CN109912437A - A kind of polyamine monomers and preparation method thereof, a kind of polyimides and preparation method thereof and a kind of Kapton - Google Patents
A kind of polyamine monomers and preparation method thereof, a kind of polyimides and preparation method thereof and a kind of Kapton Download PDFInfo
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Abstract
The present invention provides a kind of polyamine monomers and preparation method thereof, a kind of polyimides and preparation method thereof and a kind of Kaptons, belong to technical field of organic synthesis.Polyamine monomers provided by the invention have structure shown in Formulas I~any one of formula IV, there are polyamine monomers provided by the invention microcellular structure, flexible group (ehter bond) and hydroxyl structure, polyamine monomers provided by the present invention further to polymerize to obtain polyimides with dianhydride monomer.The Kapton that polyimides provided by the invention is formed has preferable selective penetrated property and permeability simultaneously.In addition, polyimides provided by the invention has preferable dissolubility.
Description
Technical field
The present invention relates to technical field of organic synthesis more particularly to a kind of polyamine monomers and preparation method thereof, a kind of polyamides
Imines and preparation method thereof and a kind of Kapton.
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
, there be important answer in the advantages that simple in terms of oxygen/nitrogen separation, dehumidification of gas, carbon dioxide recovery, Hydrogen Separation
With.
Current commercially available gas separation membrane material is mainly made of low granular media, the machinable glassy polymers of solute, it
Between be in inverse relation, i.e., permeability increase, then selectivity reduce, here it is so-called Trade-off effects.Therefore it prepares
High osmosis and highly selective polymeric gas seperation film are had both out, are had to improving gas separative efficiency and expanding application range
Unusual far-reaching influence.
Summary of the invention
The present invention provides a kind of polyamine monomers, Kapton that polyamine monomers provided by the present invention are prepared
There is preferable gas-selectively and permeability simultaneously.
The present invention provides a kind of polyamine monomers, have structure shown in Formulas I~any one of formula IV:
The present invention also provides the preparation method of the polyamine monomers described in above-mentioned technical proposal,
When structure described in the polyamine monomers have Formulas I or formula III, preparation method the following steps are included:
(1) cooling after being heated to reflux the acetum of the acetone soln of hydrogen iodide and catechol, it is molten to obtain supersaturation
Then liquid carries out hydro-thermal process to the supersaturated solution, four phenol of loop coil is precipitated；Four phenol of loop coil has structure shown in Formula V:
(2) four phenol of loop coil and halonitro methyl phenyl ethers anisole obtained the step (1) exists in catalyst and organic solvent
Under the conditions of carry out substitution reaction, obtain tetranitro-anisole spiro-compound；The halonitro methyl phenyl ethers anisole includes the halogenated -2- of 5-
Nitroanisole or the halogenated -5- Nitroanisole of 2-；The catalyst includes one or both of potassium carbonate and cesium carbonate；
When the halonitro methyl phenyl ethers anisole -2- Nitroanisole halogenated for 5-, the tetranitro-anisole spiro compounds
Object has structure shown in Formula IV；When the halonitro methyl phenyl ethers anisole -5- Nitroanisole halogenated for 2-, the tetranitro benzene first
Ether spiro-compound has structure shown in Formula VII:
(3) the tetranitro-anisole spiro-compound for obtaining the step (2) and Boron tribromide progress demethylation are anti-
It answers, is then quenched using methanol, generate tetranitro hydroxy benzenes spiro-compound；The tetranitro hydroxy benzenes spiro-compound has
Structure shown in Formula VIII or Formula IX:
(4) in the presence of sodium hydroxide, the step (3) is obtained using sodium arsenite tetranitro hydroxy benzenes spirocyclization
It closes object to be restored, obtains the polyamine monomers that structure is Formulas I or formula III；
When structure described in the polyamine monomers have Formula II or formula IV, preparation method the following steps are included:
(a) after the acetum of the acetone soln of hydrogen iodide, the acetum of catechol and hydroxy benzenes being heated to reflux
It is cooling, supersaturated solution is obtained, hydro-thermal process then is carried out to the supersaturated solution, loop coil triphenol is precipitated；The loop coil three
Phenol has structure shown in Formula X:
(b) the loop coil triphenol and halonitro methyl phenyl ethers anisole obtained the step (a) exists in catalyst and organic solvent
Under the conditions of carry out substitution reaction, obtain trinitroanisole spiro-compound；The halonitro methyl phenyl ethers anisole includes the halogenated -2- of 5-
Nitroanisole or the halogenated -5- Nitroanisole of 2-；The catalyst includes one or both of potassium carbonate and cesium carbonate；
When the halonitro methyl phenyl ethers anisole -2- Nitroanisole halogenated for 5-, the trinitroanisole spiro compounds
Object has structure shown in Formula XI；When the halonitro methyl phenyl ethers anisole -5- Nitroanisole halogenated for 2-, the trinitrobenzen first
Ether spiro-compound has structure shown in Formula XII:
(c) the trinitroanisole spiro-compound for obtaining the step (b) and Boron tribromide progress demethylation are anti-
It answers, is then quenched using methanol, generate trinitro- hydroxy benzenes spiro-compound；The trinitro- hydroxy benzenes spiro-compound has
Structure shown in Formula XIII or Formula XIV:
(d) in the presence of sodium hydroxide, the step (c) is obtained using sodium arsenite trinitro- hydroxy benzenes spirocyclization
It closes object to be restored, obtains the polyamine monomers that structure is Formula II or formula IV.
Preferably, the molar ratio of hydrogen iodide and catechol is 1:2~5 in the step (1)；Water in the step (1)
The temperature of heat treatment is 200~240 DEG C, and pressure is 1MPa~0.5GPa.
Preferably, the molar ratio of hydrogen iodide, catechol and hydroxy benzenes is 1:1~4:1~4 in the step (a)；It is described
The temperature of hydro-thermal process is 200~240 DEG C in step (a), and pressure is 1MPa~0.5GPa.
Preferably, the molar ratio of step (2) kind four phenol of loop coil and halonitro methyl phenyl ethers anisole is 1:5~9；The step
(2) temperature of substitution reaction is 150~200 DEG C in, and the time is 8~10h；
The molar ratio of loop coil triphenol and halonitro methyl phenyl ethers anisole is 1:5~9 in the step (b)；It is taken in the step (b)
The temperature of generation reaction is 150~200 DEG C, and the time is 8~10h.
Preferably, tetranitro-anisole spiro-compound and the molar ratio of Boron tribromide and methanol are in the step (3)
1:6~9:10~14；The temperature of substitution reaction is -5~-10 DEG C in the step (3), and the time is 3~6h；
The molar ratio of trinitroanisole spiro-compound and Boron tribromide and methanol is 1:6~9 in the step (c):
10~14；The temperature of substitution reaction is -5~-10 DEG C in the step (c), and the time is 1~2h.
Preferably, the molar ratio of tetranitro hydroxy benzenes spiro-compound and sodium arsenite is 1:5~8 in the step (4)；
The temperature restored in the step (4) is 100~120 DEG C, and the time is 8~10h；
The molar ratio of trinitro- hydroxy benzenes spiro-compound and sodium arsenite is 1:5~8 in the step (d)；The step
Suddenly the temperature restored in (d) is 100~130 DEG C, and the time is 8~10h.
The present invention provides a kind of polyimides, have structure shown in Formula XV:
Wherein having a R substituent in four R substituents is H, and excess-three R substituent is
Or four R substituents are
Wherein AR has any one of 1~formula of formula 3 structure:
The present invention provides the preparation methods of polyimides described in above-mentioned technical proposal, comprising the following steps:
(i) under nitrogen protection, dianhydride monomer and polyamine monomers are subjected in polar organic solvent polycondensation reaction, obtained
Polyamic acid solution；The polyamine monomers are preparation side described in polyamine monomers described in above-mentioned technical proposal or above-mentioned technical proposal
The polyamine monomers 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 a kind of Kaptons, which is characterized in that the Kapton includes above-mentioned skill
The polyimides that polyimides described in art scheme or above-mentioned technical proposal the method are prepared；The Kapton
With a thickness of 60~70um.
