CN111233842B - Phthalazinone diamine monomer and preparation method thereof, polyimide and preparation method thereof, and polyimide film - Google Patents

Phthalazinone diamine monomer and preparation method thereof, polyimide and preparation method thereof, and polyimide film Download PDF

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CN111233842B
CN111233842B CN202010200683.0A CN202010200683A CN111233842B CN 111233842 B CN111233842 B CN 111233842B CN 202010200683 A CN202010200683 A CN 202010200683A CN 111233842 B CN111233842 B CN 111233842B
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phthalazinone
heteronaphthalene
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CN111233842A (en
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陈春海
金嗣卓
王书丽
周宏伟
王大明
赵晓刚
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Jilin University
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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Abstract

The invention relates to the technical field of organic chemistry, in particular to a phthalazinone diamine monomer and a preparation method thereof, polyimide and a preparation method thereof, and a polyimide film. The polyimide film prepared from the phthalazinone diamine monomer can improve the permeability, solubility and the like of gas on the premise of maintaining selectivity; in addition, the polyimide prepared from the phthalazinone diamine monomer provided by the invention has better solubility.

Description

Phthalazinone diamine monomer and preparation method thereof, polyimide and preparation method thereof, and polyimide film
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a phthalazinone diamine 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 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 like, and the method is characterized in that2/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 permeability and high selectivity.
Disclosure of Invention
Aiming at the problems of the polyimide film, the invention provides the phthalazinone diamine monomer, and the polyimide film obtained from the phthalazinone diamine monomer has the characteristics of high permeability and good solubility while ensuring good selectivity.
The invention provides a phthalazinone diamine monomer, which has a structure shown in formula I:
Figure BDA0002419264710000021
the invention provides a phthalazinone diamine mixed monomer, which comprises four compounds in the phthalazinone diamine monomer in the technical scheme, wherein the four compounds respectively have structures shown in formulas II-1-II-4:
Figure BDA0002419264710000022
the invention also provides a preparation method of the phthalazinone diamine monomer in the technical scheme, which comprises the following steps:
(1) mixing 2-iodobenzoic acid methyl ester, 3, 4-dimethoxybenzaldehyde and hydrazine hydrate in an aromatic hydrocarbon solvent for reaction to obtain 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone;
(2) carrying out nucleophilic substitution reaction on the 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone, the 4-fluoro-1, 2-dimethoxybenzene and the catalyst obtained in the step (1) in water to obtain 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone; the catalyst is potassium carbonate or cesium carbonate;
(3) dissolving the 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone obtained in the step (2) in a polar organic solvent, dropwise adding boron tribromide under the conditions of low temperature and protective gas, and performing demethylation reaction to obtain the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone; the low temperature is-20 to-6 ℃;
(4) carrying out oxidation reaction on the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone obtained in the step (3) and an oxidant in dichloromethane to obtain 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone;
(5) carrying out dehydration reaction on the 4- (3, 4-tetracarbonyl diphenyl) hetero naphthalene-1-phthalazinone and 4-nitro o-phenylenediamine obtained in the step (4) in dimethyl sulfoxide to obtain hetero naphthalene-dinitro-1-phthalazinone;
(6) under the protective atmosphere, the naphthalene-dinitro-1-phthalazinone obtained in the step (5), hydrazine hydrate and palladium-carbon are subjected to reduction reaction in dioxane to obtain a phthalazinone diamine monomer shown in the formula I; the structural formula of the formula I is as follows:
Figure BDA0002419264710000031
preferably, the molar ratio of the methyl 2-iodobenzoate, the 3, 4-dimethoxybenzaldehyde and the hydrazine hydrate in the step (1) is 1: 1-3: 14-16; the temperature of the mixing reaction is 100-130 ℃.
Preferably, the molar ratio of the 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone to the 4-fluoro-1, 2-dimethoxybenzene in the step (2) is 1: 1-1.2; the temperature of the nucleophilic substitution reaction is 80-100 ℃, and the time is 12-15 h.
Preferably, the molar ratio of the 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone to the boron tribromide in the step (3) is 1: 1.5-2; the temperature of the demethylation reaction is-12 to-4 ℃, and the time is 1 to 6 hours.
Preferably, the oxidant in the step (4) is tetra-n-butyl ammonium chromate or dichromate, and the temperature of the oxidation reaction is 25-35 ℃ and the time is 15-20 min.
The invention provides a preparation method of polyimide, which comprises the following steps:
(i) under the protection of nitrogen, carrying out polycondensation reaction on a dianhydride monomer and a phthalazinone diamine monomer in a polar organic solvent to obtain a polyamic acid solution; the phthalazinone diamine monomer is the phthalazinone diamine monomer of claim 1 or the phthalazinone diamine mixed monomer of claim 2;
(ii) and (i) mixing the polyamic acid solution obtained in the step (i) with a catalyst and a dehydrating agent, and carrying out imidization reaction to obtain polyimide.
