CN110105189A - 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 - Google Patents
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 Download PDFInfo
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- CN110105189A CN110105189A CN201910423420.3A CN201910423420A CN110105189A CN 110105189 A CN110105189 A CN 110105189A CN 201910423420 A CN201910423420 A CN 201910423420A CN 110105189 A CN110105189 A CN 110105189A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
- C07C65/24—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups polycyclic
- C07C65/26—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups polycyclic containing rings other than six-membered aromatic rings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/93—Spiro compounds
- C07C2603/94—Spiro compounds containing "free" spiro atoms
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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Abstract
The present invention provides a kind of fluorine-containing polyacid monomer and preparation method thereof, a kind of polyamide and preparation method thereof and a kind of polyamide films, belong to technical field of organic synthesis.Fluorine-containing polyacid monomer provided by the invention has the trifluoromethyl structure of loop coil microcellular structure and flexible group and large volume, has microcellular structure and dissaving structure using the polyamide that this fluorine-containing polyacid monomer synthesizes, so that the gas permeability of polyamide is good；The presence of ehter bond increases the free volume and flexibility of polymer molecular chain, so that the favorable solubility of polyamide；The PA membrane that is prepared using polyamide of the present invention while there is preferable gas-selectively and permeability.The present invention provides the preparation methods of above-mentioned fluorine-containing polyacid monomer and polyamide, this method is simple and easy, and synthetic route is short, are suitble to industrial mass production.
Description
Technical field
The present invention relates to technical field of organic synthesis, in particular to a kind of fluorine-containing polyacid monomer and preparation method thereof, one kind
Polyamide and preparation method thereof and a kind of polyamide film.
Background technique
Most of gas separation membrane (GS) is non-porous film, and gas follows " dissolution-diffusion " mechanism through process.Aromatic series
Polyamide because on main chain aromatic ring structure and intermolecular hydrogen bonding effect, have good heat resistance, mechanical strength and separation property
Can, it has been widely used in gas separation field since the 1990s.
Gas separation membrane technology is as a kind of green separation technique, separation process and " cryogenic separation " and " pressure-variable adsorption
The isolation technics such as separation " compare, and have many advantages, such as that separative efficiency is high, easy to operate, low energy consumption, green non-pollution, are recognized
For the new gas isolation technics for being 21 century most development and application prospect, be widely used in medicine food, biochemistry,
The fields such as energy environment protection.Relative to traditional gas isolation technics, UF membrane has many advantages, such as that low energy consumption, small investment, equipment are simple,
There is important application in terms of oxygen/nitrogen separation, dehumidification of gas, carbon dioxide recovery, Hydrogen Separation.
But there is the relationship mutually restricted in usual polymer permeability of the membrane and selectivity, i.e. permeability increases, then selects
Selecting property reduces, and here it is so-called Trade-off effects.Therefore, synthesis has the polymer of microcellular structure and prepares and has both
High osmosis and highly selective polymeric gas seperation film have very to improving gas separative efficiency and expanding application range
Far-reaching influence.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of fluorine-containing polyacid monomer and preparation method thereof, a kind of polyamide and
Preparation method and a kind of polyamide film.Fluorine-containing polyacid monomer provided by the invention has loop coil microcellular structure and flexible group
And the trifluoromethyl structure of large volume, there is microcellular structure and hyperbranched knot using the polyamide that this fluorine-containing polyacid monomer synthesizes
Structure, favorable solubility；The PA membrane that is prepared using polyamide of the present invention while there is preferable gas-selectively and infiltration
Permeability.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of fluorine-containing polyacid monomers, have structure shown in Formulas I or Formula II:
The present invention provides the preparation methods of above-mentioned fluorine-containing polyacid monomer, when the fluorine-containing polyacid monomer has shown in Formulas I
When structure, the preparation method comprises the following steps:
(1) under the action of reducing agent and acid catalyst, Hexafluoro acetone and catechol is subjected to isomerization reaction, obtained
Four phenol of loop coil with structure shown in formula (a)；
(2) under the effect of the catalyst, four phenol of loop coil with structure shown in formula (a) is replaced with p-Fluorophenyl cyanide
Reaction, obtains the four cyano spiro-compound with structure shown in formula (b)；
(3) reaction is hydrolyzed in the four cyano spiro-compound with structure shown in formula (b) in basic solvent, later
The pH value of hydrolysis liquid is adjusted to acidity, obtains the fluorine-containing polyacid monomer with Formulas I depicted structure；
When the fluorine-containing polyacid monomer has structure shown in Formula II, the preparation method comprises the following steps:
(i) under the action of reducing agent and acid catalyst, it is anti-that Hexafluoro acetone, catechol and phenol are subjected to isomerization
It answers, obtains the loop coil triphenol with structure shown in formula (c)；
(ii) under the effect of the catalyst, the loop coil triphenol with structure shown in formula (c) is taken with p-Fluorophenyl cyanide
Generation reaction, obtains the tricyano spiro-compound with structure shown in formula (d)；
(iii) reaction is hydrolyzed in the tricyano spiro-compound with structure shown in formula (d) in basic solvent, it
The pH value of hydrolysis liquid is adjusted to acidity afterwards, obtains the fluorine-containing polyacid monomer with Formula II depicted structure.
Preferably, the reducing agent in the step (1) and step (i) independently is hydrazine hydrate, zinc powder, magnesium powder, iron powder, chlorine
Change one or more of stannous, frerrous chloride and sodium borohydride.
Preferably, the molar ratio of Hexafluoro acetone, catechol and reducing agent is 1~2:1~2 in the step (1):
5~10；
Hexafluoro acetone in the step (i), catechol, phenol and reducing agent molar ratio be 1.5~6:1~4:1~
4:5~10.
Preferably, the temperature of isomerization reaction independently is 117~125 DEG C in the step (1) and step (i), the time
It independently is 10~12h.
Preferably, the molar ratio of four phenol of loop coil and p-Fluorophenyl cyanide is 1:4~9 in the step (2)；The catalyst is
Sodium hydride and/or cesium fluoride；The temperature of the substitution reaction is 150~200 DEG C, and the time is 10~12h；
The molar ratio of loop coil triphenol and p-Fluorophenyl cyanide is 1:4~9 in the step (ii)；The catalyst is sodium hydride
And/or cesium fluoride；The temperature of the substitution reaction is 150~200 DEG C, and the time is 10~12h.
Preferably, the temperature of hydrolysis independently is 80~100 DEG C in the step (3) and step (iii), and the time is only
It is on the spot 15~20h.
The present invention also provides a kind of polyamide, have structure shown in formula III:
A R substituent is H in formula III, and excess-three R substituent is the substituent group with structure shown in formula (e)；Or formula
Four R substituents are the substituent group with structure shown in formula (e) in III；
AR is in formula (e)
The present invention provides the preparation methods of above-mentioned polyamide, comprising the following steps:
Under the action of salt forming agent, it is anti-that fluorine-containing polyacid monomer and diamine monomer are carried out to polycondensation in polar organic solvent
It answers, obtains polyamide；
The fluorine-containing polyacid monomer is the above-mentioned fluorine-containing polyacid monomer with structure shown in Formulas I or Formula II.
