobenzyl ethers include 5-halo-2-nitrobenzyl ether or 2-halo-5-nitrobenzyl ether; the catalyst comprises one or two of potassium carbonate and cesium carbonate;
when the halogenated nitroanisole is 5-halo-2-nitroanisole, the tetranitroanisole spiro compound has a structure shown in formula VI; when the halogenated nitroanisole is 2-halo-5-nitroanisole, the tetranitroanisole spiro compound has a structure shown in formula VII:
(3) removing the tetranitrobenzyl ether spiro compound obtained in the step (2), boron tribromide and methanol to generate a tetranitrohydroxybenzene spiro compound; the tetranitrohydroxybenzene spiro-compound has a structure shown in a formula VIII or a formula IX:
(4) and (3) in the presence of sodium hydroxide, reducing the tetranitrohydroxybenzene spiro-compound obtained in the step (3) by adopting sodium arsenite to obtain a polyamine monomer with a structure shown as a formula I or a formula III.
The method comprises the steps of heating, refluxing and cooling an acetone solution of hydrogen iodide and an acetic acid solution of catechol to obtain a supersaturated solution, and then carrying out hydrothermal treatment on the supersaturated solution to precipitate the spiro tetraphenol. In the invention, the molar ratio of hydrogen iodide in the acetone solution of hydrogen iodide to catechol in the acetic acid solution of catechol is preferably 1: 2-5, and more preferably 1: 3-4. In the present invention, the mass concentration of hydrogen iodide in the acetone solution of hydrogen iodide is preferably 80% to 99%, and more preferably 85%; the mass concentration of the catechol in the acetic acid solution of the catechol is preferably 10-55%, more preferably 20-50%, and even more preferably 30-40%; the mass concentration of acetic acid in the acetic acid solution of catechol is preferably 10% to 40%, and more preferably 20% to 30%. In the present invention, the acetone functions to provide a reaction environment, and the acetic acid functions as a catalyst. In the invention, the heating reflux temperature is preferably 117-125 ℃, and the time is preferably 10-12 h; the heating reflux is preferably carried out under nitrogen protection. In the invention, the heating reflux has the function of fully heating the system, improving the reaction progress degree and shortening the reaction progress time. After the heating reflux is finished, the mixed solution is cooled to obtain a supersaturated solution. The present invention is not particularly limited to the particular embodiment of cooling, and may be practiced in a manner well known to those skilled in the art.
After the supersaturated solution is obtained, the invention carries out hydrothermal treatment on the supersaturated solution to precipitate the spiro tetraphenol. In the invention, the temperature of the hydrothermal treatment is preferably 200-240 ℃, more preferably 210-230 ℃, the time is preferably 5-8 h, and the pressure is preferably 1-0.5 GPa, more preferably 100-400 MPa. In the present invention, it is preferable that white crystals are precipitated from the supersaturated solution under the above-mentioned conditions of high temperature and high pressure. According to the invention, the white crystals are preferably washed to obtain the spirocyclic tetraphenol, the washing detergent preferably comprises glacial acetic acid and dichloromethane, and the washing detergent preferably adopts glacial acetic acid and dichloromethane to wash alternately.
In the present invention, the spirocyclic tetraphenol has the structure represented by formula V:
after obtaining the spiro-tetraphenol, the invention carries out substitution reaction on the spiro-tetraphenol and the halogenated nitroanisole in the presence of a catalyst and an organic solvent to obtain the tetranitroanisole spiro-compound.
The method comprises the steps of mixing spirocyclic tetraphenol, halogenated nitro methyl ether, a catalyst and an organic solvent to form a mixed feed liquid, wherein the halogenated nitro methyl ether comprises 5-halogenated-2-nitro methyl ether or 2-halogenated-5-nitro methyl ether, preferably 5-fluoro-2-nitro methyl ether, 5-chloro-2-nitro methyl ether, 5-bromo-2-nitro methyl ether, 2-fluoro-5-nitro methyl ether, 2-chloro-5-nitro methyl ether or 2-bromo-5-nitro methyl ether, the molar ratio of spirocyclic tetraphenol to halogenated nitro methyl ether is preferably 1: 4-9, and further preferably 1: 5-8.
After the mixed material liquid is obtained, the invention preferably stirs for 0.5h at room temperature under the protection of nitrogen to ensure that the materials are fully contacted, and then carries out substitution reaction. In the invention, the substitution reaction is preferably carried out under the protection of nitrogen, and in the invention, after the spirocyclic tetraphenol and the halogenated nitrobenzyl ether are mixed, the temperature is raised to the substitution reaction temperature, and then the catalyst is added for the substitution reaction. In the invention, the temperature of the substitution reaction is preferably 150-200 ℃, and more preferably 160-180 ℃; the time is preferably 8-10 h, and the heating rate of heating to the substitution reaction temperature is preferably 10-12 ℃/min; the invention preferably adopts a microwave heating mode to carry out the substitution reaction, and the frequency of the microwave is preferably 2 GHz. After the substitution reaction is completed, the invention preferably discharges the substitution reaction product from n-hexane: and (3) in a mixed system of deionized water 1:1, sequentially carrying out solid-liquid separation, solid drying and recrystallization to obtain the tetranitrobenzyl ether spiro compound.
In the present invention, when the halogenated nitroanisole is 5-halo-2-nitroanisole, the tetranitroanisole spiro compound has a structure shown in formula VI; when the halogenated nitroanisole is 2-halo-5-nitroanisole, the tetranitroanisole spiro compound has a structure shown in formula VII:
after the tetranitro anisole spiro compound is obtained, the tetranitro anisole spiro compound and boron tribromide are subjected to demethylation reaction, and then methanol is adopted for quenching to generate the tetranitro hydroxyl benzene spiro compound.
