CN109535069A - A kind of diamine monomer and preparation method thereof and polyimides and preparation method thereof - Google Patents
A kind of diamine monomer and preparation method thereof and polyimides and preparation method thereof Download PDFInfo
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- CN109535069A CN109535069A CN201811520199.5A CN201811520199A CN109535069A CN 109535069 A CN109535069 A CN 109535069A CN 201811520199 A CN201811520199 A CN 201811520199A CN 109535069 A CN109535069 A CN 109535069A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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Abstract
The present invention relates to technical field of organic chemistry, and in particular to a kind of diamine monomer and preparation method thereof and a kind of polyimides and preparation method thereof.The present invention provides a kind of diamine monomers, diamine monomer provided by the invention contains " spiral shell a " center " (two rings share an atom), with non-co-planar structure, increase molecule chain rigidity, prevent high polymer main chain is from being freely rotated in the polyimides being prepared by diamine monomer of the present invention, hinder effective accumulation of molecule interchain, cause to form continuous micropore inside polyimides, hole is more, molecular structure is loose, therefore the Kapton being prepared by diamine monomer of the present invention can be under the premise of keeping selectivity, improve permeability and the dissolubility etc. of gas；In addition, the polyimides that diamine monomer provided by the invention is prepared has preferable dissolubility and light transmittance.
Description
Technical field
The present invention relates to technical field of organic chemistry, and in particular to a kind of diamine monomer and preparation method thereof and polyimides
And preparation method thereof.
Background technique
Gas membrane Seperation Technology is a kind of novel green isolation technics, have separative efficiency is high, easy to operate, low energy consumption,
The advantages that green non-pollution, has been widely used in the fields such as medicine food, biochemistry, energy environment protection.High-molecular polymerization membrane
With preferable separating property, excellent mechanical performance and physical and chemical performance, therefore become common gas separation membrane material,
Gas separation membrane technology is an important component of numerous applications in membrane separation technique, is after cryogenic separation, pressure-variable adsorption
Third generation gas separation later.Relative to traditional gas isolation technics, UF membrane is with low energy consumption, small investment, equipment
The advantages that simple, in O2/N2Separation, dehumidification of gas, CO2Recycling, H2Separation and recovery etc. has important application.
Polyimides (PI) is a kind of high molecular polymer on main chain containing imide ring, 1908 by Bogert and
Renshaw synthesis, DuPont Corporation develops Kapton product within 1962, subsequent various PI products such as plastics, layer
Pressing plate, varnished cloth, adhesive, coating and fiber impregnation material etc. are come out one after another, and Kapton is applied to gas separation
Film research.With the continuous development and progress of social science and technology, application standard of the people to Kapton in gas film field
Also higher and higher, how to develop while having separative efficiency height and the high gas separation membrane of mechanical performance be people pursue and
The emphasis of concern.Main problem existing for Kapton is that the permeability of Kapton is low, while polyamides at present
The solubility property of imines film is poor.
Summary of the invention
For the above problem existing for Kapton, the present invention passes through a kind of diamine monomer of Molecular Design, by
Diamine monomer of the present invention obtains Kapton while guaranteeing good selectivity, has permeability height, dissolubility
Good feature.
The present invention provides a kind of diamine monomers, have structure shown in Formulas I:
The R' is methyl or trifluoromethyl；
The R is selected from one of structure shown in Formula II；
Preferably, the diamine monomer has structure shown in formula III~Formula IV:
The present invention also provides the preparation method of diamine monomer described in above-mentioned technical proposal,
When R' is methyl in the Formulas I, the preparation method of the diamine monomer the following steps are included:
(1) bisphenol-A and methane sulfonic acid are subjected to microwave reaction, microwave reaction product discharge collects solid in ice-water bath；
The solid is subjected to heating sublimation, obtains methyl diphenol compound；
(2) methyl diphenol compound that the step (1) obtains, catalyst are mixed with solvent, obtains phenols ionic liquid
Body；The phenols ionic liquid and single nitro compound are subjected to substitution reaction, obtain dinitro compound；Then by described two
Nitro compound carries out reduction reaction, obtains the diamine monomer that structure R' shown in Formulas I is methyl；The catalyst is potassium carbonate
And/or cesium carbonate；
When R' is trifluoromethyl in the Formulas I, the preparation method of the diamine monomer the following steps are included:
(a) bisphenol AF and trifluoroacetic acid are subjected to heating reaction, heating reaction product discharging obtains trifluoro in ice-water bath
Methyl diphenol compound；
(b) trifluoromethyl diphenol compound that the step (a) obtains, catalyst are mixed with solvent, obtain phenols from
Sub- liquid；The phenols ionic liquid and single nitro compound are subjected to substitution reaction, obtain dinitro compound；Then by institute
It states dinitro compound and carries out reduction reaction, obtain the diamine monomer that structure R' shown in Formulas I is trifluoromethyl；The catalyst is
Potassium carbonate and/or cesium carbonate.
Preferably, the molar ratio of bisphenol-A and methane sulfonic acid is 1:5~8 in the step (1).
Preferably, the frequency of microwave reaction is 180~220GHz in the step (1), and the heating rate of microwave reaction is
18~22 DEG C/min.
Preferably, the molar ratio of bisphenol AF and trifluoroacetic acid is 1:10~12 in the step (a).
Preferably, the temperature of heating reaction is 180~220 DEG C in the step (a), the time for heating reaction is 15~
20h。
Preferably, the molar ratio of phenols ionic liquid and single nitro compound is 1:2 in the step (2) or step (b)
~2.4；The list nitro compound includes halonitro pyridine, halogenated methyl nitropyridine, halonitro quinoline, halogenated methyl
Nitroquinoline, halonitro isoquinolin or halogenated methyl nitroisoquinoline.
The present invention also provides a kind of preparation methods of polyimides, comprising the following steps:
(i) under nitrogen protection, dianhydride monomer and diamine monomer are subjected in polar organic solvent polycondensation reaction, obtained
Polyamic acid solution；The diamine monomer is preparation side described in diamine monomer described in above-mentioned technical proposal or above-mentioned technical proposal
The diamine monomer that method is prepared；
(ii) catalyst and dehydrating agent are added in the polyamic acid solution that Xiang Suoshu step (i) obtains, it is anti-to carry out imidization
It answers, obtains polyimides.
The present invention also provides the polyimides that above-mentioned technical proposal the method is prepared.
The present invention provides a kind of diamine monomer of Formulas I structure, diamine monomer provided by the invention contains one " in spiral shell
The heart " (two rings share an atom), has non-co-planar structure, molecule chain rigidity is increased, so that by of the present invention two
High polymer main chain cannot be freely rotated in the polyimides that amine monomers are prepared, and hinder effective accumulation of molecule interchain, lead
It causes to form continuous micropore inside polyimides, hole is more, and molecular structure is loose, therefore by diamine monomer system of the present invention
Standby obtained Kapton can improve the permeability of gas under the premise of keeping selectivity；In addition, the present invention provides
Diamine monomer in the presence of flexible group (ehter bond) increase the free volume and flexibility of polymer molecular chain, hold solvent
It easily penetrates into, improves the dissolubility for the polyimides that thus diamine monomer is prepared, and be conducive to improve polyimides
Optical transmission.Embodiment the result shows that, the polyimides that diamine monomer provided by the invention is prepared DMAC, DMF,
NMP、DMSO、THF、CHCl3With there is preferable dissolubility in Isosorbide-5-Nitrae-Dioxane, while there is preferable visible light transmittance；
And the Kapton being prepared by polyimides of the present invention can guarantee well to select in gas separation field
While property, have the characteristics that permeability is high.