The present invention also provides a kind of polyamide film, the polyamide film includes above-mentioned polyamide or the above method
The polyamide being prepared.
The present invention provides a kind of fluorine-containing polyacid monomers, have structure shown in Formulas I or Formula II.It is provided by the invention fluorine-containing more
Acid monomers have the trifluoromethyl (- CF of loop coil microcellular structure and flexible group (ehter bond) and large volume3) structure.By the present invention
The fluorine-containing polyacid monomer provided further polymerize to obtain polyamide with diamine monomer, has structure shown in formula III.The present invention mentions
There are microcellular structures between the polyamide molecule of confession, gas molecules can be made to easily infiltrate into；Meanwhile polyamide provided by the invention
For dissaving polymer, the presence of dissaving structure makes the bigger gap of intermolecular presence, its infiltration coefficient can be improved.In addition,
The presence of ehter bond increases the free volume and flexibility of polymer molecular chain in polyamide provided by the invention, 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；And large volume trifluoromethyl
In the presence of the volume for the degreeof tortuosity and molecule for increasing molecule, the free volume of polymer is improved, to increase the infiltration of gas
Permeability, in addition to this fluorine atom in trifluoromethyl can increase the phase interaction between organic solvent due to electronegativity
With improving the dissolubility of polymer.Embodiment the result shows that, polyamide provided by the invention DMAC, DMF, NMP, DMSO,
THF and CHCl3In have good dissolubility.
The present invention also provides a kind of polyamide film, this polyamide film has preferable gas-selectively and infiltration simultaneously
Permeability.Embodiment the result shows that, polyamide film provided by the invention is 45~99Barrer to the infiltration coefficient of oxygen, to two
The infiltration coefficient of carbonoxide is 210~395Barrer, and the gas separation coefficient to carbon dioxide and nitrogen mixed gas is 8.7
~33.8, the gas separation coefficient to carbon dioxide and methane mixed gas is 7.9~18.1, to oxygen and nitrogen mixed gas
Gas separation coefficient be 1.9~6.3.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy spectrogram for the fluorine-containing polyacid monomer that the embodiment of the present invention 1 is prepared；
Fig. 2 is the infrared spectrum for the polyamide that the embodiment of the present invention 3~5 is prepared.
Specific embodiment
The present invention provides a kind of fluorine-containing polyacid monomers, have structure shown in Formulas I or Formula II:
Fluorine-containing polyacid monomer provided by the invention has loop coil microcellular structure and flexible group (ehter bond) and large volume
Group trifluoromethyl (- CF3) structure.
The present invention provides the preparation methods of above-mentioned fluorine-containing polyacid monomer, when the fluorine-containing polyacid monomer has shown in Formulas I
When structure, the preparation method comprises the following steps:
(1) under the action of reducing agent and acid catalyst, Hexafluoro acetone and catechol is subjected to isomerization reaction, obtained
Four phenol of loop coil with structure shown in formula (a)；
(2) under the effect of the catalyst, four phenol of loop coil with structure shown in formula (a) is replaced with p-Fluorophenyl cyanide
Reaction, obtains the four cyano spiro-compound with structure shown in formula (b)；
(3) reaction is hydrolyzed in the four cyano spiro-compound with structure shown in formula (b) in alkaline solution, later
The pH value of hydrolysis liquid is adjusted to acidity, obtains the fluorine-containing polyacid monomer with Formulas I depicted structure.
The present invention carries out isomerization reaction under the action of reducing agent and acid catalyst, by Hexafluoro acetone and catechol,
Obtain four phenol of loop coil with structure shown in formula (a).In the present invention, the reducing agent be preferably hydrazine hydrate, zinc powder, magnesium powder,
One or more of iron powder, stannous chloride, frerrous chloride and sodium borohydride；The Hexafluoro acetone, catechol and reducing agent
Molar ratio be preferably 1~2:1~2:5~10.In the present invention, the effect of the Hexafluoro acetone is to provide reaction environment and mentions
For trifluoromethyl group, the effect of the reducing agent is that the F and O that generate in reaction is made further to become HF and H2O。
In the present invention, the acid catalyst is preferably acetic acid.In a specific embodiment of the present invention, preferably by adjacent benzene two
Phenol is mixed with acetic acid, obtains the acetum of catechol, and the amount ratio of the catechol and acetic acid is preferably 45~55g:
1mol, more preferably 50g:1mol.
Acidulant is further preferably added in the present invention into the isomerization reaction system, and the acidulant is preferably hydrogen iodide.
In a specific embodiment of the present invention, preferably Hexafluoro acetone and hydrogen iodide are mixed, obtains the Hexafluoro acetone solution of hydrogen iodide；Institute
The mass concentration for stating hydrogen iodide in the Hexafluoro acetone solution of hydrogen iodide is preferably 80~99%, and more preferably 85%.
During the isomerization reaction, the Hexafluoro acetone solution of hydrogen iodide and the vinegar of catechol is preferably first added in the present invention
Acid solution adds reducing agent, carries out isomerization reaction under conditions of being heated to reflux later.In the present invention, the isomery
The temperature for changing reaction is preferably 117~125 DEG C, and more preferably 118~122 DEG C；The time of the isomerization reaction is preferably 10
~12h, more preferably 11h；Described be heated to reflux preferably carries out under nitrogen protection atmosphere.In the present invention, described to heat back
The effect of stream is abundant heating systems, improves reaction carry out degree, shortens reaction and carries out the time.
After the completion of isomerization reaction, the present invention preferably post-processes the isomerization reaction liquid, and the post-processing is excellent
Choosing the following steps are included:
Cooling, hydro-thermal process, filtering and washing are successively carried out to the isomerization reaction liquid, obtained with shown in formula (a)
Four phenol of loop coil of structure.
The present invention preferably cools down the isomerization reaction liquid, obtains supersaturated solution after cooling.The present invention is to institute
Stating cooling mode does not have special requirement, uses the type of cooling well known to those skilled in the art.In the present invention, institute
The temperature for stating hydro-thermal process is preferably 220~260 DEG C, and more preferably 240~250 DEG C；The time of the hydro-thermal process is preferably 5
~8h, more preferably 6~7h；The pressure of the hydro-thermal process is preferably 1MPa~0.5GPa, more preferably 100~400MPa.
The present invention can be such that four phenol of the loop coil with structure shown in formula (a) is precipitated from reaction solution by hydro-thermal process, be by filtering
Four phenol crystal of loop coil can be obtained.The present invention preferably washs the four phenol crystal of loop coil, and the washing detergent is preferred
For glacial acetic acid and tetrahydrofuran；Present invention preferably uses glacial acetic acid and tetrahydrofuran alternately to wash to crystal, described alternately to wash
Number be preferably 3 times.