According to the invention, the dosage ratio of the tetranitro methyl ether spiro compound to boron tribromide and methanol is preferably 1mmol: 6-10 mmol: 10-14 m L, and more preferably 1mmol: 7-9 mmol: 11-13 m L. the tetranitro methyl ether spiro compound and boron tribromide are mixed and then subjected to demethylation reaction, the mixing temperature of the tetranitro methyl ether spiro compound and boron tribromide is preferably-10 to-20 ℃, after the mixing is completed, the mixture of the tetranitro methyl ether spiro compound and boron tribromide is preferably kept at-5 to-10 ℃ for 2-4 h for demethylation reaction, then the mixture is mixed with methanol at-10 to-20 ℃, and is continuously stirred for 1-2 h for quenching reaction, in the invention, the demethylation reaction is preferably carried out in a dichloromethane solvent, after the reaction is completed, the reaction product of the demethylation reaction is preferably discharged into a saturated sodium bicarbonate solution, and then the tetranitro hydroxy benzene compound is obtained through solid-liquid spiro separation and solid drying in sequence.
In the present invention, when the tetranitrobenzyl ether spiro compound has a structure represented by formula VI, the tetranitrohydroxybenzene spiro compound has a structure represented by formula VIII; when the tetranitrobenzyl ether spiro compound has a structure represented by formula VII, the tetranitrohydroxybenzene spiro compound has a structure represented by formula IX:
after the tetranitrohydroxybenzene spiro-compound is obtained, the tetranitrohydroxybenzene spiro-compound is reduced by adopting sodium arsenite in the presence of sodium hydroxide to obtain the polyamine monomer with the structure shown as the formula I or the formula III.
In the invention, sodium arsenite is preferably adopted in an organic solvent to reduce the tetranitrohydroxybenzene spiro-compound; the organic solvent is preferably 1, 4-dioxane or absolute ethyl alcohol. According to the invention, the tetranitrohydroxybenzene spiro-compound is preferably mixed with an organic solvent to form tetranitrohydroxybenzene spiro-compound dispersion liquid, and then the tetranitrohydroxybenzene spiro-compound dispersion liquid is mixed with sodium hydroxide to obtain mixed feed liquid. In the present invention, the mass concentration of the tetranitrohydroxybenzene spiro-compound dispersion is preferably 15% to 20%, and more preferably 16% to 18%; the mass ratio of the tetranitrohydroxybenzene spiro-compound to the sodium hydroxide is preferably 1: 0.1-0.5, and more preferably 1: 0.2-0.4. In the present invention, the sodium hydroxide functions as a catalyst.
After the mixed material liquid is obtained, the mixed material liquid is preferably heated and refluxed, and the heating and refluxing time is preferably 0.5-0.6 h. In the present invention, it is preferable to sufficiently disperse the tetranitrohydroxybenzene spiro-compound and sodium hydroxide in the organic solvent by heating under reflux.
After the heating reflux is completed, the invention preferably adds sodium arsenite into the reaction system to carry out the reduction reaction. In the invention, the molar ratio of the tetranitrohydroxybenzene spiro-compound to the sodium arsenite is preferably 1: 5-8, and more preferably 1: 6-7; the temperature of the reduction reaction is preferably the reflux temperature of the system, the reflux temperature is preferably 100-120 ℃, and the time of the reduction reaction is preferably 8-10 h, and further preferably 10 h.
After the reduction reaction is completed, preferably filtering a reduction reaction product while the product is hot to remove sodium arsenite, collecting filtrate, heating the filtrate to reflux, then adding zinc powder and concentrated hydrochloric acid into the filtrate, carrying out catalytic hydrogenation, finally concentrating the filtrate to obtain a crude product, and drying and recrystallizing the crude product in sequence to obtain the polyamine monomer with the structure of formula I or formula III. in the invention, the mass ratio of the zinc powder to the concentrated hydrochloric acid is preferably 1g: 3-5 m L, the mass concentration of the concentrated hydrochloric acid is preferably 70-75%, the catalytic hydrogenation temperature is preferably 90-120 ℃, and the time is preferably 9-12 h.
In the present invention, when the polyamine monomer has the structure represented by formula II or formula IV, the preparation method comprises the steps of:
(a) heating, refluxing and cooling an acetone solution of hydrogen iodide, an acetic acid solution of catechol and an acetic acid solution of hydroxybenzene to obtain a supersaturated solution, and then carrying out hydrothermal treatment on the supersaturated solution to precipitate the spiro trisphenol; the spiro triphenol has a structure shown in a formula X:
(b) carrying out substitution reaction on the spiro-trisphenol obtained in the step (a) and halogenated nitroanisole in the presence of a catalyst and a solvent to obtain a trinitroanisole spiro-compound; the halogenated nitrobenzyl ethers include 5-halo-2-nitrobenzyl ether or 2-halo-5-nitrobenzyl ether; the catalyst comprises one or two of potassium carbonate and cesium carbonate;
when the halogenated nitroanisole is 5-halo-2-nitroanisole, the trinitroanisole spiro compound has a structure shown in formula XI; when the halogenated nitroanisole is 2-halo-5-nitroanisole, the trinitroanisole spiro compound has a structure represented by formula XII:
(c) carrying out demethylation reaction on the trinitroanisole spiro-compound obtained in the step (b) and boron tribromide, and then carrying out quenching reaction by adopting methanol to generate a trinitrohydroxybenzene spiro-compound; the trinitrohydroxybenzene spiro-compound has a structure shown in a formula XIII or XIV:
(d) reducing the trinitrohydroxybenzene spiro-compound obtained in the step (c) by adopting sodium arsenite in the presence of sodium hydroxide to obtain a polyamine monomer with a structure shown as a formula II or a formula IV.