Detailed description of the invention
Fig. 1 is the nuclear-magnetism figure for the diamine monomer that embodiment 3 is prepared；
Fig. 2 is the nuclear-magnetism figure for the diamine monomer that embodiment 4 is prepared；
Fig. 3 is the infrared spectrum of polyimides prepared by embodiment 9~14；
Fig. 4 is that the DSC of Kapton prepared by embodiment 9~14 tests spectrogram；
Fig. 5 is that the light transmittance of polyimides prepared by embodiment 9~14 tests spectrogram；
Fig. 6 is the thermogravimetric curve of Kapton prepared by embodiment 9~14；
Fig. 7 is Kapton O prepared by embodiment 9~142/N2Robeson ' s selectivity curve；
Fig. 8 is Kapton CO prepared by embodiment 9~142/CH4Robeson ' s selectivity curve.
Specific embodiment
The present invention provides a kind of diamine monomers, have structure shown in Formulas I:
The R' is methyl or trifluoromethyl；
The R is selected from one of Formula II structure；
In the present invention, the diamine monomer preferably has structure shown in formula III~Formula IV:
The present invention provides the preparation methods of diamine monomer described in above-mentioned technical proposal, in the present invention, when in the Formulas I
When R' is methyl, the preparation method of the diamine monomer the following steps are included:
(1) bisphenol-A and methane sulfonic acid are subjected to microwave reaction, microwave reaction product discharge collects solid in ice-water bath；
The solid is subjected to heating sublimation, obtains methyl diphenol compound；
(2) methyl diphenol compound, the catalysts and solvents obtained the step (1) mix, and obtain phenols ionic liquid
Body；The phenols ionic liquid and single nitro compound are subjected to substitution reaction, obtain dinitro compound；Then by described two
Nitro compound carries out reduction reaction, obtains the diamine monomer that structure R' shown in Formulas I is methyl；The catalyst is potassium carbonate
And/or cesium carbonate.
Bisphenol-A and methane sulfonic acid are carried out microwave reaction by the present invention, and microwave reaction product discharge is collected solid in ice-water bath
Body；The solid is subjected to heating sublimation, obtains methyl diphenol compound.
In the present invention, the bisphenol-A and methane sulfonic acid prepare the process of methyl diphenol compound as shown in Formula VII:
Bisphenol-A and methane sulfonic acid are carried out microwave reaction by the present invention, obtain microwave reaction product.In the present invention, described
The molar ratio of bisphenol-A and methane sulfonic acid is preferably 1:5~8, further preferably 1:6~7.In the present invention, the microwave is anti-
The frequency answered is preferably 180~220GHz, further preferably 200GHz, and the heating rate of microwave reaction is preferably 18~22
DEG C/min, further preferably 20 DEG C/min.In the present invention, the microwave reaction preferably carries out under nitrogen protection.This hair
It is bright preferably by TLC detect raw material point disappear after, stop microwave reaction.
After obtaining microwave reaction product, the present invention by microwave reaction product discharge in ice-water bath, preferably through being separated by solid-liquid separation
And drying, obtain solid.In the present invention, the mode of the separation of solid and liquid preferably filters, and the present invention will be preferably separated by solid-liquid separation
Obtained solid matter is dried, and obtains solid.
After obtaining solid, the solid is carried out heating sublimation by the present invention, is preferably collected distillation gains, is obtained methyl two
Phenolic compounds.In the present invention, the temperature of the heating sublimation is preferably 155~165 DEG C, the present invention preferably by by solid into
Row heating sublimation improves the purity of product methyl diphenol compound.
After obtaining methyl diphenol compound, the present invention mixes methyl diphenol compound, catalysts and solvents, obtains phenols
Ionic liquid；The phenols ionic liquid and single nitro compound are subjected to substitution reaction, obtain dinitro compound；Then will
The dinitro compound carries out reduction reaction, obtains the diamine monomer that structure R' shown in Formulas I is methyl.
In the present invention, the system for the diamine monomer that structure R' shown in Formulas I is methyl is prepared as methyl diphenol compound
Standby principle is as shown in Formula VIII, by taking single nitro compound 2- chloro-5-nitropyridine as an example:
The present invention mixes methyl diphenol compound, catalyst with solvent, obtains phenols ionic liquid.In the present invention,
The catalyst is potassium carbonate and/or cesium carbonate；The solvent preferably includes trichloroethanes.In the present invention, the methyl two
The molar ratio of phenolic compounds and catalyst is preferably 1:2~2.4, further preferably 1:2.1~2.3；Two phenolate of methyl
The amount ratio for closing object and solvent is preferably 1g:2.7~3.3mL, further preferably 1g:2.8~3.2mL.In the present invention, institute
It states mixing preferably to carry out in the case where being ultrasonically treated part, the frequency of the ultrasonic treatment is preferably 18~22KHz, further preferably
20KHz；The time of the ultrasonic treatment is preferably 30~35min.
After obtaining phenols ionic liquid, phenols ionic liquid and single nitro compound are carried out substitution reaction by the present invention, are obtained
To dinitro compound.
In the present invention, single nitro compound preferably includes halonitro pyridine, halogenated methyl nitropyridine, halogenated
Nitroquinoline, halogenated methyl nitroquinoline, halonitro isoquinolin or halogenated methyl nitroisoquinoline；The phenols ionic liquid
Molar ratio with single nitro compound is preferably 1:2~2.4, further preferably 1:2.1~2.3.In the present invention, described to take
Generation reaction preferably carries out in organic solvent, and the organic solvent preferably includes n,N-Dimethylformamide, substitution reaction system
Solid content be preferably 15~20%.In the present invention, the temperature of the substitution reaction is preferably 75~85 DEG C, further preferably
It is 80 DEG C；After the present invention preferably detects raw material point disappearance by TLC, stop substitution reaction.
The present invention is preferably by substitution reaction product discharge in the sodium chloride solution that mass fraction is 5%, through being separated by solid-liquid separation
And drying, dinitro compound crude product is obtained, the dinitro compound crude product is dissolved in n,N-Dimethylformamide,
Heating systems are to reflux temperature, and addition deionized water, until stopping heating when system just has precipitation and do not dissolve, cooling is filtered
To dinitro compound.In the present invention, the amount ratio of the dinitro compound crude product and n,N-Dimethylformamide is excellent
It is selected as 1g:2~3mL；The amount ratio of the dinitro compound crude product and deionized water is preferably 1g:1~2mL.
After obtaining dinitro compound, the dinitro compound is carried out reduction reaction by the present invention, obtains knot shown in Formulas I
Structure R' is the diamine monomer of methyl.
In the present invention, the reduction reaction preferably carries out in Isosorbide-5-Nitrae-dioxane or anhydrous ethanol solvent；Described two
The solid content of nitro compound in the reaction system is preferably 15%~20%.In the present invention, the reduction reaction preferably exists
It is carried out under the conditions of catalyst is existing, the catalyst preferably includes caustic soda, the quality of the dinitro compound and catalyst
Than being preferably 1:0.1~0.5.
Dinitro compound and catalyst preferably are heated to flowing back by the present invention in a solvent, are then added into reaction system
Entering reducing agent sodium arsenite and hydrazine hydrate, continues back flow reaction 15~for 24 hours, TLC detects to raw material point that disappear be that reaction terminates,
Obtain reduction reaction product.In the present invention, the molar ratio of the dinitro compound and sodium arsenite is preferably 1:5~8；Institute
The molar ratio for stating dinitro compound and hydrazine hydrate is 1:15~20.
The present invention filters the reduction reaction product while hot to remove sodium arsenite, after collecting filtrate, carries out to filtrate
It is concentrated under reduced pressure, obtains diamine monomer crude product；Diamine monomer crude product is heated to flowing back in good solvent Isosorbide-5-Nitrae-dioxane,
Poor solvent deionized water is added into reflux system again, is precipitated and does not dissolve until just having, stop reflux, through being separated by solid-liquid separation and very
Sky is dry, obtains the diamine monomer that Formulas I structure R' is methyl.
In the present invention, when R' is trifluoromethyl in the Formulas I, the preparation method of the diamine monomer includes following step
It is rapid:
(a) bisphenol AF and trifluoroacetic acid are subjected to heating reaction, heating reaction product discharging obtains trifluoro in ice-water bath
Methyl diphenol compound；
(b) trifluoromethyl diphenol compound that the step (a) obtains, catalyst are mixed with solvent, obtain phenols from
Sub- liquid；The phenols ionic liquid and single nitro compound are subjected to substitution reaction, obtain dinitro compound；Then by institute
It states dinitro compound and carries out reduction reaction, obtain the diamine monomer that structure R' shown in Formulas I is trifluoromethyl；The catalyst is
Potassium carbonate and/or cesium carbonate.