The present invention provides a kind of polyamine monomers, have structure shown in Formulas I~any one of formula IV.Polyamines provided by the invention
Monomer has loop coil microcellular structure and flexible group (ehter bond), and polyamine monomers provided by the present invention are further and dianhydride monomer
Polymerization obtains super-branched polyimide polymer.Polyamine monomers provided by the invention contain multiple amino, are conducive to and dianhydride list
Body polymerize to form super-branched polyimide, and there are microcellular structure, micropore knots for super-branched polyimide polymer provided by the invention
The presence of structure easily infiltrates into gas molecules, increases the selective penetrated property of its film；In addition, polyamine monomers provided by the invention contain
There are multiple amino, be conducive to possess bigger gap between the dissaving polymer for making to be formed and polymer, there is bigger infiltration
Saturating coefficient.In addition, flexible group (ehter bond) and hydroxyl collective effect in polyimides provided by the invention, increase polyamine monomers
Interaction between solvent molecule, and the free volume and flexibility of polymer molecular chain are increased, it is easy solvent
It penetrates into, improves the problem of the traditional gas seperation film difference of the dissolubility due to caused by rigid chain.Embodiment the result shows that, the present invention
The Kapton that the polyimides is prepared is in gas separation field, while capable of guaranteeing good selectivity, tool
Have the characteristics that permeability is high；And the polyimides that is prepared of polyamine monomers provided by the present invention DMAC, DMF, NMP,
DMSO, THF and CHCl3In have preferable dissolubility.
Detailed description of the invention
Fig. 1 is the nuclear magnetic spectrogram for the polyamine monomers that the embodiment of the present invention 1 is prepared；
Fig. 2 is the infrared spectrum for the polyimides that application examples 1~5 of the present invention is prepared；
Fig. 3 is the graph of pore diameter distribution for the polyimides that application examples 1~3 of the present invention is prepared.
Specific embodiment
The present invention provides a kind of polyamine monomers, have structure shown in Formulas I~any one of formula IV:
The present invention also provides the preparation method of polyamine monomers described in above-mentioned technical proposal,
When structure described in the polyamine monomers have Formulas I or formula III, preparation method the following steps are included:
(1) cooling after being heated to reflux the acetum of the acetone soln of hydrogen iodide and catechol, it is molten to obtain supersaturation
Then liquid carries out hydro-thermal process to the supersaturated solution, four phenol of loop coil is precipitated；Four phenol of loop coil has structure shown in Formula V:
(2) four phenol of loop coil and halonitro methyl phenyl ethers anisole obtained the step (1) exists in catalyst and organic solvent
Under the conditions of carry out substitution reaction, obtain tetranitro-anisole spiro-compound；The halonitro methyl phenyl ethers anisole includes the halogenated -2- of 5-
Nitroanisole or the halogenated -5- Nitroanisole of 2-；The catalyst includes one or both of potassium carbonate and cesium carbonate；
When the halonitro methyl phenyl ethers anisole -2- Nitroanisole halogenated for 5-, the tetranitro-anisole spiro compounds
Object has structure shown in Formula IV；When the halonitro methyl phenyl ethers anisole -5- Nitroanisole halogenated for 2-, the tetranitro benzene first
Ether spiro-compound has structure shown in Formula VII:
(3) the tetranitro-anisole spiro-compound that the step (2) obtains is taken off with Boron tribromide and methanol, it is raw
At tetranitro hydroxy benzenes spiro-compound；The tetranitro hydroxy benzenes spiro-compound has structure shown in Formula VIII or Formula IX:
(4) in the presence of sodium hydroxide, the step (3) is obtained using sodium arsenite tetranitro hydroxy benzenes spirocyclization
It closes object to be restored, obtains the polyamine monomers that structure is Formulas I or formula III.
The present invention is cooling after being heated to reflux the acetum of the acetone soln of hydrogen iodide and catechol, obtains supersaturation
Then solution carries out hydro-thermal process to the supersaturated solution, four phenol of loop coil is precipitated.In the present invention, the third of the hydrogen iodide
The molar ratio of catechol is preferably 1:2~5 in the acetum of hydrogen iodide and catechol in ketone solution, further preferably
1:3~4.In the present invention, the mass concentration of hydrogen iodide is preferably 80%~99% in the acetone soln of the hydrogen iodide, into one
Step preferably 85%；The mass concentration of catechol is preferably 10%~55% in the acetum of the catechol, into one
Step preferably 20%~50%, more preferably 30%~40%；The mass concentration of acetic acid in the acetum of the catechol
Preferably 10%~40%, further preferably 20%~30%.In the present invention, the acetone, which plays, provides reaction environment
Effect, the acetic acid play the role of catalyst.In the present invention, the temperature being heated to reflux is preferably 117~125 DEG C,
Time is preferably 10~12h；Described be heated to reflux preferably carries out under nitrogen protection.In the present invention, described to be heated to reflux
Effect is abundant heating systems, improves reaction carry out degree, shortens reaction and carries out the time.After the completion of being heated to reflux, the present invention will
Mixed solution is cooled down, and supersaturated solution is obtained.The present invention does not specially require cooling specific embodiment, using this
Mode known to the technical staff of field.
After obtaining supersaturated solution, the present invention carries out hydro-thermal process to the supersaturated solution, and four phenol of loop coil is precipitated.At this
In invention, the temperature of the hydro-thermal process is preferably 200~240 DEG C, and further preferably 210~230 DEG C, the time is preferably 5
~8h, pressure are preferably 1MPa~0.5GPa, further preferably 100~400MPa.The present invention is preferably in above-mentioned high temperature and pressure
Under the conditions of, white crystal is precipitated from supersaturated solution.The present invention preferably washs the white crystal, obtains loop coil four
Phenol, the washing preferably include glacial acetic acid and methylene chloride with detergent, and present invention preferably employs glacial acetic acid and methylene chloride to hand over
For washing.
In the present invention, four phenol of loop coil has structure shown in Formula V:
After obtaining four phenol of loop coil, the present invention has four phenol of loop coil and halonitro methyl phenyl ethers anisole in catalyst and organic solvent
Under the conditions of carry out substitution reaction, obtain tetranitro-anisole spiro-compound.
The present invention mixes four phenol of loop coil, halonitro methyl phenyl ethers anisole, catalyst and organic solvent, forms mixed liquor.?
In the present invention, the halonitro methyl phenyl ethers anisole includes the halogenated -2- Nitroanisole of 5- or the halogenated -5- Nitroanisole of 2-, preferably
For the fluoro- 2- Nitroanisole of 5-, the chloro- 2- Nitroanisole of 5-, the bromo- 2- Nitroanisole of 5-, the fluoro- 5- Nitroanisole of 2-, 2-
Chloro- 5- Nitroanisole or the bromo- 5- Nitroanisole of 2-；The molar ratio of four phenol of loop coil and halonitro methyl phenyl ethers anisole is preferably
1:4~9, further preferably 1:5~8.In the present invention, the catalyst includes one of potassium carbonate and cesium carbonate or two
Kind；The molar ratio of four phenol of loop coil and catalyst is preferably 1:4~8, further preferably 1:5~7.In the present invention, institute
It states organic solvent and preferably includes N-Methyl pyrrolidone, N,N-dimethylformamide or DMAC N,N' dimethyl acetamide；The mixing
Four phenol of loop coil and the gross mass of halonitro methyl phenyl ethers anisole and the volume ratio of organic solvent are preferably 0.15~0.25g/mL in feed liquid.