The invention provides polyimide prepared by the method in the technical scheme, and the polyimide has a structure shown in a formula A:
Figure BDA0002419264710000041
in the formula A
Figure BDA0002419264710000042
Has a structure shown in formula 1, formula 2 or formula 3:
Figure BDA0002419264710000043
the polymerization degree of the polyimide is 80-100.
The invention provides a polyimide film prepared from the polyimide in the technical scheme.
Has the advantages that:
the structure of the phthalazinone diamine monomer provided by the invention contains a plurality of polar groups such as tertiary amino groups and the like, so that the interaction with a polar organic solvent can be increased, and the polar tertiary amino groups are still remained in the polyimide structure prepared from the phthalazinone diamine monomer, so that the polyimide also has better solubility. The phthalazinone diamine monomer structurally contains basic group tertiary aminoAnd the polyimide polymer prepared from the phthalazinone diamine monomer has a plurality of benzene ring structures, so that the polarity and the rigidity of the polymer are increased, the free volume of the polymer is increased, and the gas permeability of the polyimide film is better. The phthalazinone diamine monomer provided by the invention structurally has a tertiary amino group with a basic group, and CO2The molecule has strong C ═ O dipole bond, can form quadrupole moment, and the polar unit tertiary amino in the polymer can react with CO2Polar interaction of (2) increasing Polymer to CO2Permselectivity of (a).
The results of the examples show that the polyimide prepared from the phthalazinone diamine monomer provided by the invention can be used in DMAC, DMF, NMP, DMSO, THF, CHCl3And 1, 4-dioxane has better solubility; 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 an IR spectrum of a hetero-naphthalene-diamino-1-phthalazinone prepared in example 6;
FIG. 2 is the hydrogen nuclear magnetic spectrum of the hetero-naphthalene-diamino-1-phthalazinone prepared in example 6;
FIG. 3 is a carbon spectrum magnetic spectrum of the hetero naphthalene-diamino-1-phthalazinone prepared in example 6.
Detailed Description
The invention provides a phthalazinone diamine monomer, which has a structure shown in formula I:
Figure BDA0002419264710000051
in the present invention, "-" in the upper right corner of the structural formulae 1 and 2 represents a substituent position, not a methyl group.
In the invention, the phthalazinone diamine monomer is a mixture of four compounds, and the four compounds respectively have structures shown in formulas II-1 to II-4:
Figure BDA0002419264710000052
Figure BDA0002419264710000061
the invention also provides a preparation method of the phthalazinone diamine monomer in the technical scheme, which comprises the following steps:
(1) mixing 2-iodobenzoic acid methyl ester, 3, 4-dimethoxybenzaldehyde and hydrazine hydrate in an aromatic hydrocarbon solvent for reaction to obtain 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone;
(2) carrying out nucleophilic substitution reaction on the 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone, the 4-fluoro-1, 2-dimethoxybenzene and the catalyst obtained in the step (1) in water to obtain 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone; the catalyst is potassium carbonate or cesium carbonate;
(3) dissolving the 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone obtained in the step (2) in a polar organic solvent, dropwise adding boron tribromide under the conditions of low temperature and protective gas, and performing demethylation reaction to obtain the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone; the low temperature is-20 to-6 ℃;
(4) carrying out oxidation reaction on the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone obtained in the step (3) and an oxidant in dichloromethane to obtain 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone;
(5) carrying out dehydration reaction on the 4- (3, 4-tetracarbonyl diphenyl) hetero naphthalene-1-phthalazinone and 4-nitro o-phenylenediamine obtained in the step (4) in dimethyl sulfoxide to obtain hetero naphthalene-dinitro-1-phthalazinone;
(6) and (3) under a protective atmosphere, carrying out reduction reaction on the naphthalene-dinitro-1-phthalazinone obtained in the step (5), hydrazine hydrate and palladium carbon in dioxane to obtain a phthalazinone diamine monomer shown in the formula I.
The invention carries out mixed reaction on 2-iodobenzoic acid methyl ester, 3, 4-dimethoxybenzaldehyde and hydrazine hydrate in an aromatic solvent to obtain 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone.