Bisphenol AF and trifluoroacetic acid are carried out heating reaction by the present invention, and heating reaction product discharging is in ice-water bath, preferably
It is separated by solid-liquid separation and is dried, obtain trifluoromethyl diphenol compound.
In the present invention, the preparation method of the trifluoromethyl diphenol compound is as shown in Formula IX:
Bisphenol AF and trifluoroacetic acid are carried out heating reaction by the present invention, obtain heating reaction product.In the present invention, described
The molar ratio of bisphenol AF and trifluoroacetic acid is preferably 1:10~12；The temperature of the heating reaction is preferably 180~220 DEG C, into
One step is preferably 200 DEG C；The time of the heating reaction is preferably 14~16h, further preferably 15h.
After obtaining heating reaction product, the present invention discharges the heating reaction product in ice-water bath, preferably through solid-liquid
Separation and drying, obtain trifluoromethyl diphenol compound.In the present invention, the specific embodiment of the separation of solid and liquid is preferably
It filters, the present invention will preferably be separated by solid-liquid separation obtained solid matter and be dried, and obtain trifluoromethyl diphenol compound.
After obtaining trifluoromethyl diphenol compound, the present invention is by the trifluoromethyl diphenol compound, catalyst and solvent
Mixing, it is preferably sonicated, obtain phenols ionic liquid；The phenols ionic liquid and single nitro compound are replaced
Reaction, obtains dinitro compound；Then the dinitro compound is subjected to reduction reaction, obtaining structure R' shown in Formulas I is
The diamine monomer of trifluoromethyl.
In the present invention, the diamines that structure R' shown in Formulas I is trifluoromethyl is prepared as trifluoromethyl diphenol compound
The preparation method of monomer is represented by a formula X, by taking single nitro compound is the bromo- 5- nitroquinoline of 2- as an example:
The present invention mixes trifluoromethyl diphenol compound, catalyst with solvent, preferably sonicated, obtain phenols from
Sub- liquid.In the present invention, the catalyst is potassium carbonate and/or cesium carbonate, the methyl diphenol compound and catalyst
Molar ratio is preferably 1:2~2.4, further preferably 1:2.1~2.3.In the present invention, the solvent preferably includes three chloroethenes
The amount ratio of alkane, the trifluoromethyl diphenol compound and solvent is preferably 1g:2.7~3.3mL, further preferably 1g:2.8
~3.2mL.In the present invention, the frequency of the ultrasonic treatment is preferably 18~22KHz, further preferably 20KHz；It is described super
The time of sonication is preferably 30~35min.
After obtaining phenols ionic liquid, phenols ionic liquid and single nitro compound are carried out substitution reaction by the present invention, are obtained
To dinitro compound.
In the present invention, single nitro compound preferably includes halonitro pyridine, halogenated methyl nitropyridine, halogenated
Nitroquinoline, halogenated methyl nitroquinoline, halonitro isoquinolin or halogenated methyl nitroisoquinoline；The phenols ionic liquid
Molar ratio with single nitro compound is preferably 1:2~2.4, further preferably 1:2.1~2.3.In the present invention, replace anti-
The solid content for answering system is preferably 15~20%.In the present invention, the temperature of the substitution reaction is preferably 75~85 DEG C, into one
Preferably 80 DEG C of step；After the present invention preferably detects raw material point disappearance by TLC, stop substitution reaction.
The present invention is preferably by substitution reaction product discharge in the sodium chloride solution that mass fraction is 5%, through being separated by solid-liquid separation
And drying, dinitro compound crude product is obtained, dinitro compound crude product is dissolved in n,N-Dimethylformamide, is heated
To reflux temperature deionized water is added, when being precipitated and is insoluble, stopping heating, cooling, suction filtration obtains two until system just has in system
Nitro compound.In the present invention, the amount ratio of the dinitro compound crude product and n,N-Dimethylformamide is preferably
1:2~3；The amount ratio of the dinitro compound crude product and deionized water is preferably 1:1~2.
After obtaining dinitro compound, the dinitro compound is carried out reduction reaction by the present invention, obtains knot shown in Formulas I
Structure R' is the diamine monomer of methyl.
In the present invention, the reduction reaction preferably carries out in Isosorbide-5-Nitrae-dioxane or anhydrous ethanol solvent；Described two
The solid content of nitro compound in the reaction system is preferably 15%~20%.In the present invention, the reduction reaction preferably exists
It is carried out under the conditions of catalyst is existing, the catalyst preferably includes caustic soda, the quality of the dinitro compound and catalyst
Than being preferably 1:0.1~0.5.
Dinitro compound and catalyst preferably are heated to flowing back by the present invention in a solvent, are then added into reaction system
Entering reducing agent sodium arsenite and hydrazine hydrate, continues back flow reaction 15~for 24 hours, TLC detects to raw material point that disappear be that reaction terminates,
Obtain reduction reaction product.In the present invention, the molar ratio of the dinitro compound and sodium arsenite is preferably 1:5~8；Institute
The molar ratio for stating dinitro compound and hydrazine hydrate is 1:15~20.
The present invention filters the reduction reaction product while hot to remove sodium arsenite, after collecting filtrate, carries out to filtrate
It is concentrated under reduced pressure, obtains diamine monomer crude product；The present invention heats diamine monomer crude product in good solvent 1,4- dioxane
To reflux, then the addition poor solvent deionized water into reflux system, it is precipitated and does not dissolve until just having, stop reflux, through solid-liquid
Separation and vacuum drying obtain the diamine monomer that structure R' shown in Formulas I is trifluoromethyl.
The present invention also provides a kind of preparation methods of polyimides, comprising the following steps:
(i) under nitrogen protection, dianhydride monomer and diamine monomer are subjected in polar organic solvent polycondensation reaction, obtained
Polyamic acid solution；The diamine monomer is preparation side described in diamine monomer described in above-mentioned technical proposal or above-mentioned technical proposal
The diamine monomer that method is prepared；
(ii) catalyst and dehydrating agent are added in the polyamic acid solution that Xiang Suoshu step (i) obtains, it is anti-to carry out imidization
It answers, obtains polyimides.
The present invention carries out polycondensation reaction under nitrogen protection, by dianhydride monomer and diamine monomer in polar organic solvent,
Obtain polyamic acid solution.
In the present invention, the diamine monomer is described in diamine monomer described in above-mentioned technical proposal or above-mentioned technical proposal
The diamine monomer that preparation method is prepared.In the present invention, the dianhydride monomer preferably includes 4,4 '-(hexafluoro isopropyl alkene) two
Anhydride phthalic acid, 3,3 ', 4,4 '-diphenyl ether tetracid dianhydrides or 4,4 '-(4,4 '-diphenol oxygroup propyl)-dibenzoic acid acid anhydrides, the dianhydride
Monomer preferably has structure shown in Formula XI:
Wherein AR preferably has structure shown in formula 1, formula 2 or formula 3:
In the present invention, the molar ratio of the dianhydride monomer and diamine monomer is preferably 1:0.8~1.2, further preferably
For 2~3:2~3.In the present invention, the sum of the solid content of the dianhydride monomer and diamine monomer in polar organic solvent is preferred
It is 28%~32%, further preferably 20%.The present invention preferably carries out polycondensation reaction at room temperature, the polycondensation reaction when
Between preferably 3~for 24 hours.
In the present invention, the type of the polar organic solvent preferably includes N, N '-dimethyl formamide or N, N '-diformazan
Yl acetamide.
After obtaining polyamic acid solution, catalyst and dehydrating agent are added into the polyamic acid solution by the present invention, carry out
Imidization obtains polyimides.