After obtaining four phenol of loop coil, the present invention under the effect of the catalyst, will have four phenol of loop coil of structure shown in formula (a) with
P-Fluorophenyl cyanide carries out substitution reaction, obtains the four cyano spiro-compound with structure shown in formula (b).In the present invention, institute
The molar ratio for stating four phenol of loop coil and p-Fluorophenyl cyanide is preferably 1:4~9, more preferably 1:5~8.In the present invention, the catalysis
Agent is preferably sodium hydride and/or cesium fluoride, and the molar ratio of four phenol of loop coil and catalyst is preferably 1:4~8, and more preferably 1:
5~7.
After the present invention preferably mixes four phenol of loop coil and p-Fluorophenyl cyanide, it is first warming up to substitution reaction temperature, is then added again
Enter catalyst；The mixed mode is preferably stirred, and the time of the stirring is preferably 0.5h；The rate of the heating
Preferably 10~12 DEG C/min；Present invention preferably uses the modes of microwave heating to be warming up to substitution reaction temperature, the microwave
Frequency is preferably 2~3GHz.In the present invention, the substitution reaction preferably carries out under nitrogen protection, the substitution reaction
Temperature is preferably 150~200 DEG C, and more preferably 160~180 DEG C；The time of the substitution reaction is preferably 10~12h, more excellent
It is selected as 11h, since the substitution reaction time of the invention calculate being added after catalyst.
After the completion of substitution reaction, the present invention preferably post-processes substitution reaction product, obtains four cyano spiro compounds
Object solid.In the present invention, the post-processing preferably includes following steps:
Reaction product is discharged in the mixed solvent, is heated to reflux, poor solvent, which is added, is precipitated crystal, successively carries out later
It is separated by solid-liquid separation, dry and recrystallization, obtains four cyano spiro-compound solid.
In the present invention, the mixed solvent is preferably the mixed solvent of n,N-Dimethylformamide and deionized water；Institute
The volume ratio for stating in the mixed solvent N,N-dimethylformamide and deionized water is preferably 1:1.In the present invention, the poor solvent
Preferably water, the dosage of the poor solvent is not subject to so that crystal just has precipitation, and after stirring, crystal precipitation disappears.The present invention couple
The separation of solid and liquid, dry and recrystallization mode do not have special requirement, use above-mentioned behaviour well known to those skilled in the art
Make mode.
After obtaining four cyano spiro-compound, the present invention will have the four cyano spiro-compound of structure shown in formula (b) to exist
Reaction is hydrolyzed in alkaline solution, the pH value of hydrolysis liquid is adjusted to acidity later, obtains that there is Formulas I depicted structure
Fluorine-containing polyacid monomer.In the present invention, the alkaline solution is preferably sodium hydrate aqueous solution, the sodium hydrate aqueous solution
Mass concentration is preferably 40~50%, and more preferably 45%；It is molten in the four cyano spiro-compound and sodium hydrate aqueous solution
The molar ratio of matter is preferably 1:8.5~9.5, more preferably 1:8.8.
Four cyano spiro-compound and alkaline solution are preferably placed in solvent and reaction are hydrolyzed by the present invention, the solvent
The preferably mixed liquor of water and dehydrated alcohol, water and dehydrated alcohol volume ratio are preferably 1:0.5~1.5 in the mixed liquor, more
Preferably 1:1.In the present invention, the temperature of the hydrolysis is preferably 80~100 DEG C, and more preferably 90 DEG C, the hydrolysis
The time of reaction is preferably 15~20h, more preferably 16~18h.In the present invention, four cyano spiro-compound is in alkaline condition
Under be hydrolyzed, generate carboxylate.
After the completion of hydrolysis, the pH value of hydrolysis liquid is adjusted to acidity by the present invention, obtains solid product.The present invention
It is preferred that the pH value of hydrolysis liquid is adjusted to 1.5~2.5, more preferable 2.The present invention preferably first boils off the ethyl alcohol in reaction solution,
By discharging after the filtrate cooling after ethanol evaporation in deionized water, pH value is then adjusted again.In the present invention, the deionization
The dosage of water is preferably 400~500mL, more preferable 450mL.The present invention does not have special requirement to pH value regulator is adjusted,
Use acidic pH adjustor well known to those skilled in the art.In the present invention, carboxylic can be made by adjusting pH value to acidity
Carboxylate radical in hydrochlorate is converted into carboxyl, and solid product is precipitated.
After obtaining solid product, the present invention is preferably successively filtered, washs and is dried to the solid product, is had
There is the fluorine-containing polyacid monomer of Formulas I depicted structure.The present invention does not have special requirement to the suction filtration, washing and dry mode,
Use aforesaid operations well known to those skilled in the art.
When the fluorine-containing polyacid monomer has structure shown in Formula II, the preparation method comprises the following steps:
(i) under the action of reducing agent and acid catalyst, it is anti-that Hexafluoro acetone, catechol and phenol are subjected to isomerization
It answers, obtains the loop coil triphenol with structure shown in formula (c)；
(ii) under the effect of the catalyst, the loop coil triphenol with structure shown in formula (c) is taken with p-Fluorophenyl cyanide
Generation reaction, obtains the tricyano spiro-compound with structure shown in formula (d)；
(iii) reaction is hydrolyzed in the tricyano spiro-compound with structure shown in formula (d) in basic solvent, it
The pH value of hydrolysis liquid is adjusted to acidity afterwards, obtains the fluorine-containing polyacid monomer with Formula II depicted structure.
The present invention carries out isomerization under the action of reducing agent and acid catalyst, by Hexafluoro acetone, catechol and phenol
Reaction, obtains the loop coil triphenol with structure shown in formula (c).In the present invention, the reducing agent be preferably hydrazine hydrate, zinc powder,
One or more of magnesium powder, iron powder, stannous chloride, frerrous chloride and sodium borohydride；The Hexafluoro acetone, catechol, benzene
The molar ratio of phenol and reducing agent is 1.5~6:1~4:1~4:5~10, more preferably 2~4:2~3:2~3:6~9.In this hair
In bright, the effect of the Hexafluoro acetone is to provide reaction environment and provides trifluoromethyl group, and the effect of the reducing agent is to make
The F and O generated in reaction further becomes HF and H2O。
In the present invention, the acid catalyst is preferably acetic acid.In a specific embodiment of the present invention, preferably by adjacent benzene two
Phenol and phenol are mixed with acetic acid respectively, obtain the acetum of catechol and the acetum of phenol；The catechol
The mass concentration of catechol is preferably 10~55% in acetum, and more preferably 20~50%；The acetic acid of the phenol is molten
The mass concentration of phenol is preferably 10~55% in liquid, and more preferably 20~50%.
Acidulant is further preferably added in the present invention into the isomerization reaction system, and the acidulant is preferably hydrogen iodide.