The method comprises the steps of heating, refluxing and cooling an acetone solution of hydrogen iodide, an acetic acid solution of catechol and an acetic acid solution of hydroxybenzene to obtain a supersaturated solution, and then carrying out hydrothermal treatment on the supersaturated solution to precipitate the spiro trisphenol. In the invention, the molar ratio of hydrogen iodide in the acetone solution of hydrogen iodide to catechol in the acetic acid solution of catechol and the molar ratio of hydroxybenzene in the acetic acid solution of hydroxybenzene is preferably 1: 1-4, and more preferably 1: 2-3. In the present invention, the mass concentration of hydrogen iodide in the acetone solution of hydrogen iodide is preferably 80% to 99%, and more preferably 85%; the mass concentration of the catechol in the catechol acetic acid solution is preferably 10-55%, and more preferably 20-50%, and the mass concentration of the acetic acid in the catechol acetic acid solution is preferably 10-40%, and more preferably 20-30%; the mass concentration of the hydroxybenzene in the acetic acid solution of the hydroxybenzene is preferably 10-85%, and more preferably 20-50%. In the present invention, the acetone functions to provide a reaction environment, and the acetic acid functions as a catalyst. In the invention, the heating reflux time is preferably 10-15 h; the heating reflux is preferably carried out under nitrogen protection. In the invention, the heating reflux has the function of fully heating the system, improving the reaction progress degree and shortening the reaction progress time. After the heating reflux is finished, the mixed solution is cooled to obtain a supersaturated solution. The present invention is not particularly limited to the particular embodiment of cooling, and may be practiced in a manner well known to those skilled in the art.
After the supersaturated solution is obtained, the invention carries out hydrothermal treatment on the supersaturated solution to separate out the spiro trisphenol. In the present invention, the temperature of the hydrothermal treatment is preferably 200 to 240 ℃, more preferably 210 to 230 ℃, and the pressure is preferably 1 to 0.5GPa, more preferably 100 to 400 MPa. In the present invention, it is preferable that the supersaturated solution precipitate white crystals under the above-mentioned conditions of high temperature and high pressure. The white crystals are preferably washed to obtain the spiro trisphenol, the washing detergent preferably comprises glacial acetic acid and dichloromethane, and the white crystals are preferably washed alternately by the glacial acetic acid and the dichloromethane.
In the present invention, the spirocyclic trisphenol has a structure represented by formula X:
after obtaining the spiro-trisphenol, the invention carries out substitution reaction on the spiro-trisphenol and halogenated nitroanisole in the presence of a catalyst and an organic solvent to obtain the trinitroanisole spiro-compound.
The method comprises the steps of mixing spirocyclotrisphenol, halogenated nitro-anisole, a catalyst and an organic solvent to form a mixed feed liquid, wherein the halogenated nitro-anisole comprises 5-halogenated-2-nitro-anisole or 2-halogenated-5-nitro-anisole, preferably 5-fluoro-2-nitro-anisole, 5-chloro-2-nitro-anisole, 5-bromo-2-nitro-anisole, 2-fluoro-5-nitro-anisole, 2-chloro-5-nitro-anisole or 2-bromo-5-nitro-anisole, the molar ratio of spirocyclotetrashenol to the halogenated nitro-anisole is preferably 1: 4-9, and further preferably 1: 5-8.
After the mixed material liquid is obtained, the invention preferably stirs for 0.5h at room temperature under the protection of nitrogen to ensure that the materials are fully contacted, and then carries out substitution reaction. In the invention, the substitution reaction is preferably carried out under the protection of nitrogen, and in the invention, after the spirocyclic tetraphenol and the halogenated nitrobenzyl ether are mixed, the temperature is raised to the substitution reaction temperature, and then the catalyst is added for the substitution reaction. In the invention, the temperature of the substitution reaction is preferably 150-200 ℃, further preferably 160-180 ℃, the time is preferably 8-10 h, and the heating rate of heating to the substitution reaction temperature is preferably 10-12 ℃/min; the invention preferably adopts a microwave heating mode to carry out the substitution reaction, and the frequency of the microwave is preferably 2 GHz. After the substitution reaction is completed, the invention preferably discharges the substitution reaction product from n-hexane: and (3) in a mixed system of deionized water 1:1, sequentially carrying out solid-liquid separation, solid drying and recrystallization to obtain the trinitroanisole spiro-compound.
In the present invention, when the halogenated nitroanisole is 5-halo-2-nitroanisole, the trinitroanisole spiro compound has a structure represented by formula XI; when the halogenated nitroanisole is 2-halo-5-nitroanisole, the trinitroanisole spiro compound has a structure represented by formula XII:
after the trinitroanisole spiro-compound is obtained, the trinitroanisole spiro-compound and boron tribromide are subjected to demethylation reaction, and then methanol quenching is adopted to generate the trinitrohydroxy-benzene spiro-compound.
According to the invention, the dosage ratio of the trinitroanisole spiro compound to boron tribromide and methanol is preferably 1mmol: 6-10 mmol: 10-14 m L, and more preferably 1mmol: 7-9 mmol: 11-13 m L. the trinitroanisole spiro compound and boron tribromide are mixed and then subjected to demethylation reaction, the mixing temperature of the trinitroanisole spiro compound and boron tribromide is preferably-10 ℃ to-20 ℃, after the mixing is completed, the mixture of the trinitroanisole spiro compound and boron tribromide is preferably kept at-5 ℃ to-10 ℃ for 2-4 h for demethylation reaction, then the mixture is mixed with methanol at-10 ℃ to-20 ℃, and is continuously stirred for 1-2 h for quenching reaction, in the invention, the demethylation reaction is preferably carried out in a dichloromethane solvent, after the reaction is completed, the reaction product of the demethylation reaction is preferably discharged into a saturated sodium bicarbonate solution, and then the tetranitrohydroxybenzene spiro compound is obtained by solid-liquid separation and solid drying sequentially.