After obtaining mixed liquor, preferably under nitrogen protection, 0.5h is stirred at room temperature in the present invention, so as to sufficiently connect between substance
Touching, then carries out substitution reaction.In the present invention, the substitution reaction preferably carries out under nitrogen protection, and the present invention preferably will
After four phenol of loop coil and the mixing of halonitro methyl phenyl ethers anisole, it is warming up to substitution reaction temperature, catalyst is then added and replace instead
It answers.In the present invention, the temperature of the substitution reaction is preferably 150~200 DEG C, and further preferably 160~180 DEG C；Time
Preferably 8~10h, the heating rate for being warming up to substitution reaction temperature is preferably 10~12 DEG C/min；Present invention preferably employs micro-
The mode of Wave heating carries out substitution reaction, and the frequency of the microwave is preferably 2GHz.After the completion of substitution reaction, the present invention preferably will
Substitution reaction product discharge is in n-hexane: in deionized water=1:1 mixed system, being then successively separated by solid-liquid separation, solid
Dry and recrystallization, obtains tetranitro-anisole spiro-compound.
In the present invention, when the halonitro methyl phenyl ethers anisole -2- Nitroanisole halogenated for 5-, the tetranitro benzene first
Ether spiro-compound has structure shown in Formula IV；It is described when the halonitro methyl phenyl ethers anisole -5- Nitroanisole halogenated for 2-
Tetranitro-anisole spiro-compound has structure shown in Formula VII:
After obtaining tetranitro-anisole spiro-compound, the present invention is by tetranitro-anisole spiro-compound and Boron tribromide
Demethylation reaction is carried out, is then quenched using methanol, tetranitro hydroxy benzenes spiro-compound is generated.
In the present invention, the amount ratio of the tetranitro-anisole spiro-compound and Boron tribromide and methanol is preferably
1mmol:6~10mmol:10~14mL, further preferably 1mmol:7~9mmol:11~13mL.The present invention is by tetranitro benzene
Demethylation reaction is carried out after methyl ether spiro-compound and Boron tribromide mixing；The tetranitro-anisole spiro-compound and tribromo
The mixing temperature for changing boron is preferably -10~-20 DEG C, and after the completion of mixing, the present invention is preferably by tetranitro-anisole spiro-compound
2~4h is kept at -5~-10 DEG C with the mixture of Boron tribromide, carries out demethylation reaction；Then at -10~-20 DEG C
It is mixed with methanol, continues 1~2h of stirring, quenching reaction.In the present invention, the demethylation reaction is preferably molten in methylene chloride
It is carried out in agent.After the reaction was completed, the present invention preferably discharges the reaction product of demethylation reaction in saturated sodium bicarbonate solution,
Tetranitro hydroxy benzenes spiro-compound is dried to obtain with solid then in turn through being separated by solid-liquid separation.
In the present invention, when the tetranitro-anisole spiro-compound has structure shown in Formula IV, the tetranitro
Hydroxy benzenes spiro-compound has structure shown in Formula VIII；When the tetranitro-anisole spiro-compound has shown in Formula VII
When structure, the tetranitro hydroxy benzenes spiro-compound has structure shown in Formula IX:
After obtaining tetranitro hydroxy benzenes spiro-compound, the present invention is in the presence of sodium hydroxide, using sodium arsenite to four
Nitro benzene spiro-compound is restored, and the polyamine monomers that structure is Formulas I or formula III are obtained.
The present invention preferably in organic solvent restores tetranitro hydroxy benzenes spiro-compound using sodium arsenite；Institute
Stating organic solvent is preferably 1,4- dioxane or dehydrated alcohol.The present invention preferably first by tetranitro hydroxy benzenes spiro-compound and
Organic solvent mixing, forms tetranitro hydroxy benzenes spiro-compound dispersion liquid, then again by the tetranitro hydroxy benzenes spirocyclization
It closes object dispersion liquid to mix with sodium hydroxide, obtains mixed liquor.In the present invention, the tetranitro hydroxy benzenes spiro-compound point
The mass concentration of dispersion liquid is preferably 15%~20%, and further preferably 16%~18%；The tetranitro hydroxy benzenes spirocyclization
The mass ratio for closing object and sodium hydroxide is preferably 1:0.1~0.5, further preferably 1:0.2~0.4.In the present invention, described
Sodium hydroxide plays the role of catalyst.
After obtaining mixed liquor, the mixed liquor is preferably heated to reflux by the present invention, it is described be heated to reflux when
Between preferably 0.5~0.6h.The present invention, which preferably passes through, to be heated to reflux, and tetranitro hydroxy benzenes spiro-compound and sodium hydroxide is made to exist
It is fully dispersed in organic solvent.
After the completion of being heated to reflux, sodium arsenite is preferably added in the present invention into reaction system, carries out reduction reaction.In this hair
In bright, the molar ratio of the tetranitro hydroxy benzenes spiro-compound and sodium arsenite is preferably 1:5~8, further preferably 1:6
~7；The temperature of the reduction reaction is preferably the reflux temperature of system, and reflux temperature is preferably 100~120 DEG C, the reduction
The time of reaction is preferably 8~10h, further preferably 10h.
After the completion of reduction reaction, reduction reaction product is preferably filtered by the present invention while hot, to remove sodium arsenite, is received
It is heated to flowing back after collection filtrate, zinc powder and concentrated hydrochloric acid is then added into filtrate, carry out catalytic hydrogenation, be finally concentrated to give filtrate
To crude product, crude product successively by drying and is recrystallized to give the polyamine monomers that structure is Formulas I or formula III.In the present invention,
The quality of the zinc powder and the volume ratio of concentrated hydrochloric acid are preferably 1g:3~5mL, and the mass concentration of the concentrated hydrochloric acid is preferably 70%
~75%；The temperature of the catalytic hydrogenation is preferably 90~120 DEG C, and the time is preferably 9~12h.The present invention preferably passes through catalysis
Hydrogenation enables nitro in above-mentioned reduction step to be more thoroughly reduced to amino.In the present invention, the temperature of the drying
Preferably 80~100 DEG C of degree, the time is preferably 10~12h；The recrystallization is preferred are as follows: is dissolved in the crude product after drying good
It is heated to reflux temperature in solvent Isosorbide-5-Nitrae-dioxane, is then slowly added into poor solvent deionized water into this back flow reaction liquid,
Until just have Precipitation and it is insoluble when, close heating, 80~100 DEG C of vacuum dry 10~12h, obtain structure for Formulas I or
The polyamine monomers of formula III.
In the present invention, when the polyamine monomers are with structure described in Formula II or formula IV, preparation method includes following step
It is rapid:
(a) after the acetum of the acetone soln of hydrogen iodide, the acetum of catechol and hydroxy benzenes being heated to reflux
It is cooling, supersaturated solution is obtained, hydro-thermal process then is carried out to the supersaturated solution, loop coil triphenol is precipitated；The loop coil three
Phenol has structure shown in Formula X:
(b) the loop coil triphenol and halonitro methyl phenyl ethers anisole obtained the step (a) is in catalysts and solvents existence condition
Lower carry out substitution reaction, obtains trinitroanisole spiro-compound；The halonitro methyl phenyl ethers anisole includes the halogenated -2- nitro of 5-
Methyl phenyl ethers anisole or the halogenated -5- Nitroanisole of 2-；The catalyst includes one or both of potassium carbonate and cesium carbonate；
When the halonitro methyl phenyl ethers anisole -2- Nitroanisole halogenated for 5-, the trinitroanisole spiro compounds
Object has structure shown in Formula XI；When the halonitro methyl phenyl ethers anisole -5- Nitroanisole halogenated for 2-, the trinitrobenzen first
Ether spiro-compound has structure shown in Formula XII:
(c) the trinitroanisole spiro-compound for obtaining the step (b) and Boron tribromide progress demethylation are anti-
It answers, then uses methanol quenching reaction, generate trinitro- hydroxy benzenes spiro-compound；The trinitro- hydroxy benzenes spiro-compound
With structure shown in Formula XIII or Formula XIV:
(d) in the presence of sodium hydroxide, the step (c) is obtained using sodium arsenite trinitro- hydroxy benzenes spirocyclization
It closes object to be restored, obtains the polyamine monomers that structure is Formula II or formula IV.