In the present invention, the catalyst preferably includes pyridine or isoquinolin；The dehydrating agent preferably include acetic anhydride or
Pyridine and acetic anhydride is added in isoquinolin, the present invention preferably into polyamic acid solution, or is added into polyamic acid solution different
Quinoline.In the present invention, when being preferably added to pyridine and acetic anhydride, the volume ratio of the acetic anhydride and pyridine is preferably 2:1, institute
The amount ratio for stating acetic anhydride and diamine monomer is preferably 4mL:1~3mmol；In the present invention, when being preferably added to isoquinolin, institute
The amount ratio for stating isoquinolin and diamine monomer is preferably 0.2~0.3mL:1~2mmol.In the present invention, the imidization
Temperature be preferably 55~65 DEG C, further preferably 60 DEG C；The time of the imidization is preferably 24~25h.This hair
Bright cyclization dehydration occurs for the polyamic acid solution during imidization, generates polyimides.
The present invention will preferably pour into deionized water after the cooling of imidization product, successively be filtered, filter cake alcohol is washed
And vacuum drying treatment, obtain polyimides.The present invention to it is described filtering, filter cake alcohol wash and vacuum decompression be dried it is specific
Embodiment is not particularly limited, using method commonly used by those skilled in the art.In the present invention, the vacuum is dry
The temperature of dry processing is preferably 80 DEG C；The time of the vacuum drying treatment is preferably 12h.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1: the preparation of methyl diphenol compound
Into the 250mL three-neck flask equipped with mechanical stirring device, the bisphenol-A of 10mmol, the methane sulphur of 50mmol is added
Acid reacts at room temperature half an hour under the protection of sufficiently logical nitrogen, uses the microwave that frequency is 200GHz with the heating of 20 DEG C/min
Rate is warming up to 180 DEG C of melting temperature of system or more, and TLC, which detects to raw material point to disappear as to react, to be terminated, and stops reaction, instead
With ice-water bath, suction filtration, drying obtain crude product, gained crude product are placed in vacuum tube furnace for system discharging after answering,
Heating sublimation crude product collects distillation gains, obtains methyl diphenol compound, through 100 DEG C of vacuum drying 12h, obtain
The methyl diphenol compound of 1.5980g, obtained product structure such as following formula:
Embodiment 2: the preparation of trifluoromethyl diphenol compound
The bisphenol AF of addition 10mmol into the tetrafluoro reaction vessel equipped with mechanical stirring device, 100mmol trifluoroacetic acid,
Dissolution is sufficiently stirred at room temperature, the tetrafluoro reaction vessel equipped with reaction raw materials is placed in pyroreaction kettle, regulation system heating
Temperature is 200 DEG C, and frit reaction carries out 15h, stops reaction；System discharging filters in ice-water bath, is dry after reaction
Obtained crude product is completely dissolved in good solvent Isosorbide-5-Nitrae-dioxane by crude product, and poor solvent deionized water is added until rigid
It is precipitated and stirring is precipitated and does not dissolve, filter, be dried to obtain trifluoromethyl diphenol compound, obtained product structure such as following formula:
The preparation of -6,6 '-dioxy pyridine diamines of embodiment 3:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene)
First step reaction: into the 250mL three-neck flask equipped with mechanical stirring device, 20mmol methyl diphenol chemical combination is added
Object, the potassium carbonate of 44mmol make system react half an hour, obtain phenols ionic liquid, is added using 20KHz supercritical ultrasonics technology
44mmol 2- chloro-5-nitropyridine, makes the total solid content 15% of reaction system, and stirring, heat temperature raising system are to 80 DEG C, TLC
It is that reaction terminates that detection to raw material point, which disappears, and discharging is filtered with 5% NaCl salt water after system is cooling, dry, obtains and slightly produces
Gained crude product is dissolved in n,N-Dimethylformamide by product, heating systems to reflux temperature, deionized water is added, until system
It is rigid to have precipitation and do not dissolve, stop heating, cooling filters to obtain dinitro compound.
Second step reaction: by the first step react obtained in dinitro compound 8mmol be added equipped with mechanical stirring device
250mL three-neck flask in, Isosorbide-5-Nitrae-dioxane of 68mL is added, makes the total solid content of the solid content reaction system of system be
15%, 1.3291g catalyst caustic soda is added, for agitating and heating system to flowing back, system reacts half an hour, and the reduction of 40mmol is added
Agent sodium arsenite, for 24 hours, TLC detects to raw material point to disappear as to react to be terminated back flow reaction, and filtering while hot (prevents temperature cooling
Product is precipitated) reducing agent sodium arsenite is removed, it collects filtrate and is heated to flowing back, be passed through 4h hydrogen, filtrate is through catalytic hydrogenation, concentration
Filtrate obtains crude product, and through 100 DEG C of vacuum drying 12h, crude product is dissolved in good solvent Isosorbide-5-Nitrae-dioxane and is heated to reaction solution
110 DEG C of reflux temperature, be slowly added into poor solvent deionized water into this back flow reaction liquid, be precipitated and insoluble until just having,
Heating is closed, 100 DEG C of vacuum dry 12h obtain 3.9702g diamine monomer, obtained product structure such as following formula:
Diamine monomer is prepared to embodiment 3 and carries out nuclear-magnetism test, test results are shown in figure 1, as shown in Figure 1, this
Inventing the substance being prepared has above structure.
The system of -6,6 '-dioxy -3- picoline diamines of embodiment 4:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene)
It is standby
First step reaction: into the 250mL three-neck flask equipped with mechanical stirring device, 10mmol methyl diphenol chemical combination is added
Object, the potassium carbonate of 24mmol make system react half an hour, obtain phenols ionic liquid, be added 24mmol's using supercritical ultrasonics technology
The chloro- 3- methyl-5-nitro pyridine of 2-, makes the total solid content 20% of reaction system, stirring, heat temperature raising system to 100 DEG C,
TLC, which detects to raw material point to disappear as to react, to be terminated, and with deionized water, suction filtration, drying is obtained and slightly produced for discharging after system is cooling
Gained crude product is dissolved in n,N-Dimethylformamide by product, heating systems to reflux temperature, deionized water is added, until system
Just there is precipitation and do not dissolve, close heating, cooling filters, and obtains the dinitro polymerisable compounds of 6.7903g.
Second step reaction: by the first step react obtained in dinitro compound 17mmol be added equipped with mechanical stirring device
250mL three-neck flask in, Isosorbide-5-Nitrae-dioxane of 86mL is added, makes the total solid content of the solid content reaction system of system be
15%, 4.9354g catalyst caustic soda is added, for agitating and heating system to flowing back, system reacts half an hour, and the reduction of 85mmol is added
Agent sodium arsenite, back flow reaction 20h, TLC, which detects to raw material point to disappear as to react, to be terminated, and filtering while hot (prevents temperature cooling
Product is precipitated) reducing agent sodium arsenite is removed, it collects filtrate and is heated to flowing back, be passed through 6h hydrogen, filtrate is through catalytic hydrogenation, concentration
Filtrate obtains crude product, and through 100 DEG C of vacuum drying 12h, crude product is dissolved in good solvent Isosorbide-5-Nitrae-dioxane and is heated to reaction solution
110 DEG C of reflux temperature, be slowly added into poor solvent deionized water into this back flow reaction liquid, be precipitated and insoluble until just having,
Heating is closed, 100 DEG C of vacuum dry 12h obtain 8.0632g diamine monomer, obtained product structure such as following formula:
Diamine monomer is prepared to embodiment 4 and carries out nuclear-magnetism test, test results are shown in figure 2, as shown in Figure 2, this
Inventing the substance being prepared has above structure.
The preparation of embodiment 5:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) -6,6 '-dioxies-quinoline diamines
First step reaction: into the 250mL three-neck flask equipped with mechanical stirring device, 10mmol methyl diphenol chemical combination is added
Object, the potassium carbonate of 24mmol make system react half an hour, obtain phenols ionic liquid, add using the supercritical ultrasonics technology of 20KHz frequency
Enter the chloro- 5- nitroquinoline of 24mmol2-, make the total solid content 20% of reaction system, stirring, heat temperature raising system to 100 DEG C,
TLC, which detects to raw material point to disappear as to react, to be terminated, and with deionized water, suction filtration, drying is obtained and slightly produced for discharging after system is cooling
Gained crude product is dissolved in n,N-Dimethylformamide by product, heating systems to reflux temperature, deionized water is added, until system
Just there is precipitation and do not dissolve, close heating, cooling filters, and obtains the dinitro polymerisable compounds of 6.0003g.