In the present invention, when the trinitroanisole spiro compound has a structure represented by formula XI, the trinitrohydroxyanisole spiro compound has a structure represented by formula XIII; when the trinitroanisole spiro compound has a structure shown in formula XII, the trinitrohydroxyanisole spiro compound has a structure shown in formula XIV:
after the trinitrohydroxybenzene spiro-compound is obtained, the trinitrohydroxybenzene spiro-compound is reduced by adopting sodium arsenite in the presence of sodium hydroxide to obtain the polyamine monomer with the structure shown as the formula I or the formula III.
The method is characterized in that a trinitrohydroxybenzene spiro-compound is preferably reduced by adopting sodium arsenite in an organic solvent, the organic solvent is preferably 1, 4-dioxane or absolute ethyl alcohol, the trinitrohydroxybenzene spiro-compound is preferably mixed with the organic solvent to form a trinitrohydroxybenzene spiro-compound dispersion liquid, and then the trinitrohydroxybenzene spiro-compound dispersion liquid is mixed with sodium hydroxide to obtain a mixed feed liquid, in the invention, the concentration of the trinitrohydroxybenzene spiro-compound dispersion liquid is preferably 0.05-0.15 g/m L, the mass ratio of the trinitrohydroxybenzene spiro-compound to the sodium hydroxide is preferably 1: 0.1-0.5, and further preferably 1: 0.2-0.4.
After the mixed material liquid is obtained, the mixed material liquid is preferably heated and refluxed, and the heating and refluxing time is preferably 0.5-0.6 h. In the present invention, it is preferable to sufficiently disperse the trinitrohydroxybenzene spiro-compound and sodium hydroxide in the organic solvent by heating under reflux.
After the heating is completed, the present invention preferably adds sodium arsenite to the reaction system to perform the reduction reaction. In the invention, the molar ratio of the trinitrohydroxybenzene spiro-compound to the sodium arsenite is preferably 1: 5-8, and more preferably 1: 6-7; the temperature of the reduction reaction is preferably the reflux temperature of the system, the reflux temperature is preferably 100-120 ℃, and the time of the reduction reaction is preferably 8-10 h.
After the reduction reaction is finished, preferably, filtering a reduction reaction product while the reduction reaction product is hot to remove sodium arsenite, collecting filtrate, heating the filtrate to reflux, then adding zinc powder and concentrated hydrochloric acid into the filtrate, carrying out catalytic hydrogenation, finally concentrating the filtrate to obtain a crude product, and sequentially drying and recrystallizing the crude product to obtain the polyamine monomer with the structure of formula II or formula IV, wherein the mass ratio of the zinc powder to the concentrated hydrochloric acid is preferably 1g: 3-5 m L, the mass concentration of the concentrated hydrochloric acid is preferably 70-75%, the catalytic hydrogenation temperature is preferably 90-120 ℃, and the time is preferably 9-12 h.
The invention also provides polyimide, which has a structure shown in the formula XV:
wherein one of the four R substituents is H and the remaining three R substituents are
Or all four R substituents are
Wherein AR has a structure according to any one of formulas 1 to 3:
in the present invention, formula XV is a repeating structural unit of polyimide.
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 polyamine monomer in a polar organic solvent to obtain a polyamic acid solution; the polyamine monomer is the polyamine monomer 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 polyamine monomer are subjected to polycondensation reaction in a polar organic solvent to obtain the polyamic acid solution.
In the present invention, the polyamine monomer is the polyamine monomer described in the above technical scheme or the polyamine monomer prepared by the preparation method described in the above technical scheme. In the present invention, the dianhydride monomer preferably includes 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride, or 4,4' - (4,4' -diphenoloxypropyl) -dibenzoic anhydride, and the dianhydride monomer preferably has the structure shown in formula XVI:
wherein AR preferably has a structure represented by formula 1, formula 2, or formula 3:
in the present invention, the molar ratio of the polyamine monomer to the dianhydride monomer is preferably 1:1.5 to 3, and more preferably 1:1.5 to 2. In the present invention, the sum of the mass concentrations of the dianhydride monomer and the polyamine monomer in the polar organic solvent is preferably 5% to 8%, and more preferably 6% to 7%. The invention preferably carries out the polycondensation reaction at 0-25 ℃, and the time of the polycondensation reaction is preferably 3-24 h, and more preferably 5-20 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 invention, the volume ratio of the acetic anhydride to the pyridine is preferably 2:1, the using amount ratio of the acetic anhydride to the polyamine monomer is preferably 4m L: 1-3 mmol, in the invention, when the isoquinoline is preferably added, the using amount ratio of the isoquinoline to the polyamine monomer is preferably 0.2-0.3 m L: 1-2 mmol, in the invention, the temperature of the imidization reaction is preferably 60-120 ℃, further preferably 80-100 ℃, and the time of the imidization reaction is preferably 20-24 h.
In the invention, preferably, the imidization reaction product is cooled and discharged into deionized water, and then filtration, 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 invention also provides a polyimide film, which comprises the polyimide prepared by the technical scheme. In the invention, the thickness of the polyimide film is 60-70 um. In the present invention, the method for preparing the polyimide film preferably comprises the steps of:
dissolving polyimide in an organic solvent to form a polyimide solution, then coating the polyimide solution on a substrate, carrying out temperature programming treatment, and then naturally cooling to obtain the polyimide film.
In the present invention, the solid content of the polyimide solution is preferably 10% to 20%, and more preferably 15%. In the present invention, the programmed temperature rise preferably includes four stages, specifically, a first stage, a second stage, a third stage, and a fourth stage, which are sequentially performed; the temperature of the first stage is preferably 55-65 ℃, further preferably 60 ℃, and the time is preferably 3.5-4.5 h, further preferably 4 h; the temperature of the second stage is preferably 85-95 ℃, the further preferred temperature is 90 ℃, and the time is preferably 11.5-12.5 hours, the further preferred time is 12 hours; the temperature of the third stage is preferably 115-125 ℃, further preferably 120 ℃, and the time is preferably 3.5-4.5 hours, further preferably 4 hours; the temperature of the fourth stage is preferably 145-155 ℃, further preferably 150 ℃, and the time is preferably 3.5-4.5 hours, further preferably 4 hours. In the present invention, the cooling is preferably natural cooling.