The acetum of the acetone soln of hydrogen iodide, the acetum of catechol and hydroxy benzenes is heated to reflux by the present invention
After cool down, obtain supersaturated solution, then to the supersaturated solution carry out hydro-thermal process, be precipitated loop coil triphenol.In the present invention
In, the acetic acid of catechol and hydroxy benzenes is molten in the acetum of hydrogen iodide, catechol in the acetone soln of the hydrogen iodide
The molar ratio of hydroxy benzenes is preferably 1:1~4:1~4 in liquid, further preferably 1:2~3:2~3.In the present invention, the iodine
The mass concentration for changing hydrogen iodide in the acetone soln of hydrogen is preferably 80%~99%, and further preferably 85%；Neighbour's benzene two
The mass concentration of catechol is preferably 10%~55% in the acetum of phenol, and further preferably 20%~50%, it is described
The mass concentration of acetic acid is preferably 10%~40% in the acetum of catechol, and further preferably 20%~30%；Institute
The mass concentration for stating hydroxy benzenes in the acetum of hydroxy benzenes is preferably 10%~85%, and further preferably 20%~50%.
In the present invention, the acetone plays the role of providing reaction environment, and the acetic acid plays catalyst.In the present invention
In, the time being heated to reflux is preferably 10~15h；Described be heated to reflux preferably carries out under nitrogen protection.In the present invention
In, the effect being heated to reflux is abundant heating systems, improves reaction carry out degree, shortens reaction and carries out the time.It heats back
After the completion of stream, the present invention cools down mixed solution, obtains supersaturated solution.The present invention does not have cooling specific embodiment
There are special requirement, using mode well-known to those skilled in the art.
After obtaining supersaturated solution, the present invention carries out hydro-thermal process to the supersaturated solution, and loop coil triphenol is precipitated.At this
In invention, the temperature of the hydro-thermal process is preferably 200~240 DEG C, and further preferably 210~230 DEG C, pressure is preferably
1MPa~0.5GPa, further preferably 100~400MPa.For the present invention preferably under above-mentioned high-temperature and high-pressure conditions, supersaturation is molten
Liquation goes out white crystal.The present invention preferably washs the white crystal, obtains loop coil triphenol, and detergent is used in the washing
Glacial acetic acid and methylene chloride are preferably included, present invention preferably employs glacial acetic acid and methylene chloride alternately to wash.
In the present invention, the loop coil triphenol has structure shown in Formula X:
After obtaining loop coil triphenol, the present invention has loop coil triphenol and halonitro methyl phenyl ethers anisole in catalyst and organic solvent
Under the conditions of carry out substitution reaction, obtain trinitroanisole spiro-compound.
The present invention mixes loop coil triphenol, halonitro methyl phenyl ethers anisole, catalyst and organic solvent, forms mixed liquor.?
In the present invention, the halonitro methyl phenyl ethers anisole includes the halogenated -2- Nitroanisole of 5- or the halogenated -5- Nitroanisole of 2-, preferably
For the fluoro- 2- Nitroanisole of 5-, the chloro- 2- Nitroanisole of 5-, the bromo- 2- Nitroanisole of 5-, the fluoro- 5- Nitroanisole of 2-, 2-
Chloro- 5- Nitroanisole or the bromo- 5- Nitroanisole of 2-；The molar ratio of four phenol of loop coil and halonitro methyl phenyl ethers anisole is preferably
1:4~9, further preferably 1:5~8.In the present invention, the catalyst includes one of potassium carbonate and cesium carbonate or two
Kind；The molar ratio of the loop coil triphenol and catalyst is preferably 1:4~8, further preferably 1:5~7.In the present invention, institute
It states organic solvent and preferably includes N-Methyl pyrrolidone, N,N-dimethylformamide or DMAC N,N' dimethyl acetamide；The mixing
The volume ratio of the gross mass and organic solvent of loop coil triphenol and halonitro methyl phenyl ethers anisole is preferably 0.15~0.25g/mL in feed liquid.
After obtaining mixed liquor, preferably under nitrogen protection, 0.5h is stirred at room temperature in the present invention, so as to sufficiently connect between substance
Touching, then carries out substitution reaction.In the present invention, the substitution reaction preferably carries out under nitrogen protection, and the present invention preferably will
After four phenol of loop coil and the mixing of halonitro methyl phenyl ethers anisole, it is warming up to substitution reaction temperature, catalyst is then added and replace instead
It answers.In the present invention, the temperature of the substitution reaction is preferably 150~200 DEG C, and further preferably 160~180 DEG C, the time
Preferably 8~10h, the heating rate for being warming up to substitution reaction temperature is preferably 10~12 DEG C/min；Present invention preferably employs micro-
The mode of Wave heating carries out substitution reaction, and the frequency of the microwave is preferably 2GHz.After the completion of substitution reaction, the present invention preferably will
Substitution reaction product discharge is in n-hexane: in deionized water=1:1 mixed system, being then successively separated by solid-liquid separation, solid
Dry and recrystallization, obtains trinitroanisole spiro-compound.
In the present invention, when the halonitro methyl phenyl ethers anisole -2- Nitroanisole halogenated for 5-, the trinitrobenzen first
Ether spiro-compound has structure shown in Formula XI；It is described when the halonitro methyl phenyl ethers anisole -5- Nitroanisole halogenated for 2-
Trinitroanisole spiro-compound has structure shown in Formula XII:
After obtaining trinitroanisole spiro-compound, the present invention is by trinitroanisole spiro-compound and Boron tribromide
Demethylation reaction is carried out, is then quenched using methanol, trinitro- hydroxy benzenes spiro-compound is generated.
In the present invention, the amount ratio of the trinitroanisole spiro-compound and Boron tribromide and methanol is preferably
1mmol:6~10mmol:10~14mL, further preferably 1mmol:7~9mmol:11~13mL.The present invention is by trinitrobenzen
Demethylation reaction is carried out after methyl ether spiro-compound and Boron tribromide mixing；The trinitroanisole spiro-compound and tribromo
The mixing temperature for changing boron is preferably -10~-20 DEG C, and after the completion of mixing, the present invention is preferably by trinitroanisole spiro-compound
2~4h is kept at -5~-10 DEG C with the mixture of Boron tribromide, carries out demethylation reaction；Then at -10~-20 DEG C
It is mixed with methanol, continues 1~2h of stirring, quenching reaction.In the present invention, the demethylation reaction is preferably molten in methylene chloride
It is carried out in agent.After the reaction was completed, the present invention preferably discharges the reaction product of demethylation reaction in saturated sodium bicarbonate solution,
Tetranitro hydroxy benzenes spiro-compound is dried to obtain with solid then in turn through being separated by solid-liquid separation.
In the present invention, when the trinitroanisole spiro-compound has structure shown in Formula XI, the trinitro-
Hydroxy benzenes spiro-compound has structure shown in Formula XIII；When the trinitroanisole spiro-compound has shown in Formula XII
When structure, the trinitro- hydroxy benzenes spiro-compound has structure shown in Formula XIV:
After obtaining trinitro- hydroxy benzenes spiro-compound, the present invention is in the presence of sodium hydroxide, using sodium arsenite to three
Nitro benzene spiro-compound is restored, and the polyamine monomers that structure is Formulas I or formula III are obtained.
