CN110483771A - A kind of purposes of polyimide resin and its synthetic method and the resin film based on binaphthalene ether skeleton structure - Google Patents

A kind of purposes of polyimide resin and its synthetic method and the resin film based on binaphthalene ether skeleton structure Download PDF

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CN110483771A
CN110483771A CN201910738202.9A CN201910738202A CN110483771A CN 110483771 A CN110483771 A CN 110483771A CN 201910738202 A CN201910738202 A CN 201910738202A CN 110483771 A CN110483771 A CN 110483771A
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binaphthalene
ether
polyimide resin
skeleton structure
formula
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薛松
邓国雄
宗雪平
王一雷
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Tianjin University of Technology
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Tianjin University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • Polymers & Plastics (AREA)
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  • Analytical Chemistry (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention discloses a kind of polyimide resin based on binaphthalene ether skeleton structure and its purposes of synthetic method and the resin film, belong to chemical technology field, the polyimide resin is obtained using binaphthol and 4 kinds of different location chlorine substituted-nitrobenzene reactions, then through reduction using binaphthalene ether as the diamine monomer of skeleton.The diamine monomer and 6F dicarboxylic anhydride synthesis of polyimides resin, and it is prepared into seperation film.The polyimide resin film is used for H2/N2, CO2/N2, O2/N2, CO2/CH4Separation has the characteristics that high gas transit dose and highly selective.In addition, the Kapton shows excellent heat resistance (more than 500 DEG C) and mechanical property.

Description

A kind of polyimide resin and its synthetic method based on binaphthalene ether skeleton structure and The purposes of the resin film
Technical field
The invention belongs to chemical technology field, it is related to a kind of polyimide resin for taking into account excellent breathability and selectivity The preparation method and purposes of synthesis and its gas separation membrane, the gas separation membrane of preparation CO suitable for industrial waste gas2Gas Recycling, help O in combustion air2Enrichment and industrial H2And CH4The fields such as enrichment.
Background technique
Energy crisis forces high energy consumption industry to abandon original extensive style production method and leans on to highly efficient energy-saving mode Hold together.CO in industrial waste gas2The recycling of gas helps O in combustion air2Enrichment and industrial H2And CH4Enrichment is to reduce environment Pollution and the effective way for increasing resource utilization.A kind of gas separation of the gaseous jet simulation as rapid development, has concurrently The function of separation, concentration, purifying and purification, and have the features such as simple, the easily controllable and molecular level filtering of filter process.If by film Isolation technics applies to CO in industrial waste gas2The recycling of gas helps O in combustion air2Enrichment and industrial H2And CH4Enrichment Equal fields, it has also become solve one of the energy and the most important means of environmental issue, it is considered to be most economical and great market is latent The method of power.
Polyimide material has many advantages, such as that high temperature resistant, mechanical performance be excellent and solvent resistant, but permeability of the membrane and choosing Selecting property can not combine, and by researching and developing novel reaction monomers, optimize monomer structure, change the structure of macromolecular chain, construct With new type polyimide resin, it is the important means for preparing highly selective and infiltrative gas separation membrane, is conducive to improve The efficiency and reduction energy consumption of gas separation.
To sum up, it designs and prepares using binaphthalene ether as the polyimide resin film of main chain, makes it have good gas Selectivity and permeability, become the technical problem to be solved in the invention.
Summary of the invention
It is an object of the present invention to provide new class using binaphthalene ether as the synthesis side of the polyimide resin of skeleton Method；
The second object of the present invention is, provides above-mentioned using binaphthalene ether as the preparation of the polyimide resin film of skeleton Method.
The third object of the present invention is, provides above-mentioned using binaphthalene ether as the use of the polyimide resin film of skeleton On the way.
Provided by the invention using binaphthalene ether is the polyimide resin film of skeleton by using synthesizing a kind of polyamino Binaphthalene ether structure monomer, with conventional 6F dicarboxylic anhydride molecule synthesis polyamide acid polymer, main polymer chain has rigidity connection Dinaphthyl distorted-structure can obtain larger free volume, and gas is promoted smoothly to penetrate, and improve the gas flux of film, polyamino connection Dinaphthyl ether structures alone side chain changes the gas-selectively that can change film.
It is provided by the present invention it is novel using binaphthalene ether be the polyimide resin of skeleton have following general structure:
In an optimal technical scheme of the invention, Ar is that ortho position two replaces, aligns two substitutions, alkyl and trifluoromethyl The aromatic group of modification.Group shown in Formula II or formula III or formula IV or Formula V is four kinds in best Ar.