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
Adding 85g of 99% by mass HI aqueous solution into 15m L of acetone to form a mixed solution, adding the formed mixed solution into 170g of catechol-containing acetic acid aqueous solution, wherein the mass concentration of catechol in the catechol-containing acetic acid aqueous solution is 48.6%, and the mass concentration of acetic acid in the catechol-containing acetic acid aqueous solution is 40%, heating and refluxing the obtained solution at 120 ℃ for 10h, cooling to room temperature to obtain a supersaturated solution, separating out a white microcrystalline compound from the obtained supersaturated solution by a hydrothermal crystallization method at a high temperature and a high pressure of 0.3GPa at 220 ℃, filtering, and washing with glacial acetic acid and dichloromethane alternately for three times to obtain 18.0432g of the spirocyclic tetraphenol compound.
Adding 15mmol of spiro tetraphenol, 64mmol of 5-fluoro-2-nitrobenzyl ether and 96m L of N, N-dimethylformamide into a 250m L three-necked flask with a mechanical stirring device, stirring at room temperature for half an hour under the protection of nitrogen, heating to 150 ℃ at the heating rate of 10 ℃/min by using a microwave with the frequency of 2GHz, adding 64mmol of potassium carbonate, reacting for 10 hours, detecting T L C until a raw material point disappears, stopping the reaction, discharging the system after the reaction into a mixed system of deionized water and deionized water, performing suction filtration, performing vacuum drying at 100 ℃ for 12 hours, and recrystallizing to obtain a tetranitro benzyl ether spiro compound, wherein the obtained product has the following structure:
adding 12mmol of tetranitrobenzyl ether spiro compound and 163m L of dichloromethane into a 250m L three-neck flask provided with a mechanical stirring device, cooling the system to-20 ℃ by using liquid nitrogen, dropwise adding 100m L of dichloromethane solution of boron tribromide with the concentration of 1 mol/L, maintaining the temperature of the system to be-10 ℃ for about 2 hours after the dropwise adding is finished, then cooling the system to-20 ℃ again, dropwise adding 120m L of anhydrous methanol into the system until no white smoke appears, continuously stirring for 1 hour, heating the system to room temperature, discharging the material into saturated sodium bicarbonate, performing suction filtration and drying to obtain the tetranitrohydroxybenzene spiro compound, wherein the obtained product has the structure as follows:
adding 8mmol of the obtained tetranitrohydroxybenzene spiro-compound into a 250m L three-neck flask equipped with a mechanical stirring device, adding 66m L of 1, 4-dioxane to make the solid content of the system 10%, adding 2.0674g of catalyst caustic soda, stirring and heating the system to reflux, refluxing for half an hour, and adding 59mmol of reducing agent sodium arsenite (Na)3AsO3) Refluxing for 10h, detecting by T L C until the raw material point disappears, and filtering while hot (preventing the product from separating out when cooling at temperature) to remove the reducing agent sodium arsenite (Na)3AsO3) Collecting filtrate, heating to reflux, adding 6.5g of zinc powder and 30m of concentrated hydrochloric acid L with the mass concentration of 70% into the system, carrying out catalytic hydrogenation on the filtrate, filtering out the zinc powder while the filtrate is hot, concentrating the filtrate to obtain a crude product, carrying out vacuum drying at 100 ℃ for 12 hours, dissolving the crude product in a good solvent 1, 4-dioxane, heating to the reflux temperature of the reaction solution of 110 ℃, slowly adding a poor solvent deionized water into the reflux reaction solution until precipitation and insolubilization are carried out, closing heating, and carrying out vacuum drying at 100 ℃ for 12 hours to obtain 6.4903g of tetramine compound, wherein the obtained product has the structure as follows:
example 2
Adding 5g of 99% by mass HI aqueous solution into 10m L acetone to form a mixed solution, adding the formed mixed solution into 100m L acetic acid solution containing 105mmol of catechol, wherein the mass concentration of acetic acid in the acetic acid solution is 40%, then adding the mixed solution into 100m L acetic acid solution containing 150mmol of hydroxybenzene, wherein the mass concentration of acetic acid in the acetic acid solution is 40%, stirring, heating and refluxing for 15h under the protection of nitrogen gas, then cooling to room temperature to obtain a supersaturated solution, separating out a white microcrystalline compound from the obtained supersaturated solution by a hydrothermal crystallization method at the high temperature and the high pressure of 240 ℃ and 0.5GPa, filtering, and washing with glacial acetic acid and dichloromethane alternately for three times to obtain the spiro trisphenol compound.