The present invention preferably in organic solvent restores trinitro- hydroxy benzenes spiro-compound using sodium arsenite；Institute
Stating organic solvent is preferably 1,4- dioxane or dehydrated alcohol.The present invention preferably first by trinitro- hydroxy benzenes spiro-compound and
Organic solvent mixing, forms trinitro- hydroxy benzenes spiro-compound dispersion liquid, then again by the trinitro- hydroxy benzenes spirocyclization
It closes object dispersion liquid to mix with sodium hydroxide, obtains mixed liquor.In the present invention, the trinitro- hydroxy benzenes spiro-compound point
The concentration of dispersion liquid is preferably 0.05~0.15g/mL；The mass ratio of the trinitro- hydroxy benzenes spiro-compound and sodium hydroxide is excellent
It is selected as 1:0.1~0.5, further preferably 1:0.2~0.4.In the present invention, the sodium hydroxide plays the work of catalyst
With.
After obtaining mixed liquor, the mixed liquor is preferably heated to reflux by the present invention, it is described be heated to reflux when
Between preferably 0.5~0.6h.The present invention, which preferably passes through, to be heated to reflux, and trinitro- hydroxy benzenes spiro-compound and sodium hydroxide is made to exist
It is fully dispersed in organic solvent.
After the completion of heating, sodium arsenite is preferably added in the present invention into reaction system, carries out reduction reaction.In the present invention
In, the molar ratio of the trinitro- hydroxy benzenes spiro-compound and sodium arsenite is preferably 1:5~8, and further preferably 1:6~
7；The temperature of the reduction reaction is preferably the reflux temperature of system, and reflux temperature is preferably 100~120 DEG C, and the reduction is anti-
The time answered is preferably 8~10h.
After the completion of reduction reaction, the present invention is preferably filtered reduction reaction product while hot, to remove sodium arsenite, is received
It is heated to flowing back after collection filtrate, zinc powder and concentrated hydrochloric acid is then added into filtrate, carry out catalytic hydrogenation, be finally concentrated to give filtrate
To crude product, crude product successively by drying and is recrystallized to give the polyamine monomers that structure is Formula II or formula IV.In the present invention,
The quality of the zinc powder and the volume ratio of concentrated hydrochloric acid are preferably 1g:3~5mL, and the mass concentration of the concentrated hydrochloric acid is preferably 70%
~75%；The temperature of the catalytic hydrogenation is preferably 90~120 DEG C, and the time is preferably 9~12h.In the present invention, the drying
Temperature be preferably 90~100 DEG C, the time is preferably 9~12h.In the present invention, the temperature of the drying is preferably 80~100
DEG C, the time is preferably 10~12h；The recrystallization is preferred are as follows: the crude product after drying is dissolved in good solvent 1,4- dioxy six
It is heated to reflux temperature in ring, is then slowly added into poor solvent deionized water into this back flow reaction liquid, until just there is precipitating to analyse
When out and insoluble, heating is closed, 80~100 DEG C of vacuum dry 10~12h obtain the polyamines list that structure is Formula II or formula IV
Body.
The present invention also provides a kind of polyimides, have structure shown in Formula XV:
Wherein having a R substituent in four R substituents is H, and excess-three R substituent is
Or four R substituents are
Wherein AR has any one of 1~formula of formula 3 structure:
In the present invention, Formula XV is the constitutional repeating unit of polyimides.
The present invention also provides the preparation methods of polyimides described in above-mentioned technical proposal, comprising the following steps:
(i) under nitrogen protection, dianhydride monomer and polyamine monomers are subjected in polar organic solvent polycondensation reaction, obtained
Polyamic acid solution；The polyamine monomers are polyamine monomers described in above-mentioned technical proposal；
(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 polyamine monomers in polar organic solvent,
Obtain polyamic acid solution.
In the present invention, the polyamine monomers are described in polyamine monomers described in above-mentioned technical proposal or above-mentioned technical proposal
The polyamine monomers 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 XVI:
Wherein AR preferably has structure shown in formula 1, formula 2 or formula 3:
In the present invention, the molar ratio of the polyamine monomers and dianhydride monomer is preferably 1:1.5~3, further preferably
1:1.5~2.In the present invention, the sum of the mass concentration of the dianhydride monomer and polyamine monomers in polar organic solvent is preferred
It is 5%~8%, further preferably 6%~7%.The present invention preferably carries out polycondensation reaction at 0~25 DEG C, and the polycondensation is anti-
The time answered is preferably 3~for 24 hours, further preferably 5~20h.
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 polyamine monomers is preferably 4mL:1~3mmol；In the present invention, when being preferably added to isoquinolin, institute
The amount ratio for stating isoquinolin and polyamine monomers is preferably 0.2~0.3mL:1~2mmol.In the present invention, the imidization
Temperature be preferably 60~120 DEG C, further preferably 80~100 DEG C；The time of the imidization is preferably 20~
24h.During imidization, cyclization dehydration occurs the present invention for the polyamic acid solution, generates polyimides.
The present invention is successively filtered, filter cake alcohol preferably by discharging after the cooling of imidization product in deionized water
It washes and vacuum drying treatment, obtains polyimides.The present invention is to the filtering, the tool that filter cake alcohol is washed and vacuum decompression is dried
Body embodiment is not particularly limited, using method commonly used by those skilled in the art.In the present invention, the vacuum
The temperature of drying process is preferably 80 DEG C；The time of the vacuum drying treatment is preferably 12h.
The present invention also provides a kind of Kapton, the Kapton includes gathering described in above-mentioned technical proposal
Acid imide.In the present invention, the Kapton with a thickness of 60~70um.In the present invention, the polyimides is thin
The preparation method of film preferably includes following steps:
Polyimides is dissolved in organic solvent, polyimide solution is formed, then coats the polyimide solution
In substrate, natural cooling after temperature programming processing is carried out, Kapton is obtained.
In the present invention, the solid content of the polyimide solution is preferably 10%~20%, and further preferably 15%.
In the present invention, described program heating preferably includes the four-stage that successively carries out, specially first stage, second stage, the
Three stages and fourth stage；The temperature of the first stage is preferably 55~65 DEG C, and further preferably 60 DEG C, the time is preferably
3.5~4.5h, further preferably 4h；The temperature of the second stage is preferably 85~95 DEG C, and further preferably 90 DEG C, when
Between preferably 11.5~12.5h, further preferably 12h；The temperature of the phase III is preferably 115~125 DEG C, further
Preferably 120 DEG C, the time is preferably 3.5~4.5h, further preferably 4h；The temperature of the fourth stage is preferably 145~
155 DEG C, further preferably 150 DEG C, the time is preferably 3.5~4.5h, further preferably 4h.In the present invention, described cold
It but is preferably natural cooling.
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 HI aqueous solution that 85g mass concentration is 99% is added in the acetone of 15mL and forms mixed solution, formation mixes
It closes solution to be added in the aqueous acetic acid containing 170g catechol, wherein catechol in the aqueous acetic acid of catechol
Mass concentration be 48.6%, the mass concentration of acetic acid is 40% in the aqueous acetic acid of catechol.120 DEG C of obtained solution
It is heated to reflux 10h, then cools to room temperature to obtain supersaturated solution, obtained supersaturated solution is utilized into hydrothermal crystallisation methods,
220 DEG C, be precipitated white micro-crystals compound under the high temperature and pressure of 0.3GPa, filtering, with glacial acetic acid, methylene chloride, alternately washing is three times
Obtain four phenolic compounds of loop coil of 18.0432g.