It prepares of the present invention as follows using binaphthalene ether as the partially synthetic route of the polyimide resin of skeleton:
In said synthesis route Ar meaning with it is described previously identical.
That is: it using binaphthol VI as raw material, reacts to obtain lark powdered compounds VIII with chloronitrobenzene VII； By obtained lark powdered compounds VIII in being less than 2bar hydrogen, pink solid is obtained through palladium carbon catalysis reduction, i.e., Using binaphthalene ether as the diamine monomer IX of skeleton；Gained diamine monomer IX passes through chemical imidization process (1) or azeotropic amination Process (2) is obtained containing binaphthalene ether structure polyimide resin.
The preparation method of the above-mentioned polyimide resin based on binaphthalene ether skeleton structure, it is characterised in that by following Step:
(1) synthesis of nitro compound VIII:
By binaphthol VI, potassium hydroxide and N, bis- dimethyl acetamide of N- (DMAc) is added in round-bottomed flask, room temperature 30min is stirred, chlorine substituted-nitrobenzene system aromatic compound VII is then added, stirs 36h under the conditions of 120 DEG C.After reaction will Reaction solution is poured into 1L ice water, through filtering, with petrol ether/ethyl acetate mixed solution (10:1vol/vol) repeated washing three It is secondary, it is dried to obtain lark crystal powder.
(2) using binaphthalene ether as the synthesis of the diamine monomer IX of skeleton:
Nitro compound VIII, 10%Pd/C and n,N-Dimethylformamide (DMF) are added in round-bottomed flask, nitrogen is used After gas removes the air in reaction system, hydrogen is passed through in system.In 2bar hydrogen, 24 hours are reacted under room temperature. After filtering, filtrate is poured into deionized water and is settled, then sediment is filtered, and with water/alcohol mixed solution (1: 2vol/vol) repeated washing three times, is dried to obtain white solid powder, i.e. binaphthalene ether diamine monomer IX.
(3) synthesis containing binaphthalene ether structure polyimide resin I
Azeotropic imidization: by gained binaphthalene ether diamine monomer IX, hexafluorodianhydride (6FDA) and N, N- dimethylacetamide in (2) Amine is added in dry round-bottomed flask, stirs 4h under the conditions of nitrogen protection, 40~60 DEG C.Then isoquinolin, N- pyrroles is added Alkanone and o-dichlorohenzene, then in 170-200 DEG C of reflux 12h.After reaction, solid is collected in sedimentation in methyl alcohol, at 180 DEG C Degree vacuum drying 12h.
(4) prepared by Kapton: being dissolved in what is synthesized in (3) containing binaphthalene ether structure polyimide resin I N,N-Dimethylformamide is configured to 4-6wt% casting solution, filters out insoluble matter through 0.45 μm of teflon membrane filter, then will Filtrate, which is placed in culture dish, uniformly paves ware bottom, and slowly nature solvent flashing is up to film forming under the conditions of 30 DEG C, finally at 180 DEG C Dry 12h in vacuum drying oven.
The beneficial effects of the present invention are: of the present invention using binaphthalene ether as the polyimide resin preparation process of skeleton Simply, yield is higher, is easy to purify.Such polyimide resin can be modified by MOLECULE DESIGN, obtained and had excellent performance Seperation film.It is of the present invention to be used for using binaphthalene ether as the polyimide resin film of skeleton as gas separation membrane CO in industrial waste gas2The recycling of gas helps O in combustion air2Enrichment and industrial H2And CH4In enrichment, have good Gas permeability and selectivity.In addition, the Kapton shows excellent heat resistance (more than 500 DEG C) and mechanical property Energy.
Detailed description of the invention
Fig. 1 is the monomer chemistries structure for the polyimide resin that embodiment 1-4 is used
Fig. 2 is the binaphthalene ether structure polyimide resin chemical structure of embodiment 1-4 preparation
Fig. 3 is gas separating property of the Kapton of the preparation of embodiment 5 as seperation film
Specific embodiment
The present invention is further described by specific embodiment with reference to the accompanying drawing, the cited case does not limit guarantor of the invention Protect range.
The preparation method of gas separation membrane of the present invention mainly comprises the steps that polyamino binaphthalene ether monomer Synthesis, the preparation of binaphthalene ether structure polyimide resin and the preparation of binaphthalene ether structure Kapton.