In the present invention, the aromatic hydrocarbon solvent is preferably toluene or xylene; the molar ratio of the methyl 2-iodobenzoate to the 3, 4-dimethoxybenzaldehyde to the hydrazine hydrate is preferably 1: 1-3: 14-16, and more preferably 1:1: 15; the dosage ratio of the methyl 2-iodobenzoate to the organic solvent is preferably 1mmol: 3-5 mL, and more preferably 1mmol:4 mL. In the invention, the temperature of the mixing reaction is preferably 100-130 ℃, and the time of the mixing reaction is preferably as follows: TLC detection till the starting point of the methyl 2-iodobenzoate disappears. In the process of the mixed reaction, two reactions occur together, namely hydrazinolysis of an ester group in 2-iodomethyl benzoate, and nucleophilic substitution reaction between an aldehyde group on 3, 4-dimethoxybenzaldehyde and an iodine atom on a hydrazinolysis product; the mixing reaction is shown as formula (1):
Figure BDA0002419264710000071
according to the invention, preferably, after the mixed reaction is finished, the mixed reaction system is discharged into deionized water, and then the processes of suction filtration, filter cake drying and recrystallization are sequentially carried out, so as to obtain the 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone. In the present invention, the recrystallization preferably includes the steps of: dissolving the dried filter cake into enough 1, 4-dioxane, adding deionized water until crystals are precipitated and are not dissolved by stirring, then carrying out suction filtration, and drying the filter cake to obtain the 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone. The drying method of the present invention is not particularly limited, and a drying method known to those skilled in the art may be used.
After 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone is obtained, the invention carries out nucleophilic substitution reaction on 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone, 4-fluoro-1, 2-dimethoxybenzene and a catalyst in water to obtain 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone; the catalyst is potassium carbonate or cesium carbonate.
In the invention, the molar ratio of the 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone to the 4-fluoro-1, 2-dimethoxybenzene is preferably 1: 1-1.2, and the usage ratio of the 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone to the deionized water is preferably 1mmol: 3-5 mL, and more preferably 1mmol:4.5 mL. In the invention, the temperature of the nucleophilic substitution reaction is preferably 80-100 ℃, and the time is preferably 12-15 h. In the nucleophilic substitution reaction of the present invention, a reaction represented by formula (2) occurs:
Figure BDA0002419264710000081
after the nucleophilic substitution reaction is finished, the nucleophilic substitution reaction system is preferably discharged into deionized water, and then the 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone is obtained by sequentially carrying out suction filtration, filter cake drying and recrystallization treatment. In the present invention, the recrystallization preferably includes the steps of: dissolving the dried filter cake into enough 1, 4-dioxane, adding deionized water until crystals are precipitated and are not dissolved by stirring, then carrying out suction filtration and drying the filter cake to obtain the 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone. The drying method of the present invention is not particularly limited, and a drying method known to those skilled in the art may be used.
After 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone is obtained, the invention dissolves 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone in a polar organic solvent, boron tribromide is dripped under the conditions of low temperature and protective gas, and demethylation reaction is carried out, thus obtaining 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone.
In the present invention, the polar organic solvent is preferably dichloromethane or acetonitrile; the preferable dosage ratio of the 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone to the polar organic solvent is 8-12 mmol:100 mL. In the invention, the 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone is preferably dissolved in a polar organic solvent, and the obtained 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone solution is placed under the conditions of low temperature and nitrogen protection, and boron tribromide is dropwise added. In the present invention, the low temperature is-20 to-6 ℃. In the present invention, the protective gas is preferably a nitrogen gas, and the present invention is preferably carried out by continuously introducing nitrogen gas into the reaction system or under a sealed condition filled with nitrogen gas. In the invention, the molar ratio of the 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone product to boron tribromide is preferably 1: 1.5-2. In the invention, the dripping speed of the boron tribromide is preferably 0.2-0.5 mL/s; the temperature of the demethylation reaction is preferably-10 to-5 ℃, and the time is preferably 2 to 4 hours. In the present invention, the demethylation reaction time is preferably calculated from the completion of the addition of boron tribromide.
In the demethylation reaction process, the reaction shown as a formula (3) occurs:
Figure BDA0002419264710000091
after the demethylation reaction is completed, the demethylation reaction system is preferably discharged into methanol, and then filtration, filter cake washing and filter cake drying treatment are sequentially carried out to obtain the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone product. In the present invention, the cake washing detergent is preferably methanol. The filter cake drying treatment of the present invention is not particularly limited, and a drying method known to those skilled in the art may be employed.
After obtaining the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone product, the invention carries out oxidation reaction on the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone product and an oxidant in dichloromethane to obtain the 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone.
In the invention, the oxidant is preferably tetra-n-butyl ammonium chromate or dichromate, and the molar ratio of the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone to the oxidant is preferably 1: 4-6. In the invention, the dosage ratio of the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone to dichloromethane is preferably 8-12 mmol:100 mL. In the invention, the temperature of the oxidation reaction is preferably 28-30 ℃, and the time is preferably 15-18 min. In the oxidation reaction process, the reaction shown as the formula (4) occurs:
Figure BDA0002419264710000092
after the oxidation reaction is finished, the invention preferably adds distilled water into the oxidation reaction system for liquid separation treatment, takes out an organic phase, and then carries out drying and rotary evaporation treatment on the organic phase in turn to obtain the 4- (3, 4-tetracarbonyl diphenyl) heteronaphthalene-1-phthalazinone product. In the present invention, the drying desiccant is preferably anhydrous magnesium sulfate; the rotary evaporation was used to remove dichloromethane.