In a specific embodiment of the present invention, choosing mixes Hexafluoro acetone and hydrogen iodide, obtains the Hexafluoro acetone solution of hydrogen iodide；It is described
The mass concentration of hydrogen iodide is preferably 80~99% in the Hexafluoro acetone solution of hydrogen iodide, and more preferably 85%.In the present invention,
The hydrogen iodide plays the role of acidulant, and reaction rate can be improved.
During the isomerization reaction, the vinegar of the Hexafluoro acetone solution of hydrogen iodide, catechol is preferably first added in the present invention
The acetum of acid solution, phenol adds reducing agent, carries out isomerization reaction under conditions of being heated to reflux later.At this
In invention, the temperature of the isomerization reaction is preferably 117~125 DEG C, and more preferably 118~122 DEG C；The isomerization reaction
Time be preferably 10~12h, more preferably 11h；Described be heated to reflux preferably carries out under nitrogen protection atmosphere.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.
After the completion of isomerization reaction, the present invention preferably post-processes the isomerization reaction liquid, and the post-processing is excellent
Choosing the following steps are included:
Cooling, hydro-thermal process, filtering and washing are successively carried out to the isomerization reaction liquid, obtained with shown in formula (c)
The loop coil triphenol of structure.
The present invention preferably cools down the isomerization reaction liquid, obtains supersaturated solution after cooling.The present invention is to institute
Stating cooling mode does not have special requirement, uses the type of cooling well known to those skilled in the art.In the present invention, institute
The temperature for stating hydro-thermal process is preferably 220~260 DEG C, and more preferably 240~250 DEG C；The time of the hydro-thermal process is preferably 5
~8h, more preferably 6~7h；The pressure of the hydro-thermal process is preferably 1MPa~0.5GPa, more preferably 100~400MPa.
The present invention can be such that the loop coil triphenol with structure shown in formula (c) is precipitated from reaction solution by hydro-thermal process, be by filtering
Loop coil triphenol crystal can be obtained.The present invention preferably washs the loop coil triphenol crystal, and the washing detergent is preferred
For glacial acetic acid and tetrahydrofuran；Present invention preferably uses glacial acetic acid and tetrahydrofuran alternately to wash to crystal, described alternately to wash
Number be preferably 3 times.
After obtaining loop coil triphenol, the present invention under the effect of the catalyst, will have the loop coil triphenol of structure shown in formula (c) with
P-Fluorophenyl cyanide carries out substitution reaction, obtains the tricyano spiro-compound with structure shown in formula (d).In the present invention, institute
The molar ratio for stating loop coil triphenol and p-Fluorophenyl cyanide is preferably 1:4~9, more preferably 1:5~8.In the present invention, the catalysis
Agent is preferably sodium hydride and/or cesium fluoride, and the molar ratio of the loop coil triphenol and catalyst is preferably 1:4~8, and more preferably 1:
5~7.
After the present invention preferably mixes loop coil triphenol and p-Fluorophenyl cyanide, it is first warming up to substitution reaction temperature, is then added again
Enter catalyst；The mixed mode is preferably stirred, and the time of the stirring is preferably 0.5h；The rate of the heating
Preferably 10~12 DEG C/min；Present invention preferably uses the modes of microwave heating to be warming up to substitution reaction temperature, the microwave
Frequency is preferably 2~3GHz.In the present invention, the substitution reaction preferably carries out under nitrogen protection, the substitution reaction
Temperature is preferably 150~200 DEG C, and more preferably 160~180 DEG C；The time of the substitution reaction is preferably 10~12h, more excellent
It is selected as 11h, since the substitution reaction time of the invention calculate being added after catalyst.
After the completion of substitution reaction, the present invention preferably post-processes substitution reaction product, obtains tricyano spiro compounds
Object solid.In the present invention, the post-processing preferably includes following steps:
Reaction product is discharged in the mixed solvent, is heated to reflux, poor solvent, which is added, is precipitated crystal, successively carries out later
It is separated by solid-liquid separation, dry and recrystallization, obtains tricyano spiro-compound solid.
In the present invention, the mixed solvent is preferably the mixed solvent of n,N-Dimethylformamide and deionized water；Institute
The volume ratio for stating in the mixed solvent N,N-dimethylformamide and deionized water is preferably 1:1.In the present invention, the poor solvent
Preferably water, the dosage of the poor solvent is not subject to so that crystal just has precipitation, and after stirring, crystal precipitation disappears.The present invention couple
The separation of solid and liquid, dry and recrystallization mode do not have special requirement, use above-mentioned behaviour well known to those skilled in the art
Make mode.
After obtaining tricyano spiro-compound, the present invention will have the tricyano spiro-compound of structure shown in formula (d) to exist
Reaction is hydrolyzed in alkaline solution, adjusts pH value later to acidity, obtains the fluorine-containing polyacid monomer with Formula II depicted structure.
In the present invention, the alkaline solution is preferably sodium hydrate aqueous solution, and the mass concentration of the sodium hydrate aqueous solution is preferred
It is 40~50%, more preferably 45%；The molar ratio of solute is excellent in the tricyano spiro-compound and sodium hydrate aqueous solution
It is selected as 1:6~8, more preferably 1:6.6.The present invention preferably by tricyano spiro-compound and alkaline solution be placed in solvent into
Row hydrolysis, the solvent are preferably the mixed liquor of water and dehydrated alcohol, water and dehydrated alcohol volume ratio in the mixed liquor
Preferably 1:0.5~1.5, more preferably 1:1.In the present invention, the temperature of the hydrolysis is preferably 80~100 DEG C, more
Preferably 90 DEG C, the time of the hydrolysis is preferably 15~20h, more preferably 16~18h.In the present invention, tricyano
Spiro-compound is hydrolyzed under alkaline condition, generates carboxylate.
After the completion of hydrolysis, the pH value of hydrolysis liquid is adjusted to acidity by the present invention, obtains solid product.The present invention
It is preferred that the pH value of hydrolysis liquid is adjusted to 1.5~2.5, more preferable 2.The present invention preferably first boils off the ethyl alcohol in reaction solution,
By discharging after the filtrate cooling after ethanol evaporation in deionized water, pH value is then adjusted again.In the present invention, the deionization
The dosage of water is preferably 400~500mL, more preferable 450mL.The present invention does not have special requirement to pH value regulator is adjusted,
Use acidic pH adjustor well known to those skilled in the art.In the present invention, carboxylic can be made by adjusting pH value to acidity
Carboxylate radical in hydrochlorate is converted into carboxyl, and solid product is precipitated.
After obtaining solid product, the present invention is preferably successively filtered, washs and is dried to the solid product, is had
There is the fluorine-containing polyacid monomer of Formula II depicted structure.The present invention does not have special requirement to the suction filtration, washing and dry mode,
Use aforesaid operations well known to those skilled in the art.