Adding 4.8663g (15mmol) of spiro trisphenol compound, 10.9523g (64mmol) of 5-fluoro-2-nitrobenzyl ether and 72m L of N, N-dimethylformamide into a 250m L three-neck flask with a mechanical stirring device, reacting at room temperature for half an hour under the protection of nitrogen, heating to 150 ℃ by using a microwave with the frequency of 2GHz at the heating rate of 10 ℃/min, adding 8.8454g (64mmol) of potassium carbonate, reacting for 12 hours, detecting by T L C that a raw material point disappears to finish the reaction, stopping the reaction, discharging a system after the reaction, performing suction filtration in a mixed system of N-hexane and deionized water, wherein deionized water is 1:1, performing vacuum drying for 12 hours at 100 ℃, and recrystallizing to obtain a trinitroanisole spiro compound, wherein the obtained product has the following structure:
adding 9.3334g (12mmol) of trinitroanisole spiro compound and 150m L of dichloromethane into a 250m L three-neck flask with a mechanical stirring device, cooling the system to below-20 ℃ by using liquid nitrogen, dropwise adding 110m L of dichloromethane solution of boron tribromide with the concentration of 1 mol/L, maintaining the temperature of the system to be below-10 ℃ for about 2 hours after dropwise adding, then cooling the system to below-20 ℃ again, dropwise adding 125m L of methanol into the system until no white smoke appears, continuously stirring for 1 hour, heating the system to room temperature, discharging, adding saturated sodium bicarbonate, performing suction filtration and drying to obtain the trinitrohydroxybenzene spiro compound, wherein the structure of the obtained product is as follows:
5.8856g (8mmol) of trinitrohydroxybenzene spiro-compound is added into a 250m L three-necked flask with a mechanical stirring device, 60m L of 1, 4-dioxane is added, 2.1250g of catalyst caustic soda is added, the system is stirred and heated to reflux, the system reacts for half an hour, and 6.72g (52mmol) of reducing agent sodium arsenite (Na) is added3AsO3) Refluxing for 8h, detecting by T L C until the raw material point disappears, and filtering while hot (preventing the product from separating out) to remove reducing agent sodium arsenite (Na)3AsO3) Collecting filtrate, heating to reflux, adding 6.0g of zinc powder and 70% concentrated hydrochloric acid 30m L into the system, carrying out catalytic hydrogenation on the filtrate, filtering out the zinc powder while the filtrate is hot, concentrating the filtrate to obtain a crude product, carrying out vacuum drying at 100 ℃ for 12h, dissolving the crude product in a good solvent 1, 4-dioxane, heating to the reflux temperature of the reaction solution of 110 ℃, slowly adding poor solvent deionized water into the reflux reaction solution until precipitation and insolubilization just occur, closing the heating, and carrying out vacuum drying at 100 ℃ for 12h to obtain 5.0564g of triamine compound, wherein the obtained product has the following structure:
example 3
An experiment was conducted in accordance with the procedure of example 1 except that 5-fluoro-2-nitrobenzyl ether was replaced with 2-fluoro-5-nitrobenzyl ether, and the polyamine monomer structure finally obtained was as shown in the following formula:
example 4
An experiment was conducted in accordance with the procedure of example 2, except that 5-fluoro-2-nitrobenzyl ether was replaced with 2-fluoro-5-nitrobenzyl ether, and the polyamine monomer structure finally obtained was as shown in the following formula:
application example 1
In a 50m L three-necked flask equipped with a nitrogen inlet and outlet, a magnetic stirrer, a thermometer and a condenser, under the protection of nitrogen, 2.0mmol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride and 8m L of N, N-dimethylacetamide are added, after dianhydride is completely dissolved, 1mmol of N, N-dimethylacetamide 13m L containing the polyamine monomer prepared in example 1 is slowly added dropwise, the mixture reacts for 24 hours at room temperature to form viscous polyamic acid, 0.1m L isoquinoline is added dropwise into the reaction system, the temperature of the reaction system is increased to 120 ℃, the reaction is maintained for 24 hours, heating is stopped, the system is cooled to room temperature, the material is discharged into 200m L deionized water, ethanol is washed for 3 times in a reflux manner, and the material is dried in a vacuum oven at 80 ℃, so that 0.9504g of target polyimide polymer PI-1 is obtained, and the structure of the obtained product is as follows:
application example 2
In a 50m L three-necked flask equipped with a nitrogen inlet and outlet, a magnetic stirrer, a thermometer and a condenser, under the protection of nitrogen, 2.5mmol of 3,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride and 6m L of N, N-dimethylacetamide are added, after all dianhydride is dissolved, 1mmol of N, N-dimethylacetamide 12m L containing polyamine monomer prepared in example 1 is slowly added dropwise, the system is maintained in an ice-water bath for reaction for 24 hours to form viscous polyamic acid, 1m L pyridine and 2m L acetic anhydride are added dropwise into the reaction system, the temperature is increased to 60 ℃, the reaction is maintained for 24 hours, heating is stopped, the system is cooled to room temperature, the material is discharged into 200m L deionized water, ethanol is refluxed and washed for 3 times, and dried in a vacuum oven at 80 ℃, 0.7004g of target polyimide polymer PI-2 is obtained, and the structure of the obtained product is as follows:
application example 3
In a 50m L three-necked flask equipped with a nitrogen inlet and outlet, a magnetic stirrer, a thermometer and a condenser, under the protection of nitrogen, 1.5mmol of 4,4'- (4,4' -diphenol oxypropyl) -dibenzoic anhydride and 10m L of N, N-dimethylacetamide are added, after dianhydride is completely dissolved, 1mmol of N, N-dimethylacetamide 16m L containing polyamine monomer prepared in example 1 is slowly added dropwise, reaction is carried out at room temperature for 24h to form viscous polyamic acid, 1m L pyridine and 2m L acetic anhydride are added dropwise into the reaction system, the temperature is raised to 60 ℃, the reaction is maintained for 24h, heating is stopped, the system is cooled to room temperature, discharging is carried out in 200m L deionized water, ethanol is refluxed and washed for 3 times, and drying is carried out in a vacuum oven at 80 ℃ to obtain 1.0041g of target polyimide polymer PI-3, and the obtained product has the following structure:
application example 4
