CN111040158A - Polyimide containing 9,10-dihydroacridine structure and preparation method and application thereof - Google Patents

Polyimide containing 9,10-dihydroacridine structure and preparation method and application thereof Download PDF

Info

Publication number
CN111040158A
CN111040158A CN201911288076.8A CN201911288076A CN111040158A CN 111040158 A CN111040158 A CN 111040158A CN 201911288076 A CN201911288076 A CN 201911288076A CN 111040158 A CN111040158 A CN 111040158A
Authority
CN
China
Prior art keywords
monomer
polyimide
dihydroacridine
temperature
dihydroacridine structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201911288076.8A
Other languages
Chinese (zh)
Inventor
刘亦武
谭井华
赵先清
周栋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan University of Technology
Original Assignee
Hunan University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan University of Technology filed Critical Hunan University of Technology
Priority to CN201911288076.8A priority Critical patent/CN111040158A/en
Publication of CN111040158A publication Critical patent/CN111040158A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C07D219/08—Nitrogen atoms
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention discloses polyimide containing a 9,10-dihydroacridine structure, and a preparation method and application thereof. The invention utilizes the intermediate of 9,10-dihydroacridine substituted by two halogen atoms to react with ammonia water, and converts the halogen atoms into amino; grafting a nitro-containing group through Ullmann coupling reaction and reducing to obtain a diamine monomer containing a 9,10-dihydroacridine structure, and polymerizing the prepared diamine monomer with dianhydride to obtain polyimide containing the 9,10-dihydroacridine structure. The invention creatively introduces the planar rigid structure 9,10-dihydroacridine and the polar group into the polyimide main chain, the planar rigid structure is beneficial to regular stacking of molecular chains and induction of polymer crystallization, and the polar group can enhance the hydrogen bond action of the molecular chains and promote the tight stacking of the molecular chains, so that the polyimide has excellent barrier property, higher glass transition temperature and thermal stability and lower thermal expansion coefficient.