Second step reaction: by the first step react obtained in dinitro compound 10mmol be added equipped with mechanical stirring device
250mL three-neck flask in, Isosorbide-5-Nitrae-dioxane of 59mL is added, makes the total solid content of the solid content reaction system of system be
10%, 3.2636g catalyst caustic soda is added, for agitating and heating system to flowing back, system reacts half an hour, and the reduction of 80mmol is added
Agent sodium arsenite, back flow reaction 15h, TLC, which detects to raw material point to disappear as to react, to be terminated, and filtering while hot (prevents temperature cooling
Product is precipitated) reducing agent sodium arsenite is removed, it collects filtrate and is heated to flowing back, be passed through 5h hydrogen, filtrate is through catalytic hydrogenation, concentration
Filtrate obtains crude product, and through 100 DEG C of vacuum drying 12h, crude product is dissolved in good solvent Isosorbide-5-Nitrae-dioxane and is heated to reaction solution
110 DEG C of reflux temperature, be slowly added into poor solvent deionized water into this back flow reaction liquid, be precipitated and insoluble until just having,
Heating is closed, 100 DEG C of vacuum dry 12h obtain 5.0967g diamine monomer, obtained product structure such as following formula:
The preparation of embodiment 6:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) -6,6 '-dioxies-isoquinolin diamines
First step reaction: into the 250mL three-neck flask equipped with mechanical stirring device, 10mmol methyl diphenol chemical combination is added
Object, the potassium carbonate of 24mmol make system react half an hour, obtain phenols ionic liquid, be added 24mmol's using supercritical ultrasonics technology
The chloro- 5- nitroisoquinoline of 2- makes the total solid content 20% of reaction system, and to 100 DEG C, TLC is detected for stirring, heat temperature raising system
Disappearing to raw material point is that reaction terminates, and discharging is filtered with deionized water after system is cooling, dry, crude product is obtained, by gained
Crude product is dissolved in n,N-Dimethylformamide, heating systems to reflux temperature, be added deionized water, until system just have precipitation and
It is insoluble, heating is closed, cooling filters, and obtains the dinitro polymerisable compounds of 5.6503g.
Second step reaction: by the first step react obtained in dinitro compound 10mmol be added equipped with mechanical stirring device
250mL three-neck flask in, Isosorbide-5-Nitrae-dioxane of 59mL is added, makes the total solid content of the solid content reaction system of system be
10%, 3.2636g catalyst caustic soda is added, for agitating and heating system to flowing back, system reacts half an hour, and the reduction of 80mmol is added
Agent sodium arsenite, back flow reaction 22h, TLC, which detects to raw material point to disappear as to react, to be terminated, and filtering while hot (prevents temperature cooling
Product is precipitated) reducing agent sodium arsenite is removed, it collects filtrate and is heated to flowing back, be passed through 5h hydrogen, filtrate is through catalytic hydrogenation, concentration
Filtrate obtains crude product, and through 100 DEG C of vacuum drying 12h, crude product is dissolved in good solvent Isosorbide-5-Nitrae-dioxane and is heated to reaction solution
110 DEG C of reflux temperature, be slowly added into poor solvent deionized water into this back flow reaction liquid, be precipitated and insoluble until just having,
Heating is closed, 100 DEG C of vacuum dry 12h obtain 5.3109g diamine monomer, obtained product structure such as following formula:
- 6,6 '-dioxy trifluoromethyl pyridine diamines of embodiment 7:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene)
Preparation
First step reaction: into the 250mL three-neck flask equipped with mechanical stirring device, 20mmol trifluoromethyl diphenol is added
Compound, the potassium carbonate of 46mmol make system react half an hour, obtain phenols ionic liquid, is added using 20KHz supercritical ultrasonics technology
46mmol 2- chloro-5-nitropyridine, makes the total solid content 15% of reaction system, stirring, heat temperature raising system to 100 DEG C,
TLC, which detects to raw material point to disappear as to react, to be terminated, and with 5% NaCl salt water, suction filtration, drying is obtained for discharging after system is cooling
Gained crude product is dissolved in n,N-Dimethylformamide by crude product, heating systems to reflux temperature, and deionized water is added, until
System just has precipitation and does not dissolve, and stops heating, and cooling filters to obtain dinitro compound.
Second step reaction: by the first step react obtained in dinitro compound 8mmol be added equipped with mechanical stirring device
250mL three-neck flask in, Isosorbide-5-Nitrae-dioxane of 64mL is added, makes the total solid content of the solid content reaction system of system be
20%, 1.3291g catalyst caustic soda is added, for agitating and heating system to flowing back, system reacts half an hour, and the reduction of 40mmol is added
Agent sodium arsenite, for 24 hours, TLC detects to raw material point to disappear as to react to be terminated back flow reaction, and filtering while hot (prevents temperature cooling
Product is precipitated) reducing agent sodium arsenite is removed, it collects filtrate and is heated to flowing back, be passed through 4h hydrogen, filtrate is through catalytic hydrogenation, concentration
Filtrate obtains crude product, and through 100 DEG C of vacuum drying 12h, crude product is dissolved in good solvent Isosorbide-5-Nitrae-dioxane and is heated to reaction solution
110 DEG C of reflux temperature, the NaCl salt water of poor solvent 5% is slowly added into this back flow reaction liquid, until just have be precipitated and not
Heating is closed in dissolution, and 100 DEG C of vacuum dry 12h obtain 3.0602g diamine monomer, obtained product structure such as following formula:
- 6,6 '-dioxy -3- methyl trifluoro methyl pyridine of embodiment 8:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene)
The preparation of diamines
First step reaction: into the 250mL three-neck flask equipped with mechanical stirring device, 10mmol trifluoromethyl diphenol is added
Compound, the potassium carbonate of 28mmol make system react half an hour, obtain phenols ionic liquid, is added using supercritical ultrasonics technology
The chloro- 3- methyl-5-nitro pyridine of the 2- of 28mmol makes the total solid content 22% of reaction system, and stirring, heat temperature raising system are extremely
120 DEG C, TLC, which detects to raw material point to disappear as to react, to be terminated, and with deionized water, suction filtration, drying is obtained for discharging after system is cooling
Gained crude product is dissolved in n,N-Dimethylformamide by crude product, heating systems to reflux temperature, and deionized water is added, until
System just has precipitation and does not dissolve, and closes heating, and cooling filters, and obtains the dinitro polymerisable compounds of 6.4303g.