Embodiment 1:
The synthetic route of binaphthalene ether structure polyimide resin XS7:
In two mouthfuls of round-bottomed flasks of 200mL, 19.7g potassium hydroxide, 5.73g binaphthol 1 and 40mLN, N- bis- is added Dimethyl acetamide (DMAc), is stirred at room temperature 30min.After dissolution of raw material is complete, 11.7g o-chloronitrobenzene 2 is added, 120 36h is stirred under the conditions of DEG C.Reaction solution is poured into 1L ice water after reaction, through filtering gained sediment, with petroleum ether/second Acetoacetic ester mixed solution (10:1vol/vol) washes repeatedly three times, is dried to obtain lark crystal powder, i.e. nitro compound 3.
In the three neck round bottom flask of 100mL, 5.5g nitro compound 3,0.4g 10%Pd/C and 50mLN, N- bis- is added Methylformamide (DMF) is passed through hydrogen after removing the air in reaction system with nitrogen in system.In 2bar hydrogen, room temperature Under the conditions of react 24 hours.After diatomite filters, filtrate is poured into deionized water and is settled, then sediment is filtered, And three times, white solid powder, i.e. binaphthalene ether two are dried to obtain with water/alcohol mixed solution (1:2vol/vol) repeated washing Amine monomers 4.
Azeotropic imidization: in dry round-bottomed flask, 0.56g binaphthalene ether diamine monomer 4,0.58g six is added Fluorine dianhydride monomer (6FFDA) and 4mLN, N- dimethyl acetamide.4h is stirred under the conditions of nitrogen protection, 40~60 DEG C.Then A drop isoquinolin, 5mL N- pyrrolidones (NMP) and 5mL o-dichlorohenzene (o-DCB) is added, flow back 12h under the conditions of 180 DEG C. After reaction, solid is collected in sedimentation in methyl alcohol, using recrystallization method, uses n,N-dimethylacetamide as molten respectively Agent, methanol are purified twice as anti-solvent, are then filtered, and are dried in vacuo 12h in 180 DEG C of degree after cleaning 3 times with methanol to get arriving Polyimide resin XS7 based on binaphthalene ether skeleton structure.
Embodiment 2:
The synthetic route of binaphthalene ether structure polyimide resin XS8:
In two mouthfuls of round-bottomed flasks of 200mL, 19.7g potassium hydroxide, 5.73g binaphthol 1 and 40mLN, N- bis- is added Dimethyl acetamide (DMAc), is stirred at room temperature 30min.After dissolution of raw material is complete, 11.7g parachloronitrobenzene 5 is added, 120 36h is stirred under the conditions of DEG C.Reaction solution is poured into 1L ice water after reaction, through filtering gained sediment, with petroleum ether/second Acetoacetic ester mixed solution (10:1vol/vol) washes repeatedly three times, is dried to obtain lark crystal powder, i.e. nitro compound 6.
In the three neck round bottom flask of 100mL, 5.5g nitro compound 6,0.4g 10%Pd/C and 50mLN, N- bis- is added Methylformamide (DMF) is passed through hydrogen after removing the air in reaction system with nitrogen in system.In 2bar hydrogen, room temperature Under the conditions of react 24 hours.After diatomite filters, filtrate is poured into deionized water and is settled, then sediment is filtered, And three times, white solid powder, i.e. binaphthalene ether two are dried to obtain with water/alcohol mixed solution (1:2vol/vol) repeated washing Amine monomers 7.
Azeotropic imidization: in dry round-bottomed flask, 0.56g binaphthalene ether diamine monomer 7,0.58g six is added Fluorine dianhydride monomer (6FFDA) and 4mLN, N- dimethyl acetamide.4h is stirred under the conditions of nitrogen protection, 40~60 DEG C.Then A drop isoquinolin, 5mL N- pyrrolidones (NMP) and 5mL o-dichlorohenzene (o-DCB) is added, flow back 12h under the conditions of 180 DEG C. After reaction, solid is collected in sedimentation in methyl alcohol, using recrystallization method, uses n,N-dimethylacetamide as molten respectively Agent, methanol are purified twice as anti-solvent, are then filtered, and are dried in vacuo 12h in 180 DEG C of degree after cleaning 3 times with methanol to get arriving Polyimide resin XS8 based on binaphthalene ether skeleton structure.