After 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone is obtained, the invention carries out dehydration reaction on the 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone product and 4-nitrophthalenediamine in dimethyl sulfoxide to obtain the heteronaphthalene-dinitro-1-phthalazinone.
In the invention, the molar ratio of the 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone to the 4-nitrophthalenediamine is preferably 1: 2-2.5, and the dosage ratio of the 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone to the dimethyl sulfoxide is preferably 8-12 mmol:20 mL. In the invention, the temperature of the dehydration reaction is preferably 70-90 ℃, and the time of the dehydration reaction is preferably 12-14 h. TLC detection until the material spot disappeared.
In the dehydration reaction process, the reaction shown as the formula (5) occurs:
Figure BDA0002419264710000101
after the dehydration reaction is finished, the dehydration reaction system is preferably discharged into deionized water, and then filtration, filter cake washing, filter cake drying and recrystallization treatment are sequentially carried out to obtain the heteronaphthalene-dinitro-1-phthalazinone. In the present invention, the cake washing detergent is preferably deionized water. In the present invention, the recrystallization preferably includes the steps of: dissolving the dried filter cake in sufficient dichloromethane, adding ethanol until crystals are precipitated and are not dissolved by stirring, then carrying out suction filtration, and drying the filter cake to obtain the heteronaphthalene-dinitro-1-phthalazinone. The drying method of the present invention is not particularly limited, and a drying method known to those skilled in the art may be used.
After the naphthalene-dinitro-1-phthalazinone is obtained, the invention carries out reduction reaction on the naphthalene-dinitro-1-phthalazinone product, hydrazine hydrate and palladium carbon in dioxane under the protective atmosphere to obtain a phthalazinone diamine monomer.
In the present invention, the protective atmosphere is preferably an inert gas atmosphere or a nitrogen atmosphere. In the invention, the mol ratio of the heteronaphthalene-dinitro-1-phthalazinone product to hydrazine hydrate is preferably 1: 20-25, and the mass ratio of the heteronaphthalene-dinitro-1-phthalazinone product to palladium carbon is preferably 1: 0.5-1.5. In the invention, the volume ratio of the total mass of the heteronaphthalene-dinitro-1-phthalazinone product and the palladium-carbon to the dioxane is preferably 5-10 g:29 mL. In the invention, the temperature of the reduction reaction is preferably 110-120 ℃, and the time is preferably 12-15 h.
In the process of the reduction reaction, the reaction shown in the formula (6) occurs:
Figure BDA0002419264710000111
after the reduction reaction is finished, the reduction reaction system is preferably filtered to remove palladium carbon, filtrate is collected, then the filtrate is subjected to reduced pressure distillation, distillate is discharged into deionized water, and solids are collected by filtration to obtain the phthalazinone diamine monomer. The phthalazinone diamine monomer prepared by the method provided by the invention is a mixture of four phthalazinone diamine monomers shown in formulas II-1-II-4.
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 phthalazinone diamine monomer in a polar organic solvent to obtain a polyamic acid solution; the phthalazinone diamine monomer is the phthalazinone diamine monomer or the mixed phthalazinone diamine monomer in the technical scheme;
(ii) and (i) mixing the polyamic acid solution obtained in the step (i) with a catalyst and a dehydrating agent, and carrying out imidization reaction to obtain polyimide.
In the invention, under the protection of nitrogen, dianhydride monomer and phthalazinone diamine monomer are subjected to polycondensation reaction in a polar organic solvent to obtain a polyamic acid solution.
In the present invention, the phthalazinone diamine monomer is preferably a phthalazinone diamine mixed monomer 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 III:
Figure BDA0002419264710000121
wherein AR preferably has a structure represented by formula 1, formula 2, or formula 3:
Figure BDA0002419264710000122
in the present invention, the molar ratio of the dianhydride monomer to the phthalazinone diamine mixed monomer is preferably 1:0.8 to 1.2, and more preferably 1:1. In the present invention, the kind of the polar organic solvent preferably includes N, N '-dimethylformamide or N, N' -dimethylacetamide. In the present invention, the sum of the mass concentrations of the dianhydride monomer and the phthalazinone diamine mixed monomer in the polar organic solvent is preferably 28% to 32%, and more preferably 30%. The invention preferably carries out the polycondensation reaction at room temperature, and the time of the polycondensation reaction is preferably 3-24 h.
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 is preferably pyridine; the dehydrating agent is preferably acetic anhydride. In the invention, the volume ratio of the catalyst to the dehydrating agent is preferably 1:2, and the dosage ratio of the dehydrating agent to the phthalazinone diamine mixed monomer is preferably 4mL: 3-3.3 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 invention, the temperature of the vacuum drying treatment is preferably 75-85 ℃; the time of the vacuum drying treatment is preferably 12 h.