Second step reaction: by the first step react obtained in dinitro compound 17mmol be added equipped with mechanical stirring device
250mL three-neck flask in, Isosorbide-5-Nitrae-dioxane of 80mL is added, makes the total solid content of the solid content reaction system of system be
20%, 4.9354g catalyst caustic soda is added, for agitating and heating system to flowing back, system reacts half an hour, and the reduction of 85mmol is added
Agent sodium arsenite, back flow reaction 20h, TLC, which detects to raw material point to disappear as to react, to be terminated, and filtering while hot (prevents temperature cooling
Product is precipitated) reducing agent sodium arsenite is removed, it collects filtrate and is heated to flowing back, be passed through 6h hydrogen, filtrate is through catalytic hydrogenation, concentration
Filtrate obtains crude product, and through 100 DEG C of vacuum drying 12h, crude product is dissolved in good solvent Isosorbide-5-Nitrae-dioxane and is heated to reaction solution
110 DEG C of reflux temperature, be slowly added into poor solvent deionized water into this back flow reaction liquid, be precipitated and insoluble until just having,
Heating is closed, 100 DEG C of vacuum dry 12h obtain 7.0098g diamine monomer, obtained product structure such as following formula:
- 6,6 '-dioxy pyridine diamines of embodiment 9:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) and 4,4 '-(six
Fluorine isopropyl alkene) two anhydride phthalic acids prepare polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.2mmol, the N of 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy pyridine diamines, 13mL,
N- dimethyl acetamide makes the solid content 15% of system, and after diamines all dissolution, the 4 of 2.2mmol, 4 '-(hexafluoros are added
Isopropyl alkene) two anhydride phthalic acids, react form sticky polyamic acid for 24 hours at room temperature, 2mL pyridine and 4mL are added dropwise into reaction system
Acetic anhydride, the system that heats up maintain this thermotonus for 24 hours to 60 DEG C, close heating, are cooled to room temperature to system, discharge in 200mL
In deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyimide polymer of 1.7309g is obtained
PI-1, obtained product structure such as following formula:
Embodiment 10:4,4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy pyridine diamines and 3,3 ', 4,
4 '-diphenyl ether tetracid dianhydrides prepare polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.0mmol, the N of 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy pyridine diamines, 10mL,
N- dimethyl acetamide makes the solid content 15% of system, after diamines all dissolution, is added the 3 of 2.0mmol, and 3 ', 4,4 '-
Diphenyl ether tetracid dianhydride reacts form sticky polyamic acid for 24 hours at room temperature, and 2mL pyridine and 4mL second are added dropwise into reaction system
Acid anhydrides, the system that heats up maintain this thermotonus for 24 hours to 60 DEG C, close heating, are cooled to room temperature to system, discharging is gone in 200mL
In ionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyimide polymer of 1.3006g is obtained
PI-2, obtained product structure such as following formula:
- 6,6 '-dioxy pyridine diamines of embodiment 11:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) and 4,4 '-(4,
4 '-diphenol oxygroup propyl)-dibenzoic acid acid anhydride prepares polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.0mmol, the N of 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy pyridine diamines, 12mL,
N- dimethyl acetamide makes the solid content 15% of system, after diamines all dissolution, is added the 4 of 2.0mmol, and 4 '-(4,4 '-
Diphenol oxygroup propyl)-dibenzoic acid acid anhydride, reacts form sticky polyamic acid for 24 hours at room temperature, 2mL is added dropwise into reaction system
Pyridine and 4mL acetic anhydride, the system that heats up maintain this thermotonus for 24 hours to 60 DEG C, close heating, are cooled to room temperature to system, out
Expect in 200mL deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyamides of 1.8306g is obtained
Imine polymer PI-3, obtained product structure such as following formula:
- 6,6 '-dioxy -3- picoline diamines of embodiment 12:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) with
4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids prepare polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, the 4 of 3.0mmol, 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy -3- picolines, 18mL are added
N,N-dimethylacetamide, make the solid content 15% of system, after diamines all dissolution, be added the 4 of 2.0mmol, 4 '-
(hexafluoro isopropyl alkene) two anhydride phthalic acids, react form sticky polyamic acid for 24 hours at room temperature, and 2mL pyridine is added dropwise into reaction system
With 4mL acetic anhydride, the system that heats up maintains this thermotonus for 24 hours to 80 DEG C, closes heating, is cooled to room temperature to system, discharging in
In 200mL deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyimides of 2.7306g is obtained
Polymer P I-4, obtained product structure such as following formula:
- 6,6 '-dioxy -3- picoline diamines of embodiment 13:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) with
3,3 ', 4,4 '-diphenyl ether tetracid dianhydrides prepare polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 3.0mmol, 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy -3- picoline diamines,
The n,N-dimethylacetamide of 18mL makes the solid content 15% of system, and after diamines all dissolution, the 3 of 3.0mmol are added,
3 ', 4,4 '-diphenyl ether tetracid dianhydrides, react form sticky polyamic acid for 24 hours at room temperature, and 3mL pyrrole is added dropwise into reaction system
Pyridine and 6mL acetic anhydride, the system that heats up maintain this thermotonus for 24 hours to 80 DEG C, close heating, are cooled to room temperature to system, discharge
In 200mL deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyamides for obtaining 2.3106g is sub-
Amine polymer PI-5, obtained product structure such as following formula:
- 6,6 '-dioxy -3- picoline diamines of embodiment 14:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) with
4,4 '-(4,4 '-diphenol oxygroup propyl)-dibenzoic acid acid anhydrides prepare polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 3.0mmol, 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy -3- picoline diamines,
The n,N-dimethylacetamide of 19mL makes the solid content 15% of system, and after diamines all dissolution, the 4 of 3.0mmol are added,
4 '-(4,4 '-diphenol oxygroup propyl)-dibenzoic acid acid anhydrides, react form sticky polyamic acid for 24 hours at room temperature, to reaction system
Middle dropwise addition 3mL pyridine and 6mL acetic anhydride, the system that heats up maintain this thermotonus for 24 hours to 80 DEG C, close heating, cool down to system
To room temperature, discharge in 200mL deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, is obtained 3.0209g's
Target polyimide polymer PI-6, obtained product structure such as following formula:
- 6,6 '-dioxy quinoline diamines of embodiment 15:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) and 4,4 '-(six
Fluorine isopropyl alkene) two anhydride phthalic acids prepare polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.2mmol, the N of 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy quinoline diamines, 13mL,
N- dimethyl acetamide makes the solid content 15% of system, and after diamines all dissolution, the 4 of 2.2mmol, 4 '-(hexafluoros are added
Isopropyl alkene) two anhydride phthalic acids, react form sticky polyamic acid for 24 hours at room temperature, 2mL pyridine and 4mL are added dropwise into reaction system
Acetic anhydride, the system that heats up maintain this thermotonus for 24 hours to 60 DEG C, close heating, are cooled to room temperature to system, discharge in 200mL
In deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyimides polymerization of 1.9329g is obtained
Object, obtained product structure such as following formula:
Embodiment 16:4,4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy quinoline diamines and 3,3 ', 4,
4 '-diphenyl ether tetracid dianhydrides prepare polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.0mmol, the N of 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy quinoline diamines, 10mL,
N- dimethyl acetamide makes the solid content 15% of system, after diamines all dissolution, is added the 3 of 2.0mmol, and 3 ', 4,4 '-
Diphenyl ether tetracid dianhydride reacts form sticky polyamic acid for 24 hours at room temperature, and 2mL pyridine and 4mL second are added dropwise into reaction system
Acid anhydrides, the system that heats up maintain this thermotonus for 24 hours to 60 DEG C, close heating, are cooled to room temperature to system, discharging is gone in 200mL
In ionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyimide polymer of 1.4016g is obtained,
Obtained product structure such as following formula:
- 6,6 '-dioxy quinoline diamines of embodiment 17:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) and 4,4 '-(4,
4 '-diphenol oxygroup propyl)-dibenzoic acid acid anhydride prepares polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.0mmol, the N of 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy quinoline diamines, 12mL,
N- dimethyl acetamide makes the solid content 15% of system, after diamines all dissolution, is added the 4 of 2.0mmol, and 4 '-(4,4 '-