Embodiment 3:
The synthetic route of binaphthalene ether structure polyimide resin XS9:
In two mouthfuls of round-bottomed flasks of 200mL, 19.7g potassium hydroxide, 5.73g binaphthol 1 and 40mLN, N- bis- is added Dimethyl acetamide (DMAc), is stirred at room temperature 30min.After dissolution of raw material is complete, chloro- 5 nitrotoleune 8 of 12.7g 2- is added, 36h is stirred under the conditions of 120 DEG C.Reaction solution is poured into 1L ice water after reaction, through filtering gained sediment, uses petroleum Ether/ethyl acetate mixture (10:1vol/vol) washes repeatedly three times, is dried to obtain lark crystal powder, i.e. nitration Close object 9.
In the three neck round bottom flask of 100mL, 5.5g nitro compound 9,0.4g 10%Pd/C and 50mLN, N- bis- is added Methylformamide (DMF) is passed through hydrogen after removing the air in reaction system with nitrogen in system.In 2bar hydrogen, room temperature Under the conditions of react 24 hours.After diatomite filters, filtrate is poured into deionized water and is settled, then sediment is filtered, And three times, white solid powder, i.e. binaphthalene ether two are dried to obtain with water/alcohol mixed solution (1:2vol/vol) repeated washing Amine monomers 10.
Azeotropic imidization: in dry round-bottomed flask, 0.59g binaphthalene ether diamine monomer 10,0.58g six is added Fluorine dianhydride monomer (6FFDA) and 4mLN, N- dimethyl acetamide.4h is stirred under the conditions of nitrogen protection, 40~60 DEG C.Then A drop isoquinolin, 5mL N- pyrrolidones (NMP) and 5mL o-dichlorohenzene (o-DCB) is added, flow back 12h under the conditions of 180 DEG C. After reaction, solid is collected in sedimentation in methyl alcohol, using recrystallization method, uses n,N-dimethylacetamide as molten respectively Agent, methanol are purified twice as anti-solvent, are then filtered, and are dried in vacuo 12h in 180 DEG C of degree after cleaning 3 times with methanol to get arriving Polyimide resin XS9 based on binaphthalene ether skeleton structure.
Embodiment 4:
The synthetic route of binaphthalene ether structure polyimide resin XS10:
In two mouthfuls of round-bottomed flasks of 200mL, 19.7g potassium hydroxide, 5.73g binaphthol 1 and 40mLN, N- bis- is added Dimethyl acetamide (DMAc), is stirred at room temperature 30min.After dissolution of raw material is complete, the chloro- 5- nitro fluoroform of 16.7g 2- is added Benzene 11 stirs 36h under the conditions of 120 DEG C.Reaction solution is poured into 1L ice water after reaction, is filtered gained sediment, Three times, it is dried to obtain lark crystal powder, i.e., with petrol ether/ethyl acetate mixed solution (10:1vol/vol) repeated washing Nitro compound 12.
In the three neck round bottom flask of 100mL, 6.6g nitro compound 12,0.4g 10%Pd/C and 50mLN, N- is added Dimethylformamide (DMF) is passed through hydrogen after removing the air in reaction system with nitrogen in system.In 2bar hydrogen, room 24 hours are reacted under the conditions of temperature.After diatomite filters, filtrate is poured into deionized water and is settled, then by sediment mistake Filter, and three times, white solid powder, i.e. binaphthalene are dried to obtain with water/alcohol mixed solution (1:2vol/vol) repeated washing Ether diamine monomer 13.
Azeotropic imidization: in dry round-bottomed flask, 0.73g binaphthalene ether diamine monomer 13,0.58g six is added Fluorine dianhydride monomer (6FFDA) and 4mLN, N- dimethyl acetamide.4h is stirred under the conditions of nitrogen protection, 40~60 DEG C.Then A drop isoquinolin, 5mL N- pyrrolidones (NMP) and 5mL o-dichlorohenzene (o-DCB) is added, flow back 12h under the conditions of 180 DEG C. After reaction, solid is collected in sedimentation in methyl alcohol, using recrystallization method, uses n,N-dimethylacetamide as molten respectively Agent, methanol are purified twice as anti-solvent, are then filtered, and are dried in vacuo 12h in 180 DEG C of degree after cleaning 3 times with methanol to get arriving Polyimide resin XS10 based on binaphthalene ether skeleton structure.