The invention provides polyimide prepared by the preparation method in the technical scheme, and the polyimide has a structure shown in a formula A:
Figure BDA0002419264710000131
in the formula A
Figure BDA0002419264710000132
Has a structure shown in formula 1, formula 2 or formula 3:
Figure BDA0002419264710000133
the polymerization degree of the polyimide is 80-100.
In the present invention, the polyimide preferably has a structure represented by formula IV or formula V:
Figure BDA0002419264710000134
the polyimide structure provided by the invention contains a plurality of polar tertiary amino groups, so that the interaction with an organic solvent can be increased, and the solubility of the polyimide is improved; the polyimide provided by the invention has a plurality of benzene ring structures, and the polarity and the rigidity of the polyimide are improvedThe free volume of the polyimide is improved, so that the gas permeability of the polyimide film prepared from the polyimide is better; in addition, the polyimide structure contains tertiary amino of basic group, CO2The molecule has strong C ═ O dipole bond and can form quadrupole moment, and the polar unit tertiary amino in the polyimide can react with CO2Polar interaction of (2) increases polyimide to CO2Permselectivity of (a).
The invention also provides a polyimide film prepared from the polyimide. In the invention, the thickness of the polyimide film is preferably 60-70 μm; the preparation method of the polyimide film preferably comprises the following steps:
dissolving polyimide in N, N-dimethylacetamide, performing microfiltration on the obtained solution system, and removing insoluble substances to obtain a polyimide solution;
and coating the polyimide solution on a substrate, and cooling after temperature programming and heating treatment to obtain the polyimide film.
In the present invention, the microfiltration is preferably performed using a 0.45 μm Teflon filter; the mass ratio of the polyimide to the N, N-dimethylacetamide is preferably 15: 100; the filtration is preferably carried out under pressure.
The polyimide solution is coated on a substrate. In the present invention, the coating amount per unit area of the coating is preferably 0.05 to 0.1mL/cm2More preferably 0.07mL/cm2。
In the present invention, the temperature-programmed heating treatment preferably includes: sequentially carrying out first temperature rise on the obtained polyimide wet film to a first temperature for first heat preservation; secondly, raising the temperature to a second temperature for second heat preservation; thirdly, raising the temperature to a third temperature for third heat preservation; fourthly, heating to a fourth temperature for fourth heat preservation; the first temperature rising rate is 5-10 ℃/min, the first temperature is 55-65 ℃, and the first heat preservation time is 4 h; the second temperature rising rate is 5-10 ℃/min, the second temperature is 85-95 ℃, and the second heat preservation time is 12 h; the third temperature rising rate is 5-10 ℃/min, the third temperature is 115-125 ℃, and the third heat preservation time is 4 hours; the fourth temperature rising rate is 5-10 ℃/min, the fourth temperature is 145-155 ℃, and the fourth heat preservation time is 4 h. 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: preparation of 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone
A250 mL flask equipped with a stirrer was charged with 40mL of toluene, 10mmol of methyl 2-iodobenzoate, 10mmol of 3, 4-dimethoxybenzaldehyde and 150mmol of hydrazine hydrate, heated to 110 ℃ for reaction, and the reaction was terminated when the starting material spot disappeared by TLC. Discharging in deionized water, filtering, and drying to obtain crude product. Fully dissolving the crude product in enough 1, 4-dioxane, adding deionized water until crystals are precipitated and are not dissolved by stirring, then carrying out suction filtration and drying to obtain 2.0607g of 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone, wherein the yield is 60%, the purity is 98%, and the structure is as follows:
Figure BDA0002419264710000151
example 2: preparation of 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone
A250 mL flask with a stirring device is added with 45mL deionized water, 10mmol4- (3, 4-dimethoxyphenyl) naphthalene-1-phthalazinone, 12mmol 4-fluoro-1, 2-dimethoxybenzene and 25mmol potassium carbonate, heated to 80 ℃ and stirred for reaction for about 12 hours, and the reaction is finished when TLC detects that the raw material point disappears. Discharging in deionized water, filtering, and drying to obtain crude product. Fully dissolving the crude product in enough 1, 4-dioxane, adding deionized water until crystals are precipitated and are not dissolved by stirring, then carrying out suction filtration and drying to obtain 3.9002g of 4- (3, 4-tetramethoxydiphenyl) naphthalene-1-phthalazinone, wherein the yield is 85%, the purity is 96%, and the structure is as follows:
Figure BDA0002419264710000152
example 3: preparation of 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone
10mmol of 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone and 100mL of acetonitrile are added into a 250mL three-neck flask with a stirring device, the temperature is controlled at-20 ℃, 20mol of boron tribromide is dropwise added under nitrogen, and the reaction is carried out overnight at-5 ℃. Discharging the material into methanol, washing the material for three times by using the methanol, and drying the material to obtain 2.2465g of 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone, wherein the yield is 97%, the purity is 95%, and the structure is as follows:
Figure BDA0002419264710000161
example 4: preparation of 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone
10mmol of 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone, 40mmol of tetra-n-butylammonium chromate and 100mL of dichloromethane are added into a 250mL flask equipped with a reflux device, and heated and refluxed for 15 min. After cooling, 50mL of distilled water was poured, and the mixture was separated with a separatory funnel, the organic phase was retained, and the aqueous phase was discarded. The organic phase is subjected to rotary evaporation to remove the solvent, and dried to obtain 3.4389g of 4- (3, 4-tetracarbonyl diphenyl) naphthalene-1-phthalazinone, the yield is 78%, the purity is 97%, and the structure is as follows:
Figure BDA0002419264710000162
example 5: preparation of heteronaphthalene-dinitro-1-phthalazinone
Adding 10mmol of 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone, 20mmol of 4-nitrophthalenediamine and 20mL of DMSO (dimethyl sulfoxide) into a 100mL flask with a stirring device, heating to 80 ℃, reacting for 12h, and finishing the reaction when a raw material point disappears by TLC (thin layer chromatography). Discharging in deionized water, and performing suction filtration and drying to obtain a crude product. Fully dissolving the mixed solution in sufficient dichloroethane, dropwise adding ethanol until crystallization is separated out and the mixed solution is not dissolved by stirring, and performing suction filtration and drying to obtain the heteronaphthalene-dinitro-1-phthalazinone, wherein the yield is 69%, the purity is 96%, and the structure is as follows:
Figure BDA0002419264710000171
example 6: preparation of heteronaphthalene-diamino-1-phthalazinone
A three-necked flask equipped with a stirring device was charged with 5.9212g (10mmol) of heteronaphthalene-dinitro-1-phthalazinone, 0.2mol of hydrazine hydrate, 2g of palladium on carbon and 29mL of dioxane, at a solids content of 20%. Heating and refluxing for 12h under the protection of nitrogen. Filtering to remove palladium carbon, then carrying out reduced pressure distillation and concentration, discharging in deionized water, and filtering to obtain the product of the heteronaphthalene-diamino-1-phthalazinone, wherein the yield is 92%, the purity is 99%, and the structure is as follows:
Figure BDA0002419264710000172
example 7: preparation of polyimide from heteronaphthalene-diamino-1-phthalazone and 4,4' - (hexafluoro-isopropylene) diphthalic anhydride
In a 50mL three-necked flask provided with a nitrogen inlet and outlet, a magnetic stirrer, a thermometer and a condenser, 3.0mmol of the heteronaphthalene-diamino-1-phthalazinone and 18mL of N, N-dimethylacetamide are added under the protection of nitrogen, and after the heteronaphthalene-diamino-1-phthalazinone is completely dissolved, 3.0mmol of 4,4' - (hexafluoroisopropylene) diphthalic anhydride is added, wherein the solid content of the system is about 15%. Reacted at room temperature for 24h to form a polyamic acid with high viscosity. Dropwise adding 2mL of pyridine and 4mL of acetic anhydride into a reaction system, heating to 60 ℃, maintaining the temperature for reaction for 24 hours, then stopping heating and naturally cooling, discharging into 200mL of deionized water, refluxing and washing with ethanol for 3 times, and drying in a vacuum oven at 80 ℃ to obtain 2.3768g of target polymer PI-1, wherein the yield is 97%, and the obtained product has the following structure:
Figure BDA0002419264710000181
example 8: preparation of polyimide from naphthalene-diamino-1-phthalazone and 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride
In a 50mL three-necked flask provided with a nitrogen inlet and outlet, a magnetic stirrer, a thermometer and a condenser, 3.3mmol of the heteronaphthalene-diamino-1-phthalazinone and 17mL of N, N-dimethylacetamide are added under the protection of nitrogen, and after the heteronaphthalene-diamino-1-phthalazinone is completely dissolved, 3.3mmol of 3,3',4,4' -diphenyl ether tetracid dianhydride is added, wherein the solid content of the system is 15%. Reacted at room temperature for 24h to form a polyamic acid with high viscosity. Dropwise adding 2mL of pyridine and 4mL of acetic anhydride into a reaction system, heating to 60 ℃, maintaining the temperature for reaction for 24 hours, stopping heating, naturally cooling, discharging into 200mL of deionized water, refluxing and washing with ethanol for 3 times, and drying in a vacuum oven at 80 ℃ to obtain 2.2966g of target polymer polyimide PI-2, wherein the polymerization degree is 80-100, the yield is 96%, and the obtained product has the following structure:
Figure BDA0002419264710000182
example 9: preparation of polyimide from heteronaphthalene-diamino-1-phthalazinone and 4,4'- (4,4' -diphenoloxy propyl) -dibenzoic anhydride
In a 50mL three-necked flask provided with a nitrogen inlet and outlet, a magnetic stirrer, a thermometer and a condenser, 3.2mmol of the heteronaphthalene-diamino-1-phthalazinone and 17mL of N, N-dimethylacetamide are added under the protection of nitrogen, and after the heteronaphthalene-diamino-1-phthalazinone is completely dissolved, 3.2mmol of 4,4'- (4,4' -diphenoloxypropyl) -dibenzoic anhydride is added, wherein the solid content of the system is 15%. Reacted at room temperature for 24h to form a polyamic acid with high viscosity. Dropwise adding 2mL of pyridine and 4mL of acetic anhydride into a reaction system, heating to 60 ℃, maintaining the temperature for reaction for 24 hours, then stopping heating and naturally cooling, discharging into 200mL of deionized water, refluxing and washing with ethanol for 3 times, and drying in a vacuum oven at 80 ℃ to obtain 2.2827g of target polymer PI-3, wherein the yield is 98%, and the obtained product has the following structure:
Figure BDA0002419264710000191
structural characterization
As a result of TLC spotting of the final reaction product of example 6, example 6 obtained a mixture, but the mixture was found to be a single substance by nuclear magnetic resonance because the difference in polarity was extremely small. The infrared spectrum and nuclear magnetic spectrum of the hetero-naphthalene-diamino-1-phthalazinone prepared in example 6 are shown in fig. 1-3, and the results are shown in fig. 1, fig. 2 and fig. 3, wherein fig. 1 is the infrared spectrum, fig. 2 is the hydrogen nuclear magnetic spectrum, and fig. 3 is the carbon nuclear magnetic spectrum. The structural formula in fig. 2 corresponds to the nuclear magnetic characteristic peak, represented by the structural formula in fig. 2. As can be seen from fig. 1,2 and 3, the product prepared in example 6 of the present invention has the structure shown in formula I.
Performance testing
(I) solubility test
The solubility of the polyimides prepared in examples 7 to 9 was tested by the following method: 10mg of polyimide is weighed at room temperature and added with DMAC, DMF, NMP, DMSO, THF and CHCl respectively3And 1, 4-dioxane, the concentration of the polyimide in different solvents is 10mg/mL, and the dissolution of the polyimide is observed after the polyimide is placed for 12 hours. The test results are shown in table 1, in table 1: ++: fully dissolving at room temperature; +: heating to 50 ℃ to fully dissolve.
TABLE 1 solubility of polyimides of examples 7 to 9
Figure BDA0002419264710000192
Figure BDA0002419264710000201
As shown in the test results in Table 1, the polyimide prepared from the phthalazinone diamine monomer provided by the invention has better solubility. The phthalazinone diamine monomer structurally contains polar group tertiary amino, so that tertiary amino is still reserved in the polyimide prepared by the invention, the polar group tertiary amino can increase the interaction with an organic solvent, the solubility of the polyimide is further improved, and the polyimide prepared by the phthalazinone diamine monomer has good solubility in most polar solvents.
(II) gas separability test
The polyimide film prepared from the polyimide prepared in the embodiment 7-9 of the invention is prepared by the following specific preparation method:
polyimide was dissolved in N, N-dimethylacetamide at a mass concentration of 15 wt%, and the solution was passed through a 0.45 μm Teflon filter under pressure to remove insoluble matter to obtain a uniform polyimide solution, which was uniformly coated on a clean 9cm X9 cm glass plate at a rate of 0.07mL/cm per unit area2Placing the polyimide film in an oven, adopting programmed heating, sequentially carrying out heat preservation at 60 ℃ for 4h, heat preservation at 90 ℃ for 12h, heat preservation at 120 ℃ for 4h and heat preservation at 150 ℃ for 4h, wherein the heating rate of each stage is 8 ℃/min, and naturally cooling to room temperature to obtain the transparent polyimide film after treatment.