The present invention provides a kind of polyamide, have structure shown in formula III:
A R substituent is H in formula III, and excess-three R substituent is substituent group or formula with structure shown in formula (e)
Four R substituents are the substituent group with structure shown in formula (e) in III；
AR is in formula (e)
In the present invention, structure shown in formula III is the constitutional repeating unit of polyamide.
There are microcellular structures between polyamide molecule provided by the invention, gas molecules can be made to easily infiltrate into；Meanwhile this
The polyamide that invention provides is dissaving polymer, and the presence of dissaving structure makes the bigger gap of intermolecular presence, can be improved
Its infiltration coefficient.In addition, in polyamide provided by the invention the presence of ehter bond increase polymer molecular chain free volume and
Flexibility easily infiltrates into solvent, improves the problem of the traditional gas seperation film difference of the dissolubility due to caused by rigid chain；And
The presence of large volume trifluoromethyl increases the degreeof tortuosity of molecule and the volume of molecule, improves the free volume of polymer,
To increase the permeability of gas, in addition to this fluorine atom in trifluoromethyl can increase and have due to electronegativity
Interaction between solvent improves the dissolubility of polymer.
The present invention provides the preparation methods of above-mentioned polyamide, comprising the following steps:, will be fluorine-containing under the action of salt forming agent
Polyacid monomer and diamine monomer carry out polycondensation reaction in polar organic solvent, obtain polyamide；
The fluorine-containing polyacid monomer is the above-mentioned fluorine-containing polyacid monomer with structure shown in Formulas I or Formula II.
In the present invention, when fluorine-containing polyacid monomer has structure shown in Formulas I, four R substituents are to have in formula III
The substituent group of structure shown in formula (e)；When fluorine-containing polyacid monomer has structure shown in Formula II, a R substituent is H in formula III,
Its excess-three R substituent is the substituent group with structure shown in formula (e).
In the present invention, the salt forming agent is preferably one or more of potassium carbonate, cesium carbonate and sodium carbonate, and described two
The structure of amine monomers is preferred are as follows: H2N-AR-NH2, wherein AR be
It is anti-that the present invention carries out polycondensation under nitrogen protection, by diamine monomer and fluorine-containing polyacid monomer in polar organic solvent
It answers, obtains polyamide.In the present invention, the molar ratio of the fluorine-containing polyacid monomer, diamine monomer and salt forming agent be preferably 1:2~
4:2~2.5, more preferably 1:3:2.25；In the present invention, the polar organic solvent preferably includes N, N '-dimethyl formyl
Amine or N, N '-dimethyl acetamide；The fluorine-containing polyacid monomer, the quality summation of salt forming agent and diamine monomer and organic solvent
Mass ratio is preferably 15~20:100, more preferably 16~18:100.In the present invention, the temperature of the polycondensation reaction is preferably
0~25 DEG C, more preferably 20~25 DEG C, the time is preferably 3~for 24 hours, more preferably 5~20h.The present invention passes through polycondensation reaction,
Obtain sticky polyamide.
After the completion of polycondensation reaction, polycondensation reaction liquid is preferably successively cooled down, washed and dried by the present invention, obtains polyamides
Amine.The present invention does not have special requirement to the mode of the cooling, using the type of cooling well known to those skilled in the art,
Specific such as natural cooling.The present invention obtains sticky polyamide by cooling treatment.In the present invention, washing washing
Agent is preferably deionized water and ethyl alcohol；Present invention preferably uses deionized waters and the alternating of ethyl alcohol to wash, the alternately washing
Number is preferably 3 times, wherein deionized water washing can remove salt forming agent when alternately washing, and ethanol washing can remove remnants
Organic solvent.In the present invention, the mode of the drying is preferably dried under reduced pressure；The temperature of the drying is preferably 100 DEG C,
Time is preferably 12h.
The present invention also provides a kind of polyamide film, the polyamide film includes polyamide described in above-mentioned technical proposal
Or the polyamide that the above method is prepared.
In the present invention, the thickness of the polyamide film is preferably 60~70 μm, and more preferably 64~68 μm.The present invention
The polyamide film of offer has preferable gas-selectively and permeability simultaneously.
In the present invention, the preparation method of the polyamide film preferably includes following steps:
The polyamide is dissolved in n,N-dimethylacetamide solvent, polyamide solution is obtained；
After the polyamide solution is coated on substrate surface, temperature programming and cooling are successively carried out, it is thin to obtain polyamide
Film.
The polyamide is dissolved in n,N-dimethylacetamide solvent by the present invention, obtains polyamide solution.In this hair
In bright, the quality of the polyamide is preferably the 10~20% of solvent quality, further preferably 15%.
After obtaining polyamide solution, the polyamide solution is coated on substrate surface by the present invention, then successively carries out journey
Sequence heating and cooling, obtain polyamide film.The present invention does not have special requirement to the mode of the coating, uses this field skill
Coating method known to art personnel；The present invention does not specially require the material of the substrate, uses those skilled in the art
The substrate for preparing film known to member.
In the present invention, described program heating preferably include four-stage, be followed successively by a stage, the two-stage, three stages and
Four stages；The temperature in one stage is preferably 60~80 DEG C, and the time is preferably 4~5h；The temperature of the two-stage is preferably
80~100 DEG C, more preferably 90 DEG C, the time is preferably 12~14h；The triphasic temperature is preferably 110~130 DEG C, more
Preferably 120 DEG C, the time is preferably 4~5h；The temperature in four stage is preferably 140~160 DEG C, and more preferably 150 DEG C, when
Between preferably 4~5h.In the present invention, the mode of the cooling is preferably natural cooling.
Below with reference to embodiment to fluorine-containing polyacid monomer provided by the invention and preparation method thereof, polyamide and its preparation side
Method and polyamide film are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The HI aqueous solution that 85g mass concentration is 99% is added in the Hexafluoro acetone of 15mL and forms mixed solution, is formed
Mixed solution be added in the aqueous acetic acid containing 170g catechol, the mass concentration of aqueous acetic acid is 48.6g/
mol.Then the hydrazine hydrate of 4.2g is added dropwise into solution, 120 DEG C of obtained solution is heated to reflux 10h, then cools to room temperature
To supersaturated solution, obtained supersaturated solution is utilized into hydrothermal crystallisation methods, is precipitated under 240 DEG C, the high temperature and pressure of 0.3GPa
White micro-crystals compound, filtering are closed with four phenolate of loop coil that alternately washing obtains 13.0908g three times of glacial acetic acid, methylene chloride
Object.
Into the 250mL three-neck flask equipped with mechanical stirring device, the loop coil four that adds 8.3445g (15mmol) to be prepared
Phenol, 7.7510g (64mmol) p-Fluorophenyl cyanide, the N-Methyl pyrrolidone of 12mL, the total solid content of reaction system are 15%, are stirred
Mix to raw material and all dissolve, and under the protection of nitrogen, half an hour is stirred at room temperature, use frequency be 2GHz microwave with 10 DEG C/
The heating rate of min is warming up to 150 DEG C, and the cesium fluoride of 9.6640g (64mmol) is added, and system reacts 10h, and TLC is detected to original
It is that reaction terminates that shots, which disappear, stops reaction；System discharging is in N,N-dimethylformamide after reaction: deionization water body
Product is than being added poor solvent deionized water until just there is analysis in the mixed system of 1:1, to carry out being warming up to reflux temperature to system
Out, it stirs and is precipitated and do not disappear, obtain four phenolic compounds of four cyano loop coil of 8.2616g.