Embodiment 5:
Kapton preparation: by synthesis containing binaphthalene ether structure polyimide resin XS7, XS8, XS9 and XS10 is dissolved separately in appropriate n,N-Dimethylformamide, is configured to 5wt% casting solution, filters through 0.45 μm of teflon membrane filter Except insoluble matter, then filtrate is placed in culture dish and uniformly paves ware bottom, under the conditions of 30 DEG C slowly nature solvent flashing until Film forming, finally the dry 12h in 180 DEG C of vacuum drying ovens, obtains four kinds of polyimide resin films.
Embodiment 6:
The Molecular Sieving Properties test method of Kapton prepared by embodiment 5 is " variant area method ": In Under 302.15K, 0.2MPa operating pressure conditions, 1.5cm is used2Kapton test H respectively2、N2、O2、CH4And CO2 Permeability.Wherein, O2Transmission coefficient be more than 5barrer, H2Transmission coefficient be more than 37barrer, CO2Transmission efficiency it is super Cross 26barrer；To CH4Transmission efficiency be lower than 0.5barrer, N2Transmission coefficient be lower than 0.8barrer；O2/N2Selection Property coefficient is more than 8, H2/N2Selectivity factor be more than 53, CO2/N2Selectivity factor be more than 38, CO2/CH4Selectivity system Number is more than 70.
As seen from Figure 3, the gas separation membrane prepared using the polyimide resin containing binaphthalene ether skeleton structure, Has the characteristics that high gas transit dose and highly selective.

Claims (9)

1. a kind of polyimide resin based on binaphthalene ether skeleton structure, it is characterised in that have following chemical structure:
In formula (I), Ar is aromatic ring yl, or is-CX3Substituted aromatic ring yl, wherein X is H, F.
2. the polyimide resin as described in claim 1 based on binaphthalene ether skeleton structure, which is characterized in that therein two Amine monomers skeleton contains a binaphthalene group and two ether groups.
3. the polyimide resin as described in claim 1 based on binaphthalene ether skeleton structure, which is characterized in that wherein Ar is One of group shown in Formula II or formula III or formula IV or Formula V
4. the polyimide resin as described in any one of claims 1-3 based on binaphthalene ether skeleton structure, which is characterized in that The polyimide resin based on binaphthalene ether skeleton structure is Formula X S7, Formula X S8, compound shown in Formula X S9 or Formula X S10
5. a kind of synthetic method of the polyimide resin based on binaphthalene ether skeleton structure, it is characterised in that process is as follows:
(1) synthesis of nitro compound: by binaphthol, potassium hydroxide and N, bis- dimethyl acetamide DMAc of N- is added to round bottom In flask, 30min is stirred at room temperature, chlorine substituted-nitrobenzene system aromatic compound is then added, stirs 36h under the conditions of 120 DEG C, reacts After reaction solution is poured into 1L ice water, through filtering, with the petrol ether/ethyl acetate mixed solution weight of 10:1vol/vol After backwashing is washed three times, and lark crystal powder, i.e. nitro compound are dried to obtain；
(2) using binaphthalene ether as the synthesis of the diamine monomer of skeleton: by gained nitro compound, 10%Pd/C and N, N- in (1) Dimethylformamide DMF is added in round-bottomed flask, and after the air in reaction system is removed with nitrogen, hydrogen is passed through in system Gas, in 2bar hydrogen, filtrate is poured into deionized water and settles after filtering by 24 hours of reaction under room temperature, then will Sediment filtering, and three times with the water of 1:2vol/vol/alcohol mixed solution repeated washing, it is dried to obtain white solid powder, That is binaphthalene ether diamine monomer；
(3) synthesis containing binaphthalene ether structure polyimide resin: azeotropic imidization is used: by gained union II in (2) Naphthalene ether diamine monomer, hexafluorodianhydride (6FDA) and n,N-dimethylacetamide are added in dry round-bottomed flask, in nitrogen protection, 40~60 4h is stirred under the conditions of DEG C, isoquinolin, N- pyrrolidones and o-dichlorohenzene is then added, then in 170-200 DEG C of reflux 12h, instead After answering, solid is collected in sedimentation in methyl alcohol, is dried in vacuo 12h in 180 DEG C of degree.
6. the synthetic method of the polyimide resin based on binaphthalene ether skeleton structure according to right 5, it is characterised in that Wherein with the synthesis of polyamino binaphthalene ether monomer molecule, obtain that there are different Ar skeletons to replace by nitrification, reduction step Polyamino modify binaphthalene ether monomer.