Diphenol oxygroup propyl)-dibenzoic acid acid anhydride, reacts form sticky polyamic acid for 24 hours at room temperature, 2mL is added dropwise into reaction system
Pyridine and 4mL acetic anhydride, the system that heats up maintain this thermotonus for 24 hours to 60 DEG C, close heating, are cooled to room temperature to system, out
Expect in 200mL deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyamides of 1.9006g is obtained
Imine polymer, obtained product structure such as following formula:
Embodiment 18:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) -6,6 '-dioxies-isoquinolin diamines and 4,4 ' -
(hexafluoro isopropyl alkene) two anhydride phthalic acids prepare polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.2mmol, the N of 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy quinoline diamines, 13mL,
N- dimethyl acetamide makes the solid content 15% of system, and after diamines all dissolution, the 4 of 2.2mmol, 4 '-(hexafluoros are added
Isopropyl alkene) two anhydride phthalic acids, react form sticky polyamic acid for 24 hours at room temperature, 2mL pyridine and 4mL are added dropwise into reaction system
Acetic anhydride, the system that heats up maintain this thermotonus for 24 hours to 60 DEG C, close heating, are cooled to room temperature to system, discharge in 200mL
In deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyimides polymerization of 1.6904g is obtained
Object, obtained product structure such as following formula:
Embodiment 19:4,4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxies-isoquinolin diamines and 3,3 ',
4,4 '-diphenyl ether tetracid dianhydrides prepare polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.0mmol, the N of 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy quinoline diamines, 10mL,
N- dimethyl acetamide makes the solid content 15% of system, after diamines all dissolution, is added the 3 of 2.0mmol, and 3 ', 4,4 '-
Diphenyl ether tetracid dianhydride reacts form sticky polyamic acid for 24 hours at room temperature, and 2mL pyridine and 4mL second are added dropwise into reaction system
Acid anhydrides, the system that heats up maintain this thermotonus for 24 hours to 60 DEG C, close heating, are cooled to room temperature to system, discharging is gone in 200mL
In ionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyimide polymer of 1.0126g is obtained,
Obtained product structure such as following formula:
Embodiment 20:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) -6,6 '-dioxies-isoquinolin diamines and 4,4 ' -
(4,4 '-diphenol oxygroup propyl)-dibenzoic acid acid anhydride prepares polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.0mmol, the N of 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy quinoline diamines, 12mL,
N- dimethyl acetamide makes the solid content 15% of system, after diamines all dissolution, is added the 4 of 2.0mmol, and 4 '-(4,4 '-
Diphenol oxygroup propyl)-dibenzoic acid acid anhydride, reacts form sticky polyamic acid for 24 hours at room temperature, 2mL is added dropwise into reaction system
Pyridine and 4mL acetic anhydride, the system that heats up maintain this thermotonus for 24 hours to 60 DEG C, close heating, are cooled to room temperature to system, out
Expect in 200mL deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyamides of 1.7006g is obtained
Imine polymer, obtained product structure such as following formula:
- 6,6 '-dioxy trifluoromethyl pyridine diamines of embodiment 21:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) with
4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids prepare polyimides, and detailed process is as follows
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.2mmol, 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy trifluoromethyl pyridine diamines,
The n,N-Dimethylformamide of 16mL makes the solid content 15% of system, and after diamines all dissolution, the 4 of 2.2mmol are added,
4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids, react form sticky polyamic acid for 24 hours at room temperature, be added dropwise into reaction system
0.35ml drop isoquinolin, the system that heats up maintain this thermotonus for 24 hours to 120 DEG C, close heating, are cooled to room temperature to system, out
Expect in 200mL deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyamides of 1.6399g is obtained
Imines, obtained product structure such as following formula:
- 6,6 '-dioxy Trifluoromethylquinocarboxylic diamines of embodiment 22:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene) with
3,3 ', 4,4 '-diphenyl ether tetracid dianhydrides prepare polyimides, and detailed process is as follows:
In the 50mL three-neck flask that import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are housed, in the guarantor of nitrogen
Under shield, it is added the 4 of 2.0mmol, 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy Trifluoromethylquinocarboxylic diamines,
The n,N-Dimethylformamide of 10mL makes the solid content 15% of system, and after diamines all dissolution, the 3 of 2.0mmol are added,
3 ', 4,4 '-diphenyl ether tetracid dianhydrides, react form sticky polyamic acid for 24 hours at room temperature, 0.2ml is added into reaction system
Isoquinolin, the system that heats up maintains this thermotonus for 24 hours to 160 DEG C, closes heating, be cooled to room temperature to system, discharging in
In 200mL deionized water, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, and the target polyimides of 1.7916g is obtained
Polymer, obtained product structure such as following formula:
- 6,6 '-dioxy trifluoromethyl -3- methyl quinoline of embodiment 23:4,4 '-(2,2 ' 3,3 '-tetrahydros -1,1 '-spirobiindene)
Quinoline diamines and 4,4 '-(4,4 '-diphenol oxygroup propyl)-dibenzoic acid acid anhydrides prepare polyimides, and detailed process is as follows:
Import and export of nitrogen, magnetic stir bar, thermometer, condenser pipe are being housed, in the 50mL three-neck flask with water installations,
Under the protection of nitrogen, the 4 of 2.0mmol, 4 '-(2,2 ' 3,3 '-tetrahydro -1,1 '-spirobiindene) -6,6 '-dioxy trifluoromethyls-are added
The n,N-Dimethylformamide of 3- methylquinoline diamines, 10mL makes the solid content 15% of system, after diamines all dissolution,
4,4 '-(4,4 '-diphenol oxygroup propyl)-dibenzoic acid acid anhydrides of 2.0mmol are added, reacts form sticky polyamides for 24 hours at room temperature
Amino acid, 2mL pyridine and 4mL acetic anhydride, 5mL toluene are added into reaction system, and the system that heats up maintains this temperature anti-to 180 DEG C
Heating should be closed for 24 hours, be cooled to room temperature to system, discharge in 200mL deionized water, alcohol reflux is washed 3 times, is dried in vacuum
It is dried at 80 DEG C of case, obtains the target polyimide polymer of 2.2016g, obtained product structure such as following formula:
Performance test
Infrared spectrum test is carried out to the polyimides that embodiment 9~14 is prepared, test results are shown in figure 3.?
In the present invention, the polyimides that embodiment 9~14 synthesizes successively is indicated with PI-1, PI-2, PI-3, PI-4, PI-5 and PI-6.By
Fig. 3 is it is found that there are the characteristic peaks of polyimides in infrared spectrum provided by the invention, it was demonstrated that successfully synthesizes subject polymer.
DSC test is carried out to the polyimides that embodiment 9~14 is prepared, test results are shown in figure 4, can by Fig. 4
Know, the glass transition temperature of polyimides provided by the invention is at 230 DEG C or more, better heat stability.
The light transmittance of the polyimides that embodiment 9~14 is prepared under ultraviolet light is tested, and test result is such as
Shown in Fig. 5, as shown in Figure 5, polyimides provided by the invention has high permeability in visible-range, in visible light model
It encloses interior mean transmissivity and has reached 85%.In the present invention, light transmittance is tried using ultraviolet waves general survey, specifically: using Japanese saliva
The UV2550 type ultra-violet and visible spectrophotometer of island company measures, and scanning range is 200~800nm.
The thermal weight loss performance for the polyimides that embodiment 9~14 is prepared is tested, test result such as Fig. 6 institute
Show, it will be appreciated from fig. 6 that polyimides provided by the invention has good thermal stability, in a nitrogen atmosphere 5% thermal weight loss temperature
At 480 DEG C or more.The present invention is measured in a nitrogen atmosphere using TA2050 type thermogravimetric analyzer, and temperature elevating range is 100~800
DEG C, the flow of atmosphere gas is 10ml/min.
Test can be carried out to the gas-selectively for the polyimides that embodiment 9~14 is prepared, test result such as Fig. 7 and
Shown in shown in Fig. 8, by Fig. 7 and Fig. 8 it is found that the present invention is preferable to the separating effect of oxygen and nitrogen, while to carbon dioxide and
The separating effect of methane is preferable.
Dissolubility test
The dissolubility of polyimides prepared by embodiment 9~14 is tested, test method are as follows: distinguish polyimides
It is dissolved in DMAC, DMF, NMP, DMSO, THF, CHCl3In Isosorbide-5-Nitrae-Dioxane, concentration of the polyimides in different solvents is
10mg/mL.Solubility property of the polyimides in different solvents is tested, ++: room temperature is entirely molten；+: heating is complete molten；+-: part is molten
Solution；--: heating is insoluble.Test result is as shown in table 1.