The product structure such as formula (b) for four phenolic compounds of four cyano loop coil that the present invention is prepared:
Into the 250mL three-neck flask equipped with mechanical stirring device, the four cyano spirocyclization of 8.2616g (8mmol) is added
Object is closed, the deionized water of 68mL is added and hybrid reaction system and mass concentration that dehydrated alcohol volume ratio is 1:1 is 45%
Sodium hydrate aqueous solution (sodium hydroxide containing 70.4mmol), use frequency for 3GHz, output power be 900W microwave
System is carried out for 20 DEG C/min with heating rate as energy source to be warming up to 90 DEG C, system reacts 20h, and TLC is detected to raw material
It is that reaction terminates that point, which disappears, boils off ethyl alcohol, and collection filtrate is cooling and in deionized water, and adjusting pH value is 2, up to being precipitated
White object collects precipitate, filters, and deionized water washs filter cake to neutrality, and product is obtained through 100 DEG C of vacuum drying 12h
5.5435g fluorine-containing polyacid monomer.
The fluorine-containing polyacid monomer structure such as Formulas I that embodiment 1 obtains:
Embodiment 2
The HI aqueous solution that 5g mass content is 99% is added in the Hexafluoro acetone of 10mL and forms mixed solution, formation
Mixed solution is added to the 100mL for containing 11.5165g (105mmol) catechol and 14.1165g (150mmol) phenol simultaneously
In acetum, the hydrazine hydrate of 3.6g is then slowly added dropwise into solution.Under stirring, the protection of sufficiently logical nitrogen, it is heated to reflux
15h then cools to room temperature to obtain supersaturated solution, by obtained supersaturated solution utilize hydrothermal crystallisation methods, 240 DEG C,
White micro-crystals compound is precipitated under the high temperature and pressure of 0.5GPa, filtering, alternately washing obtains spiral shell three times with glacial acetic acid, tetrahydrofuran
Three phenolic compounds of ring.
Into the 250mL three-neck flask equipped with mechanical stirring device, add three phenolic compounds of 15mmol loop coil, 64mmol is to fluorine
Benzonitrile, the N-Methyl pyrrolidone of 11mL, stirring to raw material is all dissolved, and under the protection of nitrogen, use frequency for
150GHz microwave is warming up to 150 DEG C with the heating rate of 10 DEG C/min, and the fluorination cesium-promoted catalyst of 105mmol is added.TLC detect to
It is that reaction terminates that raw material point, which disappears, stops reaction；System discharging is in N,N-dimethylformamide after reaction: deionized water
Volume ratio is to carry out being warming up to reflux temperature to system in the mixed system of 1:1, and poor solvent deionized water is added until just there is analysis
It stirs and is precipitated out and do not disappear, obtain the tricyano spiro-compound of 7.3247g, the structure of the tricyano spiro-compound is such as
Formula (d):
Into the 250mL three-neck flask equipped with mechanical stirring device, the tricyano spirocyclization of 7.3247g (8mmol) is added
Object is closed, the deionized water of 68mL is added and hybrid reaction system and mass concentration that dehydrated alcohol volume ratio is 1:1 is 45%
Sodium hydrate aqueous solution (sodium hydroxide containing 70.4mmol), use frequency for 3GHz, output power be 900W microwave
System is carried out for 20 DEG C/min with heating rate as energy source to be warming up to 90 DEG C, system reacts 20h, and TLC is detected to raw material
It is that reaction terminates that point, which disappears, boils off ethyl alcohol, and collection filtrate is cooling and in deionized water, and adjusting pH value is 2, up to being precipitated
White object collects precipitate, filters, and deionized water washs filter cake to neutrality, and product is obtained through 100 DEG C of vacuum drying 12h
The fluorine-containing polyacid monomer of 4.8629g, the structure such as Formula II of the fluorine-containing polyacid monomer:
Embodiment 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, the n,N-dimethylacetamide of four acid compound of loop coil, 13mL that addition 2mmol embodiment 1 is prepared makes system
Solid content is 15%, to whole dissolutions, is slowly added to the potassium carbonate of 4mmol, reacts 3h at room temperature, and 5mmol phenylenediamine, nitrogen is added
The lower 200 DEG C of reactions 20h of gas shielded, is then slowly warming up to 265 DEG C, further polycondensation 2h, Temperature fall obtains polyamide, by institute
Sticky polyamide is obtained using deionization and ethyl alcohol alternately washing three times, sufficiently removing remaining salt forming agent and solvent, 100 DEG C of decompressions
12h obtains 2.8981g dry resin, is labeled as PA-1, obtained product structure such as formula (1):
Embodiment 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 n,N-dimethylacetamide of four acid compound of loop coil, 13mL that addition 2mmol embodiment 1 is prepared, to all molten
Solution, is slowly added to the potassium carbonate of 4mmol, reacts 2h at room temperature, is added 6mmol benzidine, the lower 200 DEG C of reactions 15h of nitrogen protection,
Then 300 DEG C are slowly warming up to, further polycondensation 2h, Temperature fall obtains polyamide, by the sticky polyamide of gained using go from
Son and ethyl alcohol alternately washing three times, sufficiently remove remaining salt forming agent and solvent, and 100 DEG C of decompression 12h obtain the dry tree of 3.4764g
Rouge is labeled as PA-2, obtained product structure such as formula (2):
Embodiment 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 n,N-dimethylacetamide of four acid compound of loop coil, 13mL that addition 2mmol embodiment 1 is prepared, to all molten
Solution, is slowly added to the potassium carbonate of 4mmol, reacts 2.5h at room temperature, is added 7mmol diaminodiphenyl ether, and lower 200 DEG C of nitrogen protection
18h is reacted, is then slowly warming up to 280 DEG C, further polycondensation 2h, Temperature fall obtains polyamide, by the sticky polyamide of gained
Using alternately washing three times of deionization and ethyl alcohol, remaining salt forming agent and solvent are sufficiently removed, 100 DEG C of decompression 12h obtain 3.5980g
Dry resin is labeled as PA-3, obtained product structure such as formula (3):
Embodiment 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, the n,N-dimethylacetamide of four acid compound of loop coil, 13mL that addition 2mmol embodiment 1 is prepared, to all molten
Solution, is slowly added to the potassium carbonate of 4mmol, reacts 3h at room temperature, the 4 of 8mmol, 4 '-diaminobenzophenones, nitrogen protection is added
Lower 200 DEG C of reactions 20h, is then slowly warming up to 300 DEG C, further polycondensation 2h, Temperature fall obtains polyamide, and gained is sticky
Polyamide sufficiently removes remaining salt forming agent and solvent, 100 DEG C of decompression 12h are obtained using deionization and ethyl alcohol alternately washing three times