In a 50m L three-necked flask equipped with a nitrogen inlet and outlet, a magnetic stirrer, a thermometer and a condenser, under the protection of nitrogen, 1.5mmol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride and 8m L of N, N-dimethylacetamide are added, after dianhydride is completely dissolved, 1mmol of N, N-dimethylacetamide 11m L containing the polyamine monomer prepared in example 2 is slowly added dropwise, the mixture reacts for 24 hours at room temperature to form viscous polyamic acid, 1m L of pyridine and 2m L of acetic anhydride are added dropwise into the reaction system, the temperature of the reaction system is increased to 80 ℃, the reaction is maintained for 24 hours, the heating is closed, the system is cooled to room temperature, the material is discharged into 200m L of deionized water, ethanol is washed for 3 times by reflux, and the material is dried in a vacuum oven at 80 ℃ to obtain 0.8003g of target polyimide polymer PI-4, and the obtained product has the following structure as follows:
application example 5
In a 50m L three-necked flask equipped with a nitrogen inlet and outlet, a magnetic stirrer, a thermometer and a condenser, under the protection of nitrogen, 1.5mmol of 3,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride and 6m L of N, N-dimethylacetamide are added, after dianhydride is completely dissolved, 1mmol of N, N-dimethylacetamide 10m L containing polyamine monomer prepared in example 2 is slowly dropped to react for 24h at room temperature to form viscous polyamic acid, 1m L pyridine and 2m L acetic anhydride are dropped to the reaction system, the temperature of the reaction system is raised to 80 ℃, the reaction is maintained for 24h, heating is stopped, the system is cooled to room temperature, the material is discharged into 200m L deionized water, ethanol is refluxed and washed for 3 times, and dried in a vacuum oven at 80 ℃, 0.6024g of target polyimide polymer PI-5 is obtained, and the structure of the obtained product is as follows:
application example 6
In a 50m L three-necked flask equipped with a nitrogen inlet and outlet, a magnetic stirrer, a thermometer and a condenser, under the protection of nitrogen, 1.5mmol of 4,4'- (4,4' -diphenol oxypropyl) -dibenzoic anhydride and 10m L of N, N-dimethylacetamide are added, after dianhydride is completely dissolved, 1mmol of N, N-dimethylacetamide 13m L prepared in example 2 is slowly added dropwise, reaction is carried out at room temperature for 24h to form viscous polyamic acid, 1m L of pyridine and 2m L of acetic anhydride are added dropwise into the reaction system, the temperature of the reaction system is raised to 80 ℃, the reaction is maintained for 24h, heating is stopped, the system is cooled to room temperature, the material is discharged into 200m L deionized water, ethanol is washed for 3 times by reflux, and the material is dried in a vacuum oven at 80 ℃ to obtain 0.9003g of target polyimide polymer PI-6, and the obtained product has the following structure:
structural characterization
The polyamine monomer prepared in example 1 was subjected to nuclear magnetic resonance test, and the test results are shown in FIG. 1. it can be seen from FIG. 1 that the polyamine monomer prepared according to the present invention has a structure consistent with the expected structure.
The polyimide prepared by the method of the invention is subjected to infrared test, the test result is shown in fig. 2, and as can be seen from fig. 2, the polyimide structure prepared by the method of the invention is in accordance with the expectation.
The pore size distribution of the polyimide obtained by the method of application examples 1 to 3 was obtained by performing a carbon dioxide adsorption-desorption test on the polyimide obtained by the method of application examples 1 to 3, the pore size distribution of the polyimide obtained by the method of application examples 1 to 3 was shown in FIG. 3, the pore size distribution of the polyimide obtained by the method of application examples 1 to 3 was obtained from FIG. 3, the unit of abscissa of the pore size distribution graph shown in FIG. 3 was nm, and the unit of ordinate was (cm)3.nm-1.g-1) (ii) a The pore size distribution range of application examples 1 to 3 is about 0.55 to 0.65nm, and thus, the hyperbranched polyimide polymer provided by the invention has a microporous structure, and the existence of the microporous structure enables small gas molecules to easily permeate into the hyperbranched polyimide polymer, so that the selective permeability of the film is improved.
Performance testing
Solubility test
The solubility of the polyimide prepared in the application examples 1 to 6 was tested, and the test method was: the polyimide was dissolved in DMAC, DMF, NMP, DMSO, THF and CHCl, respectively3The concentration of the polyimide in different solvents is 10mg/m L. the solubility of the polyimide in different solvents is tested, wherein the polyimide is completely soluble at room temperature, the polyimide is completely soluble by heating, the polyimide is partially soluble, the polyimide is insoluble by heating, and the test results are shown in Table 1.
TABLE 1 solubility of polyimide obtained by application examples 1 to 6
As can be seen from the test results in Table 1, the polyimide prepared from the polyamine monomer provided by the invention has better solubility. The polyamine monomer provided by the invention introduces groups such as aliphatic structures, ether bonds and the like, so that the polyimide prepared from the polyamine monomer has good solubility in most polar solvents.
Gas separation test
The polyimide film prepared from the polyimide prepared in application examples 1-6 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 the examples 1 to 6 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 application examples 1 to 6
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 for nitrogen of 5-33 Barrer, a permeability coefficient for methane of 7-62 Barrer, a permeability coefficient for oxygen of 25-119 Barrer and a permeability coefficient for carbon dioxide of 98-540 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 14.2-21.8 for a mixed gas of carbon dioxide and nitrogen, a gas separation coefficient of 8.0-20.2 for a mixed gas of carbon dioxide and methane, and a gas separation coefficient of 3.6-5.3 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 polyamine monomer provided by the invention is applied to DMAC, DMF, NMP, DMSO, THF and CHCl3The polyimide film prepared from the polyimide has better solubility, can ensure good selectivity in the field of gas separation, and has the characteristic of high permeability.