The dissolubility for the polyimides that 1 embodiment 9~14 of table is prepared
| Solvent/sample | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 |
| DMAC | ++ | ++ | ++ | ++ | ++ | ++ |
| DMF | ++ | ++ | ++ | ++ | ++ | ++ |
| NMP | ++ | ++ | ++ | ++ | ++ | ++ |
| DMSO | + | + | + | + | + | + |
| THF | ++ | ++ | ++ | ++ | ++ | ++ |
| CHCl3 | ++ | ++ | ++ | ++ | ++ | ++ |
| 1,4-Dioxane | ++ | ++ | ++ | ++ | ++ | ++ |
By 1 test result of table it is found that the polyimides that is prepared of diamine monomer provided by the invention have it is preferable molten
Xie Xing.Diamine monomer provided by the invention introduces the groups such as aliphatic structure, ehter bond, makes by diamine monomer system of the present invention
The dissolubility that standby obtained polyimides is all done well in most of polar solvents.
Gas separation test
The polyimides that the embodiment of the present invention 9~14 is prepared is prepared into Kapton, specific preparation side
Method are as follows:
Polyimides is dissolved in n,N-dimethylacetamide with 15% solid content, through 0.45 μm of Teflon filter mistake
It filters out insoluble matter and obtains uniform polyimide solution, which is coated uniformly on clean 9cm × 9cm glass plate, is placed in
In baking oven use temperature programming, pass sequentially through 60 DEG C/4h, 90 DEG C/12h, 120 DEG C/4h and 150 DEG C/4h processing after, natural cooling
Obtain transparent polyimide film.
Gas separation test, test result such as 2 institute of table are carried out to the Kapton that embodiment 9~14 is prepared
Show, test method are as follows:
Test of the polyimides prepared by the present invention in terms of gas separation is using self-control gas permeability tester, and specific method is such as
Shown in lower: using the gas permeability matter of pressure differential method (the strong method of constant volume transformation) test polymer film.During the test,
Testing film is sealed in test pond with epoxy resin, upstream pressure is set as 2atm, and downstream is evacuated to vacuum, to downstream
Pressure after a period of stabilisation, is tested at 35 DEG C, and thin polymer film is characterized with gas permeability coefficient and is divided gas
From effect, gas separation coefficient indicates the selectivity of perfect gas.
The gas separating property of 2 embodiment of table, 9~14 Kapton
As shown in Table 2, after polyimides provided by the invention is prepared into Kapton, there is the separation of preferable gas
Performance, Kapton provided by the invention are 1.92~3.59Barrer to the infiltration coefficient of nitrogen, the infiltration to methane
Coefficient is 1.42~12.72Barrer, and the infiltration coefficient to oxygen is 2.33~16.9Barrer, to the infiltration system of carbon dioxide
Number is 48~63.18Barrer.Thus illustrate Kapton that polyimides provided by the invention is prepared to gas
Permeability it is higher.
Kapton provided by the invention is 17.4 to the gas separation coefficient of carbon dioxide and nitrogen mixed gas
~25.7, the gas separation coefficient to carbon dioxide and methane mixed gas is 16.2~36.9, to oxygen and nitrogen mixture
The gas separation coefficient of body is 4.4~6.9.In the present invention, the calculation method of gas separation coefficient is αA/B=PA/PB, PAWith
PBThe infiltration coefficient of two kinds of gas of respectively A and B.Thus illustrate, the polyamides that polyimides provided by the invention is prepared is sub-
Amine film is higher to the selectivity of gas, i.e., good in guarantee after polyimides provided by the invention is prepared into Kapton
While good selectivity, have the characteristics that permeability is high.
In conclusion the polyimides that is prepared of diamine monomer provided by the invention DMAC, DMF, NMP, DMSO,
THF、CHCl3Gather in Isosorbide-5-Nitrae-Dioxane with preferable dissolubility, and by what polyimides of the present invention was prepared
Imide membrane is in gas separation field, while capable of guaranteeing good selectivity, has the characteristics that permeability is high.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of diamine monomer has structure shown in Formulas I:
The R' is methyl or trifluoromethyl；
The R is selected from one of structure shown in Formula II；
2. diamine monomer according to claim 1, which is characterized in that the diamine monomer has shown in formula III~Formula IV
Structure:
3. the preparation method of diamine monomer of any of claims 1 or 2,
When R' is methyl in the Formulas I, the preparation method of the diamine monomer the following steps are included:
(1) bisphenol-A and methane sulfonic acid are subjected to microwave reaction, microwave reaction product discharge collects solid in ice-water bath；By institute
It states solid and carries out heating sublimation, obtain methyl diphenol compound；
(2) methyl diphenol compound, the catalysts and solvents obtained the step (1) mix, and obtain phenols ionic liquid；It will
The phenols ionic liquid and single nitro compound carry out substitution reaction, obtain dinitro compound；Then by the dinitro
Compound carries out reduction reaction, obtains the diamine monomer that structure R' shown in Formulas I is methyl；The catalyst be potassium carbonate and/or
Cesium carbonate；
When R' is trifluoromethyl in the Formulas I, the preparation method of the diamine monomer the following steps are included:
(a) bisphenol AF and trifluoroacetic acid are subjected to heating reaction, heating reaction product discharging obtains trifluoromethyl in ice-water bath
Diphenol compound；
(b) trifluoromethyl diphenol compound, the catalysts and solvents obtained the step (a) mix, and obtain phenols ionic liquid
Body；The phenols ionic liquid and single nitro compound are subjected to substitution reaction, obtain dinitro compound；Then by described two
Nitro compound carries out reduction reaction, obtains the diamine monomer that structure R' shown in Formulas I is trifluoromethyl；The catalyst is carbonic acid
Potassium and/or cesium carbonate.
4. preparation method according to claim 3, which is characterized in that bisphenol-A and methane sulfonic acid rubs in the step (1)
You are than being 1:5~8.
5. preparation method according to claim 3 or 4, which is characterized in that the frequency of microwave reaction is in the step (1)
180~220GHz, the heating rate of microwave reaction are 18~22 DEG C/min.
6. preparation method according to claim 3, which is characterized in that bisphenol AF and trifluoroacetic acid in the step (a)
Molar ratio is 1:10~12.
7. the preparation method according to claim 3 or 6, which is characterized in that the temperature of heating reaction is in the step (a)
180~220 DEG C, the time for heating reaction is 15~20h.
8. preparation method according to claim 3, which is characterized in that phenols ionic liquid in the step (2) or step (b)
The molar ratio of body and single nitro compound is 1:2~2.4；The list nitro compound includes halonitro pyridine, halogenated methyl
Nitropyridine, halonitro quinoline, halogenated methyl nitroquinoline, halonitro isoquinolin or halogenated methyl nitroisoquinoline.
9. a kind of preparation method of polyimides, comprising the following steps:
(i) under nitrogen protection, dianhydride monomer and diamine monomer are subjected in polar organic solvent polycondensation reaction, obtain polyamides
Amino acid solution；The diamine monomer is the preparation of any one of diamine monomer as claimed in claim 1 or 2 or claim 3~8
The diamine monomer that method is prepared；
(ii) catalyst and dehydrating agent are added in the polyamic acid solution that Xiang Suoshu step (i) obtains, carries out imidization, obtains
To polyimides.
10. the polyimides that claim 9 the method is prepared.
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Cited By (9)
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| CN110041212A (en) * | 2019-05-21 | 2019-07-23 | 吉林大学 | A kind of fluorine-containing polyamine monomers and preparation method thereof, a kind of polyimides and preparation method thereof and a kind of polyimide film |
| CN110105189A (en) * | 2019-05-21 | 2019-08-09 | 吉林大学 | A kind of fluorine-containing polyacid monomer and preparation method thereof, a kind of polyamide and preparation method thereof and a kind of polyamide film |
| CN111362963A (en) * | 2020-04-14 | 2020-07-03 | 吉林大学 | Diamine monomer containing spiropyran structure, preparation method and application thereof, polyimide, preparation method and application thereof |
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| US4734482A (en) * | 1985-08-30 | 1988-03-29 | Mitsui Toatsu Chemicals, Inc. | Polyimide from ether diamine having the indane structure and high-temperature adhesive of polyimide |
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| US4734482A (en) * | 1985-08-30 | 1988-03-29 | Mitsui Toatsu Chemicals, Inc. | Polyimide from ether diamine having the indane structure and high-temperature adhesive of polyimide |
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