3.6893g dry resin is labeled as PA-4, obtained product structure such as formula (4):
Embodiment 7
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 n,N-dimethylacetamide of three acid compound of loop coil, 13mL that addition 2mmol embodiment 2 is prepared, to all molten
Solution, is slowly added to the potassium carbonate of 4mmol, reacts 2h at room temperature, is added 5mmol phenylenediamine, the lower 200 DEG C of reactions 20h of nitrogen protection,
Then 265 DEG C are slowly warming up to, further polycondensation 2h, Temperature fall obtains polyamide, by the sticky polyamide of gained using go from
Son and ethyl alcohol alternately washing three times, sufficiently remove remaining salt forming agent and solvent, and 100 DEG C of decompression 12h obtain the dry tree of 2.4416g
Rouge is labeled as PA-5, obtained product structure such as formula (5):
Embodiment 8
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 n,N-dimethylacetamide of three acid compound of loop coil, 13mL that addition 2mmol embodiment 2 is prepared, to all molten
Solution, is slowly added to that (potassium carbonate of 4mmol, reacts 2h at room temperature, and 6mmol benzidine, the lower 200 DEG C of reactions of nitrogen protection is added
Then 20h is slowly warming up to 300 DEG C, further polycondensation 2h, Temperature fall obtains polyamide, and the sticky polyamide of gained is used
Deionization and ethyl alcohol alternately washing three times, sufficiently remove remaining salt forming agent and solvent, it is dry that 100 DEG C of decompression 12h obtain 2.8754g
Resin is labeled as PA-6, obtained product structure such as formula (6):
Embodiment 9
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 n,N-dimethylacetamide of three acid compound of loop coil, 13mL that addition 2mmol embodiment 2 is prepared, to all molten
Solution, is slowly added to the potassium carbonate of 4mmol, reacts 3h at room temperature, and 4mmol diaminodiphenyl ether is added, and lower 200 DEG C of nitrogen protection anti-
20h is answered, is then slowly warming up to 265 DEG C, further polycondensation 2h, Temperature fall obtains polyamide, and the sticky polyamide of gained is adopted
With alternately washing three times of deionization and ethyl alcohol, remaining salt forming agent and solvent are sufficiently removed, it is dry that 100 DEG C of decompression 12h obtain 2.9665g
Dry resin is labeled as PA-7, obtained product structure such as formula (7):
Embodiment 10
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 n,N-dimethylacetamide of three acid compound of loop coil, 13mL that addition 2mmol embodiment 2 is prepared, to all molten
Solution, is slowly added to the potassium carbonate of 4mmol, reacts 3h at room temperature, the 4 of 6mmol, 4 '-diaminobenzophenones, nitrogen protection is added
Lower 200 DEG C of reactions 20h, is then slowly warming up to 300 DEG C, further polycondensation 2h, Temperature fall obtains polyamide, and gained is sticky
Polyamide sufficiently removes remaining salt forming agent and solvent, 100 DEG C of decompression 12h are obtained using deionization and ethyl alcohol alternately washing three times
3.0349g dry resin is labeled as PA-8, obtained product structure such as formula (8):
Structural characterization
Nuclear magnetic resonance spectroscopy test, test result such as Fig. 1 institute are carried out to the fluorine-containing polyacid monomer that embodiment 1 is prepared
Show, as shown in Figure 1, the fluorine-containing polyacid monomer structure that the present invention is prepared is consistent with expection.
Nuclear magnetic resonance spectroscopy test is carried out to the fluorine-containing polyacid monomer that embodiment 2 is prepared, test result shows this hair
The bright fluorine-containing polyacid monomer structure being prepared is consistent with expection.
Infrared test is carried out to the polyamide that embodiment 3~5 is prepared, test results are shown in figure 2, as shown in Figure 2,
The polyamide structure that the present invention is prepared is consistent with expection.
Infrared test is carried out to the polyamide that embodiment 6~10 is prepared, test result shows that the present invention is prepared
Polyamide structure with expection be consistent.
Performance test
1. dissolubility is tested
The dissolubility of polyamide prepared by embodiment 3~10 is tested, test method are as follows: dissolve polyamide respectively
In DMAC, DMF, NMP, DMSO, THF and CHCl3In, concentration of the polyamide in different solvents is 10mg/mL.Test polyamide
Solubility property in different solvents, wherein ++ indicate that room temperature is entirely molten；+ indicate that heating is complete molten；+-indicates to be partly dissolved；-- table
Show that heating is insoluble.Test result is as shown in table 1.
The dissolubility of 1 embodiment of table, 3~10 gained polyamide
| Solvent/sample | PA-1 | PA-2 | PA-3 | PA-4 | PA-5 | PA-6 | PA-7 | PA-8 |
| DMAC | ++ | ++ | ++ | ++ | ++ | ++ | ++ | ++ |
| DMF | ++ | ++ | ++ | ++ | ++ | ++ | ++ | ++ |
| NMP | ++ | ++ | ++ | ++ | ++ | ++ | ++ | ++ |
| DMSO | ++ | ++ | ++ | ++ | ++ | ++ | ++ | ++ |
| THF | ++ | ++ | ++ | ++ | ++ | ++ | ++ | ++ |
| CHCl3 | ++ | ++ | ++ | ++ | ++ | ++ | ++ | ++ |
By 1 test result of table it is found that the polyamide being prepared using fluorine-containing polyacid monomer provided by the invention have compared with
Good dissolubility.Fluorine-containing polyacid monomer provided by the invention introduces the groups such as aliphatic structure, ehter bond, trifluoromethyl, makes institute
Obtain the dissolubility that polyamide is all done well in most of polar solvents.
2. gas separation test
3~10 gained polyamide of the embodiment of the present invention is prepared into polyamide film respectively, by gained polyamide film point
It Bian Hao not be 1., 2., 3., 4., 5., 6., 7., 8..
It is specific the preparation method comprises the following steps:
Polyamide is dissolved in n,N-dimethylacetamide with 15% solid content, is filtered through 0.45 μm of Teflon filter
It removes insoluble matter and obtains uniform polyamide solution, which is coated uniformly on clean 9cm × 9cm glass plate, is placed in baking oven
It is middle 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 obtains
Bright polyamide film.
To 1.~8. number polyamide film carry out respectively gas separation test, test result is as shown in table 2, test method
Are as follows:
Using the gas permeability matter of pressure differential method (the strong method of constant volume transformation) test polymer film, testing instrument is
Make gas permeability tester by oneself.During the test, testing film is sealed in test pond with epoxy resin, upstream pressure setting
For 2atm, and downstream is evacuated to vacuum, after a period of stabilisation to downstream pressure, is tested at 35 DEG C, permeated with gas
Coefficient characterizes thin polymer film to the separating effect of gas, and gas separation coefficient indicates the selectivity of perfect gas.Wherein, gas
The calculation method of body separation is αA/B=PA/PB, PAAnd PBThe infiltration coefficient of two kinds of gas of respectively A and B.