Into the 250mL three-neck flask equipped with mechanical stirring device, four phenol of loop coil of 15mmol, the 5- of 64mmol is added
Fluoro- 2- Nitroanisole, the n,N-Dimethylformamide of 96mL are stirred at room temperature half an hour under the protection of sufficiently logical nitrogen, adopt
150 DEG C are warming up to the heating rate of 10 DEG C/min with the microwave that frequency is 2GHz, the potassium carbonate of 64mmol, system reaction is added
10h, TLC, which detect to raw material point to disappear as to react, to be terminated, and reaction is stopped；After reaction system discharging in n-hexane: go from
In the mixed system of sub- water=1:1, filters, through 100 DEG C of vacuum drying 12h, be recrystallized to give tetranitro-anisole spiro compounds
Object, obtained product structure such as following formula:
Into the 250mL three-neck flask equipped with mechanical stirring device, the tetranitro-anisole spiro compounds of 12mmol are added
Object, the methylene chloride of 163mL carry out system with liquid nitrogen to be cooled to -20 DEG C, and the tribromide that 100mL concentration is 1mol/L is added dropwise
The dichloromethane solution of boron, it is -10 DEG C of about 2h that maintenance system temperature, which is added dropwise, and then system is cooled to -20 DEG C again, Xiang Ti
120mL anhydrous methanol is added dropwise in system to emerging without white cigarette, continues to stir 1h, system is warming up to room temperature discharging in unsaturated carbonate hydrogen
It in sodium, filters, dry tetranitro hydroxy benzenes spiro-compound, obtained product structure such as following formula:
Tri- neck of 250mL equipped with mechanical stirring device is added in obtained tetranitro hydroxy benzenes spiro-compound 8mmol to burn
In bottle, Isosorbide-5-Nitrae-dioxane of 66mL is added, makes the solid content 10% of system, the catalyst caustic soda of 2.0674g is added, stirs
Heating systems flow back after half an hour to flowing back, the reducing agent sodium arsenite (Na of 59mmol are added3AsO3), back flow reaction 10h,
TLC, which detects to raw material point to disappear as to react, to be terminated, and filtering while hot (temperature cooled product is prevented to be precipitated) removes reducing agent arsenous
Sour sodium (Na3AsO3), it collects filtrate and is heated to flowing back, the zinc powder and 30mL mass concentration that 6.5g is added into system are 70%
Concentrated hydrochloric acid, filtrate filter out zinc powder through catalytic hydrogenation while hot, and concentrating filter liquor obtains crude product, through 100 DEG C of vacuum drying 12h,
Crude product, which is dissolved in, is heated to 110 DEG C of reflux temperature of reaction solution in good solvent Isosorbide-5-Nitrae-dioxane, into this back flow reaction liquid
It is slowly added into poor solvent deionized water, is precipitated and does not dissolve until just having, close heating, 100 DEG C of vacuum dry 12h are obtained
6.4903g tetramine compound, obtained product structure such as following formula:
Embodiment 2
The HI aqueous solution that 5g mass content is 99% is added in the acetone of 10mL and forms mixed solution, the mixing of formation
Solution is added in the 100mL acetum containing 105mmol catechol, and the mass concentration of acetic acid is in acetum
40%, it is then then added in the 100mL acetum containing 150mmol hydroxy benzenes, the mass concentration of acetic acid in acetum
It is 40%.Under stirring, the protection of sufficiently logical nitrogen, it is heated to reflux 15h, then cools to room temperature to obtain supersaturated solution, will
The supersaturated solution arrived utilizes hydrothermal crystallisation methods, and white micro-crystals compound, mistake are precipitated under 240 DEG C, the high temperature and pressure of 0.5GPa
Filter, with glacial acetic acid, methylene chloride, alternately washing obtains three phenolic compounds of loop coil three times.
Into the 250mL three-neck flask equipped with mechanical stirring device, the loop coil triphenol chemical combination of 4.8663g (15mmol) is added
Object, the fluoro- 2- Nitroanisole of the 5- of 10.9523g (64mmol), the n,N-Dimethylformamide of 72mL, the guarantor of sufficiently logical nitrogen
Shield is lower to react at room temperature half an hour, and using frequency is that the microwave of 2GHz is warming up to 150 with the heating rate of 10 DEG C/min
DEG C, the potassium carbonate of 8.8454g (64mmol) is added, system reacts 12h, and TLC, which detects to raw material point to disappear as to react, to be terminated, and is stopped
Only react；After reaction system discharging and n-hexane: in deionized water=1:1 mixed system, filter, through 100 DEG C of vacuum
Dry 12h, is recrystallized to give trinitroanisole spiro-compound, obtained product structure such as following formula:
Into the 250mL three-neck flask equipped with mechanical stirring device, the trinitroanisole of 9.3334g (12mmol) is added
Spiro-compound, the methylene chloride of 150mL be cooled to -20 DEG C hereinafter, dropwise addition 110mL concentration is to system with liquid nitrogen
The dichloromethane solution of the Boron tribromide of 1mol/L, it is -10 DEG C of about 2h that maintenance system temperature, which is added dropwise, and then system drops again
125mL methanol is added dropwise into system to emerging without white cigarette to -20 DEG C for temperature, continues to stir 1h, system be warming up to room temperature discharging with
It in saturated sodium bicarbonate, filters, dry trinitro- hydroxy benzenes spiro-compound, obtained product structure such as following formula:
Trinitro- hydroxy benzenes spiro-compound 5.8856g (8mmol) is added to tri- neck of 250mL that mechanical stirring device is housed
In flask, Isosorbide-5-Nitrae-dioxane of 60mL is added, the catalyst caustic soda of 2.1250g, agitating and heating system to reflux, system is added
Half an hour is reacted, the reducing agent sodium arsenite (Na of 6.72g (52mmol) is added3AsO3), back flow reaction 8h, TLC are detected to raw material
It is that reaction terminates that point, which disappears, and filtering while hot (temperature cooled product is prevented to be precipitated) removes reducing agent sodium arsenite (Na3AsO3),
Collect filtrate to be heated to flowing back, the zinc powder of 6.0g and 70% concentrated hydrochloric acid of 30mL be added into system, filtrate through catalytic hydrogenation,
Zinc powder is filtered out while hot, and concentrating filter liquor obtains crude product, and through 100 DEG C of vacuum drying 12h, crude product is dissolved in good solvent Isosorbide-5-Nitrae-
It is heated to 110 DEG C of reflux temperature of reaction solution in dioxane, is slowly added into poor solvent deionized water into this back flow reaction liquid,
It is precipitated and does not dissolve until just having, close heating, 100 DEG C of vacuum dry 12h obtain 5.0564g triamine compound, obtained production
Object structure such as following formula:
Embodiment 3
It is tested according to the method for embodiment 1, difference is, the fluoro- 2- Nitroanisole of 5- is replaced with the fluoro- 5- nitre of 2-
Base methyl phenyl ethers anisole, finally obtained polyamine monomers structure are shown below:
Embodiment 4
It is tested according to the method for embodiment 2, difference is, the fluoro- 2- Nitroanisole of 5- is replaced with the fluoro- 5- nitre of 2-
Base methyl phenyl ethers anisole, finally obtained polyamine monomers structure are shown below:
Application examples 1
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 2.0mmol, the n,N-dimethylacetamide of 4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids, 8mL, to dianhydride whole is added
After dissolution, the n,N-dimethylacetamide 13mL for the polyamine monomers that the embodiment 1 containing 1mmol is prepared, room is slowly added dropwise
The lower reaction of temperature forms sticky polyamic acid for 24 hours, 0.1mL isoquinolin is added dropwise into reaction system, the system that heats up is to 120 DEG C, dimension
It holds this thermotonus for 24 hours, closes heating, be cooled to room temperature to system, discharge in 200mL deionized water, alcohol reflux washes 3