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 polyamine monomer having a structure represented by any one of formulas I to IV:
2. the method of preparing a polyamine monomer according to claim 1, wherein when the polyamine monomer has the structure of formula I or formula III, the method comprises the steps of:
(1) heating, refluxing and cooling an acetone solution of hydrogen iodide and an acetic acid solution of catechol to obtain a supersaturated solution, and then carrying out hydrothermal treatment on the supersaturated solution to precipitate spiro tetraphenol; the spiro tetraphenol has a structure represented by formula V:
(2) carrying out substitution reaction on the spiro tetraphenol obtained in the step (1) and halogenated nitro methyl ether in the presence of a catalyst and an organic solvent by adopting a microwave heating mode to obtain a tetranitro methyl ether spiro compound; the halogenated nitrobenzyl ether is 5-halogenated-2-nitrobenzyl ether or 2-halogenated-5-nitrobenzyl ether; the catalyst is one or two of potassium carbonate and cesium carbonate;
when the halogenated nitroanisole is 5-halo-2-nitroanisole, the tetranitroanisole spiro compound has a structure shown in formula VI; when the halogenated nitroanisole is 2-halo-5-nitroanisole, the tetranitroanisole spiro compound has a structure shown in formula VII:
(3) performing demethylation reaction on the tetranitrobenzyl ether spiro compound obtained in the step (2) and boron tribromide, and then quenching by adopting methanol to generate a tetranitrohydroxybenzene spiro compound; the tetranitrohydroxybenzene spiro-compound has a structure shown in a formula VIII or a formula IX:
(4) in the presence of sodium hydroxide, reducing the tetranitrohydroxybenzene spiro-compound obtained in the step (3) by adopting sodium arsenite to obtain a polyamine monomer with a structure shown as a formula I or a formula III;
when the polyamine monomer has the structure of formula II or formula IV, the preparation method comprises the following steps:
(a) heating, refluxing and cooling an acetone solution of hydrogen iodide, an acetic acid solution of catechol and an acetic acid solution of hydroxybenzene to obtain a supersaturated solution, and then carrying out hydrothermal treatment on the supersaturated solution to precipitate the spiro trisphenol; the spiro triphenol has a structure shown in a formula X:
(b) carrying out substitution reaction on the spiro-trisphenol obtained in the step (a) and halogenated nitroanisole in the presence of a catalyst and an organic solvent by adopting a microwave heating mode to obtain a trinitroanisole spiro-compound; the halogenated nitrobenzyl ether is 5-halogenated-2-nitrobenzyl ether or 2-halogenated-5-nitrobenzyl ether; the catalyst is one or two of potassium carbonate and cesium carbonate;
when the halogenated nitroanisole is 5-halo-2-nitroanisole, the trinitroanisole spiro compound has a structure shown in formula XI; when the halogenated nitroanisole is 2-halo-5-nitroanisole, the trinitroanisole spiro compound has a structure represented by formula XII:
(c) carrying out demethylation reaction on the trinitroanisole spiro-compound obtained in the step (b), boron tribromide and methanol, and then quenching by adopting methanol to generate a trinitrohydroxy benzene spiro-compound; the trinitrohydroxybenzene spiro-compound has a structure shown in a formula XIII or XIV:
(d) reducing the trinitrohydroxybenzene spiro-compound obtained in the step (c) by adopting sodium arsenite in the presence of sodium hydroxide to obtain a polyamine monomer with a structure shown as a formula II or a formula IV.
3. The preparation method according to claim 2, wherein the molar ratio of hydrogen iodide to catechol in the step (1) is 1: 2-5; the temperature of the hydrothermal treatment in the step (1) is 200-240 ℃, and the pressure is 1 MPa-0.5 GPa.
4. The method according to claim 2, wherein the molar ratio of hydrogen iodide, catechol, and hydroxybenzene in the step (a) is 1:1 to 4; the temperature of the hydrothermal treatment in the step (a) is 200-240 ℃, and the pressure is 1 MPa-0.5 GPa.
5. The preparation method according to claim 2, wherein the molar ratio of the spirocyclic tetraphenol to the halogenated nitroanisole in the step (2) is 1: 4-9; the temperature of the substitution reaction in the step (2) is 150-200 ℃, and the time is 8-10 h;
the molar ratio of the spiro trisphenol to the halogenated nitrobenzyl ether in the step (b) is 1: 4-9; the temperature of the substitution reaction in the step (b) is 150-200 ℃, and the time is 8-10 h.
6. The preparation method according to claim 2, wherein the dosage ratio of the tetranitrobenzyl ether spiro compound to the boron tribromide and the methanol in the step (3) is 1mmol: 6-10 mmol: 10-14 m L, the temperature of the demethylation reaction in the step (3) is-5 to-10 ℃, and the time is 2-4 h;
the dosage ratio of the trinitroanisole spiro-compound to the boron tribromide and the methanol in the step (c) is 1mmol: 6-10 mmol: 10-14 m L, the temperature of the demethylation reaction in the step (c) is-5 to-10 ℃, and the time is 2-4 hours.
7. The preparation method according to claim 2, wherein the molar ratio of the tetranitrohydroxybenzene spiro-compound to the sodium arsenite in the step (4) is 1: 5-8; the temperature of reduction in the step (4) is 100-120 ℃, and the time is 8-10 h;
the molar ratio of the trinitrohydroxybenzene spiro-compound to the sodium arsenite in the step (d) is 1: 5-8; the temperature of the reduction in the step (d) is 100-130 ℃, and the time is 8-10 h.
8. A polyimide having a structure represented by formula XV:
wherein one of the four R substituents is H and the remaining three R substituents are
Or all four R substituents are
Wherein AR has a structure according to any one of formulas 1 to 3:
9. a method for preparing the polyimide according to claim 8, comprising the steps of:
(i) under the protection of nitrogen, carrying out polycondensation reaction on a dianhydride monomer and a polyamine monomer in a polar organic solvent to obtain a polyamic acid solution; the polyamine monomer is the polyamine monomer of claim 1 or the polyamine monomer prepared by the preparation method of any one of claims 2 to 7;
(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 film comprising the polyimide according to claim 8 or the polyimide produced by the method according to claim 9; the thickness of the polyimide film is 60-70 mu m.
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