Table 2 1.~gas separating property of 8. number polyamide film
As shown in Table 2, after polyamide provided by the invention is prepared into polyamide film, there is preferable gas permeability
Can, polyamide film provided by the invention is 8~45Barrer to the infiltration coefficient of nitrogen, the infiltration coefficient to methane is 15~
50Barrer, the infiltration coefficient to oxygen are 45~99Barrer, and the infiltration coefficient to carbon dioxide is 210~395Barrer.
Thus illustrate that the polyamide film that polyamide provided by the invention is prepared is higher to the permeability of gas.
Polyamide film provided by the invention to the gas separation coefficient of carbon dioxide and nitrogen mixed gas be 8.7~
33.8, it is 7.9~18.1 to the gas separation coefficient of carbon dioxide and methane mixed gas, to oxygen and nitrogen mixed gas
Gas separation coefficient is 1.9~6.3.Thus illustrate, the polyamide film that polyamide provided by the invention is prepared is to gas
Selectivity it is higher, i.e., after polyamide provided by the invention is prepared into polyamide film, while guaranteeing good selectivity, tool
Have the characteristics that permeability is high.
In conclusion the polyamide that is prepared of fluorine-containing polyacid monomer provided by the invention DMAC, DMF, NMP, DMSO,
THF and CHCl3In the polyamide film that there is preferable dissolubility, and be prepared by polyamide of the present invention for gas
When body separates, while there is preferable gas-selectively and permeability.
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 fluorine-containing polyacid monomer, which is characterized in that have structure shown in Formulas I or Formula II:
2. the preparation method of fluorine-containing polyacid monomer described in claim 1, which is characterized in that when the fluorine-containing polyacid monomer has formula
Shown in I when structure, the preparation method comprises the following steps:
(1) under the action of reducing agent and acid catalyst, Hexafluoro acetone and catechol is subjected to isomerization reaction, had
Four phenol of loop coil of structure shown in formula (a)；
(2) under the effect of the catalyst, four phenol of loop coil with structure shown in formula (a) and p-Fluorophenyl cyanide replace anti-
It answers, obtains the four cyano spiro-compound with structure shown in formula (b)；
(3) reaction is hydrolyzed in the four cyano spiro-compound with structure shown in formula (b) in basic solvent, later by water
The pH value of solution reaction solution is adjusted to acidity, obtains the fluorine-containing polyacid monomer with Formulas I depicted structure；
When the fluorine-containing polyacid monomer has structure shown in Formula II, the preparation method comprises the following steps:
(i) under the action of reducing agent and acid catalyst, Hexafluoro acetone, catechol and phenol is subjected to isomerization reaction, obtained
To the loop coil triphenol with structure shown in formula (c)；
(ii) under the effect of the catalyst, the loop coil triphenol with structure shown in formula (c) and p-Fluorophenyl cyanide replace anti-
It answers, obtains the tricyano spiro-compound with structure shown in formula (d)；
(iii) reaction is hydrolyzed in basic solvent in the tricyano spiro-compound with structure shown in formula (d), later will
The pH value of hydrolysis liquid is adjusted to acidity, obtains the fluorine-containing polyacid monomer with Formula II depicted structure.
3. preparation method according to claim 2, which is characterized in that the reducing agent in the step (1) and step (i) is only
It is on the spot one or more of hydrazine hydrate, zinc powder, magnesium powder, iron powder, stannous chloride, frerrous chloride and sodium borohydride.
4. preparation method according to claim 2, which is characterized in that Hexafluoro acetone in the step (1), catechol and
The molar ratio of reducing agent is 1~2:1~2:5~10；
Hexafluoro acetone in the step (i), catechol, phenol and reducing agent molar ratio be 1.5~6:1~4:1~4:5~
10。
5. preparation method according to claim 2, which is characterized in that isomerization reaction in the step (1) and step (i)
Temperature independently be 117~125 DEG C, the time independently is 10~12h.
6. preparation method according to claim 2, which is characterized in that four phenol of loop coil and to fluorobenzene first in the step (2)
The molar ratio of nitrile is 1:4~9；The catalyst is sodium hydride and/or cesium fluoride；The temperature of the substitution reaction is 150~200
DEG C, the time is 10~12h；
The molar ratio of loop coil triphenol and p-Fluorophenyl cyanide is 1:4~9 in the step (ii)；The catalyst be sodium hydride and/
Or cesium fluoride；The temperature of the substitution reaction is 150~200 DEG C, and the time is 10~12h.
7. preparation method according to claim 2, which is characterized in that hydrolysis in the step (3) and step (iii)
Temperature independently be 80~100 DEG C, the time independently is 15~20h.
8. a kind of polyamide, which is characterized in that have structure shown in formula III:
A R substituent is H in formula III, and excess-three R substituent is the substituent group with structure shown in formula (e)；Or formula III
In four R substituents be the substituent group with structure shown in formula (e)；
AR is in formula (e)
9. the preparation method of polyamide described in claim 8, which comprises the following steps:
Under the action of salt forming agent, fluorine-containing polyacid monomer and diamine monomer are subjected to polycondensation reaction in polar organic solvent, obtained
To polyamide；
The fluorine-containing polyacid monomer is side described in fluorine-containing polyacid monomer described in claim 1 or claim 2~7 any one
The fluorine-containing polyacid monomer that method obtains.
10. a kind of polyamide film, which is characterized in that the polyamide film includes polyamide or power described in claim 8
The polyamide that benefit requires 9 the methods to be prepared.
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| CN114177744A (en) * | 2022-02-17 | 2022-03-15 | 中国气象科学研究院 | Trapezoidal polymer with micropores for gas separation, membrane and application |
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| CN109535069A (en) * | 2018-12-12 | 2019-03-29 | 吉林大学 | A kind of diamine monomer and preparation method thereof and polyimides and preparation method thereof |
| CN109627212A (en) * | 2018-12-12 | 2019-04-16 | 吉林大学 | A kind of diacid monomer and preparation method thereof and polyamide and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109535069A (en) * | 2018-12-12 | 2019-03-29 | 吉林大学 | A kind of diamine monomer and preparation method thereof and polyimides and preparation method thereof |
| CN109627212A (en) * | 2018-12-12 | 2019-04-16 | 吉林大学 | A kind of diacid monomer and preparation method thereof and polyamide and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114177744A (en) * | 2022-02-17 | 2022-03-15 | 中国气象科学研究院 | Trapezoidal polymer with micropores for gas separation, membrane and application |
| CN114177744B (en) * | 2022-02-17 | 2022-04-15 | 中国气象科学研究院 | Trapezoidal polymer with micropores for gas separation, membrane and application |
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