It is secondary, it is dried at 80 DEG C of vacuum drying oven, obtains the target polyimide polymer PI-1 of 0.9504g, obtained product structure is such as
Following formula:
Application examples 2
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 3 of 2.5mmol are added, the n,N-dimethylacetamide of 3 ', 4,4 '-diphenyl ether tetracid dianhydrides, 6mL is all molten to dianhydride
The n,N-dimethylacetamide 12mL for the polyamine monomers that the embodiment 1 containing 1mmol is prepared is slowly added dropwise in Xie Hou, maintains
System is reacted in ice-water bath forms sticky polyamic acid for 24 hours, and 1mL pyridine and 2mL acetic anhydride are added dropwise into reaction system, rises
Warm system maintains this thermotonus for 24 hours to 60 DEG C, closes heating, is cooled to room temperature to system, discharges in 200mL deionized water
In, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, is obtained the target polyimide polymer PI-2 of 0.7004g, is obtained
The product structure arrived such as following formula:
Application examples 3
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 1.5mmol, the n,N-dimethylacetamide of 4 '-(4,4 '-diphenol oxygroup propyl)-dibenzoic acid acid anhydrides, 10mL,
After dianhydride all dissolution, the N for the polyamine monomers that the embodiment 1 containing 1mmol is prepared, N- dimethylacetamide is slowly added dropwise
Amine 16mL reacts form sticky polyamic acid for 24 hours at room temperature, and 1mL pyridine and 2mL acetic anhydride are added dropwise into reaction system, rises
Warm system maintains this thermotonus for 24 hours to 60 DEG C, closes heating, is cooled to room temperature to system, discharges in 200mL deionized water
In, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, is obtained the target polyimide polymer PI-3 of 1.0041g, is obtained
The product structure arrived such as following formula:
Application examples 4
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 1.5mmol, the n,N-dimethylacetamide of 4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids, 8mL, to dianhydride whole is added
After dissolution, the n,N-dimethylacetamide 11mL for the polyamine monomers that the embodiment 2 containing 1mmol is prepared, room is slowly added dropwise
The lower reaction of temperature forms sticky polyamic acid for 24 hours, and 1mL pyridine and 2mL acetic anhydride, heating system to 80 are added dropwise into reaction system
DEG C, it maintains this thermotonus for 24 hours, closes heating, be cooled to room temperature to system, discharge in 200mL deionized water, alcohol reflux
It washes 3 times, is dried at 80 DEG C of vacuum drying oven, obtain the target polyimide polymer PI-4 of 0.8003g, obtained product structure
Such as following formula:
Application examples 5
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 3 of 1.5mmol are added, the n,N-dimethylacetamide of 3 ', 4,4 '-diphenyl ether tetracid dianhydrides, 6mL is all molten to dianhydride
The n,N-dimethylacetamide 10mL for the polyamine monomers that the embodiment 2 containing 1mmol is prepared, room temperature is slowly added dropwise in Xie Hou
Lower reaction forms sticky polyamic acid for 24 hours, and 1mL pyridine and 2mL acetic anhydride, heating system to 80 are added dropwise into reaction system
DEG C, it maintains this thermotonus for 24 hours, closes heating, be cooled to room temperature to system, discharge in 200mL deionized water, alcohol reflux
It washes 3 times, is dried at 80 DEG C of vacuum drying oven, obtain the target polyimide polymer PI-5 of 0.6024g, obtained product structure
Such as following formula:
Application examples 6
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, 4,4'- (4,4'- diphenol oxygroup propyl)-dibenzoic acid acid anhydride of 1.5mmol, the n,N-dimethylacetamide of 10mL is added,
After dianhydride all dissolution, the N for the polyamine monomers that the embodiment 2 containing 1mmol is prepared, N- dimethylacetamide is slowly added dropwise
Amine 13mL reacts form sticky polyamic acid for 24 hours at room temperature, and 1mL pyridine and 2mL acetic anhydride are added dropwise into reaction system, rises
Warm system maintains this thermotonus for 24 hours to 80 DEG C, closes heating, is cooled to room temperature to system, discharges in 200mL deionized water
In, alcohol reflux is washed 3 times, is dried at 80 DEG C of vacuum drying oven, is obtained the target polyimide polymer PI-6 of 0.9003g, is obtained
The product structure arrived such as following formula:
Structural characterization
Nuclear-magnetism test is carried out to the polyamine monomers that embodiment 1 is prepared, test results are shown in figure 1, as shown in Figure 1,
The polyamine monomers structure that the present invention is prepared is consistent with expection.
Infrared test is carried out to the polyimides that application examples 1~5 is prepared, test results are shown in figure 2, can by Fig. 2
Know, the polyimide structures that the present invention is prepared are consistent with expection.
Carbon dioxide adsorption-desorption test is carried out to the polyimides that application examples 1~3 is prepared, it can be deduced that poly-
Imido pore-size distribution, the pore-size distribution result for the polyimides that application examples 1~3 is prepared is as shown in figure 3, can by Fig. 3
With the pore-size distribution for 1~3 polyimides of example that is applied, the unit of graph of pore diameter distribution abscissa shown in Fig. 3 is nm, ordinate
Unit is (cm3.nm-1.g-1)；The pore size distribution range of application examples 1~3 is 0.55~0.65nm or so, it follows that of the invention
There are microcellular structure, the presence of microcellular structure to easily infiltrate into gas molecules for the super-branched polyimide polymer of offer, increases
Add the selective penetrated property of its film.
Performance test
Dissolubility test
The dissolubility of polyimides prepared by application examples 1~6 is tested, test method are as follows: distinguish polyimides
It is dissolved in DMAC, DMF, NMP, DMSO, THF and CHCl3In, concentration of the polyimides in different solvents is 10mg/mL.Test
Solubility property of the polyimides in different solvents, ++: room temperature is entirely molten；+: heating is complete molten；+-: is partly dissolved；--: heating is not
It is molten.Test result is as shown in table 1.
The dissolubility for the polyimides that 1 application examples 1~6 of table is prepared
By 1 test result of table it is found that the polyimides that is prepared of polyamine monomers provided by the invention have it is preferable molten
Xie Xing.Polyamine monomers provided by the invention introduce the groups such as aliphatic structure, ehter bond, make by polyamine monomers 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 application examples 1~6 of the present invention is prepared is prepared into Kapton, specific preparation 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 is carried out to the Kapton that application examples 1~6 is prepared, test result is as shown in table 2,
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 application examples of table, 1~6 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 5~33Barrer to the infiltration coefficient of nitrogen, and the infiltration coefficient to methane is
7~62Barrer is 25~119Barrer to the infiltration coefficient of oxygen, the infiltration coefficient to carbon dioxide is 98~
540Barrer.Thus illustrate Kapton that polyimides provided by the invention is prepared to the permeability of gas compared with
It is high.
Kapton provided by the invention is 14.2 to the gas separation coefficient of carbon dioxide and nitrogen mixed gas
~21.8, the gas separation coefficient to carbon dioxide and methane mixed gas is 8.0~20.2, to oxygen and nitrogen mixed gas
Gas separation coefficient be 3.6~5.3.In the present invention, the calculation method of gas separation coefficient is αA/B=PA/PB, PAAnd PB
The infiltration coefficient of two kinds of gas of respectively A and B.Thus illustrate, the polyimides that polyimides provided by the invention is prepared
Film is higher to the selectivity of gas, i.e., after polyimides provided by the invention is prepared into Kapton, is guaranteeing well
While selective, have the characteristics that permeability is high.