7. a kind of preparation method of the polyimide resin film based on binaphthalene ether skeleton structure, it is characterised in that process is such as Under:
It is dissolved in n,N-Dimethylformamide containing binaphthalene ether structure polyimide resin by what is synthesized in claim 5, is matched It is set to 4-6wt% casting solution, insoluble matter is filtered out through 0.45 μm of teflon membrane filter, is then placed in filtrate in culture dish uniformly Ware bottom is paved, slowly nature solvent flashing is until film forming under the conditions of 30 DEG C, the last dry 12h in 180 DEG C of vacuum drying ovens.
8. a kind of use that the polyimide resin film as claimed in claim 7 based on binaphthalene ether skeleton structure is separated in gas On the way.
9. the use that the polyimide resin film according to claim 8 based on binaphthalene ether skeleton structure is separated in gas On the way, it is characterised in that: under 302.15K, 0.2MPa operating pressure conditions, use 1.5cm2Kapton test respectively H2、N2、O2、CH4And CO2Permeability, wherein O2Transmission coefficient be more than 5barrer, H2Transmission coefficient be more than 37barrer, CO2Transmission efficiency be more than 26barrer；To CH4Transmission efficiency be lower than 0.5barrer, N2Transmission coefficient be lower than 0.8barrer；O2/N2Selectivity factor be more than 8, H2/N2Selectivity factor be more than 53, CO2/N2Selectivity factor be more than 38, CO2/CH4Selectivity factor be more than 70.
CN201910738202.9A 2019-08-12 2019-08-12 A kind of purposes of polyimide resin and its synthetic method and the resin film based on binaphthalene ether skeleton structure Pending CN110483771A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111363148A (en) * 2020-03-26 2020-07-03 天津理工大学 Preparation method of binaphthyl network type polyimide resin and film and application of binaphthyl network type polyimide resin and film in gas separation
CN112275147A (en) * 2020-09-01 2021-01-29 中国科学院山西煤炭化学研究所 Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof
CN114195608A (en) * 2021-11-08 2022-03-18 北京化工大学 Purification method of Suzuki reaction monomer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112941A (en) * 1989-07-05 1992-05-12 Mitsubishi Kasei Corporation Aromatic polymide separation membrane
JPH05310932A (en) * 1992-05-06 1993-11-22 Yoshio Imai Polyimide resin
CN101274914A (en) * 2008-05-15 2008-10-01 东华大学 Asymmetric aromatic diamine having naphthalenone binaphthyl structure, preparation and use thereof
CN102643544A (en) * 2012-03-08 2012-08-22 中国科学院宁波材料技术与工程研究所 Fluorine-containing polyimide infrared low-emissivity thin film material and preparation method thereof
CN109821426A (en) * 2019-01-22 2019-05-31 天津理工大学 A kind of Preparation method and use containing binaphthyl structure Kapton

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112941A (en) * 1989-07-05 1992-05-12 Mitsubishi Kasei Corporation Aromatic polymide separation membrane
JPH05310932A (en) * 1992-05-06 1993-11-22 Yoshio Imai Polyimide resin
CN101274914A (en) * 2008-05-15 2008-10-01 东华大学 Asymmetric aromatic diamine having naphthalenone binaphthyl structure, preparation and use thereof
CN102643544A (en) * 2012-03-08 2012-08-22 中国科学院宁波材料技术与工程研究所 Fluorine-containing polyimide infrared low-emissivity thin film material and preparation method thereof
CN109821426A (en) * 2019-01-22 2019-05-31 天津理工大学 A kind of Preparation method and use containing binaphthyl structure Kapton

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHIN-PING YANG ET AL.: "Novel, Organosoluble, Light-Colored Fluorinated Polyimides Based on 2,2 -Bis(4-amino-2-trifluoromethylphenoxy)biphenyl or 2,2 -Bis(4-amino-2-trifluoromethylphenoxy)-1,1 -binaphthyl", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 *
江谷: "《软包装材料及复合技术》", 31 December 2007, 印刷工业出版社 *
王丽娜等: "共聚聚酰亚胺膜材料的合成及其气体渗透性能研究", 《高分子学报》 *
王湛 等: "《膜分离技术基础》", 30 June 2006, 化学工业出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111363148A (en) * 2020-03-26 2020-07-03 天津理工大学 Preparation method of binaphthyl network type polyimide resin and film and application of binaphthyl network type polyimide resin and film in gas separation
CN112275147A (en) * 2020-09-01 2021-01-29 中国科学院山西煤炭化学研究所 Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof
CN114195608A (en) * 2021-11-08 2022-03-18 北京化工大学 Purification method of Suzuki reaction monomer

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