The polyimide films prepared from the polyimides of examples 7 to 9 were subjected to a gas separation test, and the test results are shown in table 2, and the test method was:
the gas separation performance of the polyimide prepared by the invention is tested, and the test method comprises the following steps: 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 7 to 9
Figure BDA0002419264710000202
Figure BDA0002419264710000211
As can be seen from Table 2, the polyimide film provided by the invention has good gas separation performance, and specifically has a permeability coefficient for nitrogen of 2.68-3.14 Barrer, a permeability coefficient for methane of 2.92-3.25 Barrer, a permeability coefficient for oxygen of 13.96-14.42 Barrer, and a permeability coefficient for carbon dioxide of 49.66-56.22 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 17.1-19.5 for a mixed gas of carbon dioxide and nitrogen, a gas separation coefficient of 16.5-18.6 for a mixed gas of carbon dioxide and methane, and a gas separation coefficient of 4.5-5.2 for a mixed gas of oxygen and nitrogen. In the present invention, the gas separation coefficient is calculated by a method of 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 summary, the polyimide prepared from the phthalazinone diamine monomer provided by the invention is prepared by adding DMAC, DMF, NMP, DMSO, THF and CHCl3And 1, 4-dioxane has better solubility, and the 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 phthalazinone diamine monomer having a structure represented by formula I:
Figure FDA0002827968310000011
2. a phthalazinone diamine hybrid monomer, comprising four compounds of the phthalazinone diamine monomer of claim 1, the four compounds each having a structure represented by formula II-1 to formula II-4:
Figure FDA0002827968310000012
3. the preparation method of the phthalazinone diamine monomer comprises the following steps:
(1) mixing 2-iodobenzoic acid methyl ester, 3, 4-dimethoxybenzaldehyde and hydrazine hydrate in an aromatic hydrocarbon solvent for reaction to obtain 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone, wherein the structure of the 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone is as follows:
Figure FDA0002827968310000021
(2) carrying out nucleophilic substitution reaction on the 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone, the 4-fluoro-1, 2-dimethoxybenzene and the catalyst obtained in the step (1) in water to obtain 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone; the catalyst is potassium carbonate or cesium carbonate, and the structure of the 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone is as follows:
Figure FDA0002827968310000022
(3) dissolving the 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone obtained in the step (2) in a polar organic solvent, dropwise adding boron tribromide under the conditions of low temperature and protective gas, and performing demethylation reaction to obtain the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone; the low temperature is-20 to-6 ℃, and the structure of the 4- (3, 4-tetrahydroxydiphenyl) naphthalene-1-phthalazinone is as follows:
Figure FDA0002827968310000023
(4) carrying out oxidation reaction on the 4- (3, 4-tetrahydroxydiphenyl) heteronaphthalene-1-phthalazinone obtained in the step (3) and an oxidant in dichloromethane to obtain the 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone, wherein the structure of the 4- (3, 4-tetracarbonyldiphenyl) heteronaphthalene-1-phthalazinone is as follows:
Figure FDA0002827968310000031
(5) and (3) carrying out dehydration reaction on the 4- (3, 4-tetracarbonyl diphenyl) hetero naphthalene-1-phthalazinone and 4-nitro o-phenylenediamine obtained in the step (4) in dimethyl sulfoxide to obtain the hetero naphthalene-dinitro-1-phthalazinone, wherein the structure of the hetero naphthalene-dinitro-1-phthalazinone is as follows:
Figure FDA0002827968310000032
(6) under the protective atmosphere, the naphthalene-dinitro-1-phthalazinone obtained in the step (5), hydrazine hydrate and palladium-carbon are subjected to reduction reaction in dioxane to obtain a phthalazinone diamine monomer shown in the formula I; the structural formula of the formula I is as follows:
Figure FDA0002827968310000033
4. the preparation method according to claim 3, wherein the molar ratio of methyl 2-iodobenzoate, 3, 4-dimethoxybenzaldehyde and hydrazine hydrate in the step (1) is 1:1 to 3:14 to 16; the temperature of the mixing reaction is 100-130 ℃.
5. The preparation method according to claim 3, wherein the molar ratio of 4- (3, 4-dimethoxyphenyl) heteronaphthalene-1-phthalazinone to 4-fluoro-1, 2-dimethoxybenzene in the step (2) is 1:1 to 1.2; the temperature of the nucleophilic substitution reaction is 80-100 ℃, and the time is 12-15 h.
6. The method according to claim 3, wherein the molar ratio of 4- (3, 4-tetramethoxydiphenyl) heteronaphthalene-1-phthalazinone to boron tribromide in the step (3) is 1: 1.5-2; the temperature of the demethylation reaction is-12 to-4 ℃, and the time is 1 to 6 hours.
7. The preparation method according to claim 3, wherein the oxidant in the step (4) is tetra-n-butylammonium chromate or dichromate, and the temperature of the oxidation reaction is 25-35 ℃ and the time is 15-20 min.
8. 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 phthalazinone diamine monomer in a polar organic solvent to obtain a polyamic acid solution; the phthalazinone diamine monomer is the phthalazinone diamine monomer of claim 1 or the phthalazinone diamine mixed monomer of claim 2;
(ii) (ii) mixing the polyamic acid solution obtained in the step (i) with a catalyst and a dehydrating agent, and carrying out imidization reaction to obtain polyimide;
the polyimide has a structure represented by formula a:
Figure FDA0002827968310000041
in the formula A
Figure FDA0002827968310000042
Has a structure shown in formula 1, formula 2 or formula 3:
Figure FDA0002827968310000043
the polymerization degree of the polyimide is 80-100.
9. A polyimide prepared by the process of claim 8, the polyimide having a structure according to formula a:
Figure FDA0002827968310000051
in the formula A
Figure FDA0002827968310000052
Has a structure shown in formula 1, formula 2 or formula 3:
Figure FDA0002827968310000053
the polymerization degree of the polyimide is 80-100.
10. A polyimide film prepared from the polyimide of claim 9.
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