In conclusion the polyimides that is prepared of polyamine monomers provided by the invention DMAC, DMF, NMP, DMSO,
THF and CHCl3In there is preferable dissolubility, and existed by the Kapton that polyimides of the present invention is prepared
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 polyamine monomers have structure shown in Formulas I~any one of formula IV:
2. the preparation method of polyamine monomers described in claim 1, when the polyamine monomers have structure described in Formulas I or formula III
When, the preparation method comprises the following steps:
(1) cooling after being heated to reflux the acetum of the acetone soln of hydrogen iodide and catechol, supersaturated solution is obtained, so
Hydro-thermal process is carried out to the supersaturated solution afterwards, four phenol of loop coil is precipitated；Four phenol of loop coil has structure shown in Formula V:
(2) four phenol of loop coil and halonitro methyl phenyl ethers anisole obtained the step (1) is in catalyst and organic solvent existence condition
Lower carry out substitution reaction, obtains tetranitro-anisole spiro-compound；The halonitro methyl phenyl ethers anisole includes the halogenated -2- nitro of 5-
Methyl phenyl ethers anisole or the halogenated -5- Nitroanisole of 2-；The catalyst includes one or both of potassium carbonate and cesium carbonate；
When the halonitro methyl phenyl ethers anisole -2- Nitroanisole halogenated for 5-, the tetranitro-anisole spiro-compound tool
There is structure shown in Formula IV；When the halonitro methyl phenyl ethers anisole -5- Nitroanisole halogenated for 2-, the tetranitro-anisole spiral shell
Cycle compound has structure shown in Formula VII:
(3) the tetranitro-anisole spiro-compound for obtaining the step (2) and Boron tribromide carry out demethylation reaction, so
It is quenched afterwards using methanol, generates tetranitro hydroxy benzenes spiro-compound；The tetranitro hydroxy benzenes spiro-compound has formula
Structure shown in VIII or Formula IX:
(4) in the presence of sodium hydroxide, the step (3) is obtained using sodium arsenite tetranitro hydroxy benzenes spiro-compound
It is restored, obtains the polyamine monomers that structure is Formulas I or formula III；
When the polyamine monomers are with structure described in Formula II or formula IV, the preparation method comprises the following steps:
It is (a) cooling after being heated to reflux the acetum of the acetone soln of hydrogen iodide, the acetum of catechol and hydroxy benzenes,
Supersaturated solution is obtained, hydro-thermal process then is carried out to the supersaturated solution, loop coil triphenol is precipitated；The loop coil triphenol has
Structure shown in Formula X:
(b) the loop coil triphenol and halonitro methyl phenyl ethers anisole obtained the step (a) is in catalyst and organic solvent existence condition
Lower carry out substitution reaction, obtains trinitroanisole spiro-compound；The halonitro methyl phenyl ethers anisole includes the halogenated -2- nitro of 5-
Methyl phenyl ethers anisole or the halogenated -5- Nitroanisole of 2-；The catalyst includes one or both of potassium carbonate and cesium carbonate；
When the halonitro methyl phenyl ethers anisole -2- Nitroanisole halogenated for 5-, the trinitroanisole spiro-compound tool
There is structure shown in Formula XI；When the halonitro methyl phenyl ethers anisole -5- Nitroanisole halogenated for 2-, the trinitroanisole spiral shell
Cycle compound has structure shown in Formula XII:
(c) the trinitroanisole spiro-compound for obtaining the step (b) and Boron tribromide and methanol carry out demethylation
Reaction, is then quenched using methanol, and trinitro- hydroxy benzenes spiro-compound is generated；The trinitro- hydroxy benzenes spiro-compound tool
There is structure shown in Formula XIII or Formula XIV:
(d) in the presence of sodium hydroxide, the step (c) is obtained using sodium arsenite trinitro- hydroxy benzenes spiro-compound
It is restored, obtains the polyamine monomers that structure is Formula II or formula IV.
3. preparation method according to claim 2, which is characterized in that hydrogen iodide and catechol in the step (1)
Molar ratio is 1:2~5；The temperature of hydro-thermal process is 200~240 DEG C in the step (1), and pressure is 1MPa~0.5GPa.
4. preparation method according to claim 2, which is characterized in that hydrogen iodide, catechol and hydroxyl in the step (a)
The molar ratio of base benzene is 1:1~4:1~4；The temperature of hydro-thermal process is 200~240 DEG C in the step (a), pressure 1MPa
~0.5GPa.
5. preparation method according to claim 2, which is characterized in that step (2) kind four phenol of loop coil and halonitro
The molar ratio of methyl phenyl ethers anisole is 1:4~9；The temperature of substitution reaction is 150~200 DEG C in the step (2), and the time is 8~10h；
The molar ratio of loop coil triphenol and halonitro methyl phenyl ethers anisole is 1:4~9 in the step (b)；Replace in the step (b) anti-
The temperature answered is 150~200 DEG C, and the time is 8~10h.
6. preparation method according to claim 2, which is characterized in that tetranitro-anisole spirocyclization in the step (3)
The amount ratio for closing object and Boron tribromide and methanol is 1mmol:6~10mmol:10~14mL；Demethylation in the step (3)
The temperature of reaction is -5~-10 DEG C, and the time is 2~4h；
In the step (c) amount ratio of trinitroanisole spiro-compound and Boron tribromide and methanol be 1mmol:6~
10mmol:10~14mL；The temperature of demethylation reaction is -5~-10 DEG C in the step (c), and the time is 2~4h.
7. preparation method according to claim 2, which is characterized in that tetranitro hydroxy benzenes spirocyclization in the step (4)
The molar ratio for closing object and sodium arsenite is 1:5~8；The temperature restored in the step (4) is 100~120 DEG C, the time is 8~
10h；
The molar ratio of trinitro- hydroxy benzenes spiro-compound and sodium arsenite is 1:5~8 in the step (d)；The step (d)
The temperature of middle reduction is 100~130 DEG C, and the time is 8~10h.
8. a kind of polyimides has structure shown in Formula XV:
Wherein having a R substituent in four R substituents is H, and excess-three R substituent is
Or four R substituents are
Wherein AR has any one of 1~formula of formula 3 structure:
9. the preparation method of polyimides described in claim 8, comprising the following steps:
(i) under nitrogen protection, dianhydride monomer and polyamine monomers are subjected in polar organic solvent polycondensation reaction, obtain polyamides
Amino acid solution；The polyamine monomers are any one of polyamine monomers described in claim 1 or claim 2~7 preparation side
The polyamine monomers 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. a kind of Kapton, which is characterized in that the Kapton includes polyimides described in claim 8
Or the polyimides that claim 9 the method is prepared；The Kapton with a thickness of 60~70um.
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| CN111410617A (en) * | 2020-04-14 | 2020-07-14 | 吉林大学 | Tetramine monomer containing spiro structure, preparation method and application thereof, polyamide, and preparation method and application thereof |
| CN112940250A (en) * | 2021-02-02 | 2021-06-11 | 武汉柔显科技股份有限公司 | Resin, photosensitive resin composition, and photosensitive resin film |
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| CN107551835A (en) * | 2017-10-09 | 2018-01-09 | 辽宁科技大学 | The preparation method of high flux graphene oxide/polyimides mixed-matrix membrane material |
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| US20020010370A1 (en) * | 2000-03-10 | 2002-01-24 | Haussmann J?Ouml;Rg | Bis-o-aminophenols and o-aminophenolcarboxylic acids and process for preparing the same |
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| CN111410617A (en) * | 2020-04-14 | 2020-07-14 | 吉林大学 | Tetramine monomer containing spiro structure, preparation method and application thereof, polyamide, and preparation method and application thereof |
| CN112940250A (en) * | 2021-02-02 | 2021-06-11 | 武汉柔显科技股份有限公司 | Resin, photosensitive resin composition, and photosensitive resin film |
| CN112940250B (en) * | 2021-02-02 | 2022-09-23 | 武汉柔显科技股份有限公司 | Photosensitive resin composition and photosensitive resin film |
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