Description

Polyimide containing 9,10-dihydroacridine structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of material science, in particular to polyimide containing a 9,10-dihydroacridine structure, a preparation method and application thereof.
Background
Organic light-emitting diodes (OLEDs) are self-luminous and have high brightness (over 10)5cd/m2) The display has the advantages of ultrathin and light weight, quick response (more than 1000 times of LCD), wide viewing angle (close to 180 degrees), low driving voltage, wide working temperature range, full solid state and the like, and is considered as a new generation display which is most likely to replace a Liquid Crystal Display (LCD). The flexible organic electroluminescent device (FOLED) made by packaging the OLED by adopting the flexible polymer material has the characteristics of light weight, convenience in carrying, bending, folding, even being wearable and the like, and is an important development direction of a future display technology.
However, FOLED has problems of insufficient stability and life span, limiting its popularization and application. When the FOLED is manufactured, the manufacturing process temperature of a Thin Film Transistor (TFT) is far higher than the glass transition temperature of a common polymer, and the manufacturing process of the TFT is difficult to complete, so that the improvement of the performance of the FOLED is greatly limited, and the service temperature of a substrate material is generally required to be more than 350 ℃. Currently, the intrinsic polymer commonly used as the substrate of the FOLED is polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polyimide (PI), or the like. Among these, some polymers have better barrier properties, but still require a certain distance from the FOLED substrate; more importantly, except for PI, the high temperature resistance of the polymers can not meet the requirement of the substrate material on the use temperature. Therefore, the preparation of a polymer substrate material with excellent thermal stability and high barrier property is the key to accelerate the industrialization of the FOLED.
At present, a commercial polyimide film cannot meet the packaging requirement of a flexible display device, and the prior art for improving the barrier property of the film comprises the step of improving the barrier property by adopting a multi-layer high-barrier film compounding mode, for example, in the CN201811084597.7 packaging material for a flexible lithium ion battery and a preparation method thereof, a high-barrier polymer film layer, a copper foil layer and a heat sealing layer are compounded together by gluing to improve the barrier property; or a layer of material is evaporated on the surface of the film to improve the air tightness, for example, CN201821403857.8 a high-barrier aluminized PET composite film is aluminized to improve the barrier property. In polyimide materials, the most common method for improving the barrier property of the polyimide materials is to add a nano inorganic substance to prepare a composite membrane, and the nano inorganic substance is selected, stripped, modified and the like to improve the dispersion of the nano inorganic substance in a matrix, for example, in a high-barrier transparent flexible display material of CN201810971444.8 and a preparation method thereof, and a high-thermal-conductivity high-barrier polyimide membrane of CN201510464312.2 with sulfonated graphene added and a preparation method thereof, the barrier property of polyimide is improved by sheet stripping and modification of the inorganic substance. The method can obviously improve the barrier property of the polyimide, but the barrier improvement can only be improved on the original basic material in a limited way, and the practical requirements of the FOLED can not be met.
Disclosure of Invention
The invention aims to solve the technical problem of providing polyimide containing a 9,10-dihydroacridine structure, which is high-temperature resistant, has high barrier property and low thermal expansion coefficient, aiming at the defects of heat resistance and barrier property of the existing FOLED substrate material.
The invention also provides a preparation method of the diamine monomer containing the 9,10-dihydroacridine structure and polyimide.
The invention also solves the technical problem of providing the application of the polyimide containing the 9,10-dihydroacridine structure in multiple fields.
The purpose of the invention is realized by the following technical scheme:
a polyimide containing a 9,10-dihydroacridine structure has a structural general formula as follows:
Figure BDA0002318591720000021
wherein Ar is1Any one selected from the following structural formulas:
Figure BDA0002318591720000031
ar is2And Ar3Any one selected from the following structural formulas:
Figure BDA0002318591720000032
x is selected from any one of the following structures:
Figure BDA0002318591720000041
wherein y is 1-10000; n is 0-6, m is 0-6, and n and m in the same structural formula are not 0 at the same time.
Further, said Ar2Preferably, it is
Figure BDA0002318591720000042
One or more of, Ar3Preferably, it is
Figure BDA0002318591720000043
One or more of (a); said X is preferably
Figure BDA0002318591720000044
The preparation method of the polyimide containing the 9,10-dihydroacridine structure comprises the following preparation steps: dissolving diamine containing 9,10-dihydroacridine structure and dianhydride containing X structure in a polar aprotic solvent according to a molar ratio of 1: 0.95-1.05 in an inert gas protective atmosphere, stirring and reacting at-15-30 ℃ for 2-48 h to obtain homogeneous polyamic acid glue solution, and then performing thermal imidization or chemical imidization dehydration on the polyamic acid glue solution to obtain polyimide.
Further, the thermal imidization step is: scraping the polyamide acid glue solution on a glass plate to form a thin layer with the thickness of 0.3-3 mm, then placing the glass plate in an oven, and heating, wherein the heating process is as follows: heating to 100 ℃ and keeping the temperature constant for 0.5-1 h, heating from 100 ℃ to 200 ℃ and keeping the temperature constant for 0.5-1 h, heating from 200 ℃ to 300 ℃ and keeping the temperature constant for 0.5-1 h, finally heating from 200 ℃ to 300 ℃ and keeping the temperature constant for 0.5-1 h, and cooling to obtain the polyimide film containing the 9,10-dihydroacridine structure.
Further, the chemical imidization step is: adding the polyamic acid glue solution into a mixed solution of pyridine and acetic anhydride, heating to 60-170 ℃, stirring for 0.5-6 h, cooling, pouring into methanol or acetone to obtain polyimide precipitate, filtering and drying to obtain polyimide powder, dissolving the polyimide powder in N-methyl pyrrolidone, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, m-phenol or tetrahydrofuran, heating and dissolving, coating the polyimide powder on a glass plate in a scraping manner, drying at 70-300 ℃ in vacuum, and cooling to obtain the polyimide film.
Further, the method for producing the diamine monomer used in the polyimide having a 9,10-dihydroacridine structure includes:
s1, 9,10-dihydroacridine monomer substituted by two halogen atoms
Figure BDA0002318591720000051
Figure BDA0002318591720000052
Reacting with ammonia water under the atmosphere of protective gas, purifying, and drying to obtain a monomer 1, a monomer 2 or a monomer 3;
s2, adding the monomer 1, the monomer 2 or the monomer 3 in the step S1, an Ar1 monomer containing a halogen atom and a nitro substituent and a solvent, adding alkali in a protective gas atmosphere, performing Ullmann coupling reaction, purifying and drying to obtain a monomer 4, a monomer 5 or a monomer 6 containing two nitro groups;
s3, adding the monomer 4, the monomer 5 or the monomer 6 in the step S2 into a solvent, adding a reducing agent, carrying out reduction reaction in an atmosphere of protective gas, purifying, and drying to obtain a diamine monomer containing a 9,10-dihydroacridine structure and shown in a structural general formula I, II or III;
the monomer 1, the monomer 2 and the monomer 3 in the step S1, and the monomer 4, the monomer 5 and the monomer 6 in the step S2 respectively have the following structural characteristics:
Figure BDA0002318591720000053
further, in S2, the ratio of the amount of the monomer 1, the monomer 2 or the monomer 3 to the amount of the substance containing a halogen atom and a nitro-substituted Ar1 monomer is 1: 2-4, and the ratio of the amount of the added alkali to the amount of the substance containing the monomer 1, the monomer 2 or the monomer 3 is 1: 0.5-2; the mass ratio of the monomer 4, the monomer 5 or the monomer 6 to the reducing agent in S3 is 1: 2-32.
Further, the protective gas from S1 to S3 is one or more of nitrogen, helium, neon, argon, krypton, xenon and radon.
Further, the base in S2 is one or more of sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium fluoride, n-butyl lithium, potassium tert-butoxide, sodium tert-butoxide, and lithium hexamethyldisilazide.
Further, in S3, the reducing agent is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder, and zinc powder.
Further, the solvent in S1 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene, and xylene; the solvent in S2 is one or more of dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, toluene, xylene, acetone, acetonitrile and diphenyl ether; the solvent in S3 is one or more of ethanol, methanol, N-propanol, tert-butanol, tert-amyl alcohol, ethanol, hexanol, tetrahydrofuran, 1,4 dioxane, dimethyl sulfoxide, N-dimethylformamide, ethyl acetate and toluene.
Further, the reaction temperature of S1-S3 is 50-170 ℃, the reaction time is 10-48 h, the drying temperature is 40-120 ℃, and the drying time is 6-30 h. Preferably, in the step S1, the reaction temperature is 100 ℃, the reaction time is 24 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in the S2, the reaction temperature is 150 ℃, the reaction time is 24 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in S3, the reaction temperature is 80 ℃, the reaction time is 24h, the drying temperature is 80 ℃, and the drying time is 24 h.
The polyimide containing the 9,10-dihydroacridine structure is applied to microelectronics, military industry, aerospace, packaging and protection and electronic device packaging.
Compared with the prior art, the beneficial effects are:
the invention designs and synthesizes an angle through a molecular structure, creatively introduces a 9,10-dihydroacridine structure and a polar group into a diamine monomer at the same time, and prepares the diamine monomer with high planarity containing the polar group. The 9,10-dihydroacridine is a good electron donor with aromaticity, is easy to form a D-pi-D or S-pi-S system, and has high electron density and good rigid structure. A plane rigid structure and a polar group are introduced into a polyimide main chain, the plane rigid structure is beneficial to regular stacking of molecular chains and induces polymer crystallization, and the polar group can enhance the hydrogen bond effect of molecular chain bonds and promote the tight stacking of the molecular chains. The synergy of the effects can ensure that molecular chains are regularly arranged and tightly piled, and the barrier property of the polyimide is obviously improved.
The diamine monomer with high planarity and 9,10-dihydroacridine structure has simple preparation process and low requirement on conditions, and is suitable for industrial production. And the diamine monomer containing 9,10-dihydro acridine structure has high planarity and strong rigidity, and contains polar group, the prepared polyimide molecular chain has regular arrangement, strong intermolecular force, and tight molecular chain stacking, thereby having excellent barrier property, higher glass transition temperature and thermal stability, and lower thermal expansion coefficient, and being suitable for microelectronics, military industry, aerospace, packaging and protection, and electronic device packaging
Detailed Description
The following examples are further explained and illustrated, but the present invention is not limited in any way by the specific examples. Unless otherwise indicated, the methods and equipment used in the examples are conventional in the art and all materials used are conventional commercially available materials.
Example 1
This example provides the synthesis of N1, N1' - (9,10-dihydroacridine-3,6-diyl) bis (bezene-1, 4-diamine):
Figure BDA0002318591720000071
s1, synthesizing an intermediate 9,10-dihydroacridine-3, 6-diamine:
adding 3.39g (0.01mol) of 3,6-dibromo-9,10-dihydroacridine, a proper amount of cuprous oxide, 50ml of NMP and 13ml of ammonia water (29%, 0.2mol) into a 200ml pressure resistant bottle, carrying out argon protection, carrying out reaction at 100 ℃, pouring the reaction solution into ice water after the reaction is finished, extracting with dichloromethane, removing the solvent under reduced pressure, purifying the product by taking dichloromethane: n-hexane: 2: 1 (volume ratio) as a mobile phase silica gel as a stationary phase for column chromatography, collecting the product, carrying out spin drying, and drying at 80 ℃ for 24 hours in vacuum to obtain the intermediate. The intermediate has the following structure:
Figure BDA0002318591720000072
s2, synthesizing an intermediate N3, N6-bis (4-nitrophenyl) -9,10-dihydroacridine-3, 6-diamine:
2.11g (0.01mol) of 9,10-dihydroacridine-3,6-diamine, 7.50g (0.05mol) of p-fluoronitrobenzene and 13.8g (0.1mol) of potassium carbonate are added into a 250ml three-neck flask, 150ml of dimethyl sulfoxide is added, magnetic stirring is carried out, argon gas is introduced, the temperature is increased to 150 ℃ for reaction for 12 hours, then the reaction solution is poured into cold water, precipitates are filtered out, and hydrochloric acid and water are used for washing, thus obtaining the intermediate. The intermediate has the following structure:
Figure BDA0002318591720000081
s3, synthesizing N1, N1' - (9,10-dihydroacridine-3,6-diyl) bis (bezene-1, 4-diamine):
adding 4.53g (0.01mol) of N3, N6-bis (4-nitrophenyl) -9,10-dihydroacridine-3,6-diamine into a 500ml three-neck flask, adding 450ml of absolute ethyl alcohol, magnetically stirring and introducing argon, heating in an oil bath to 70 ℃, adding 0.1g of 10% wt palladium carbon, gradually dropwise adding 10ml of hydrazine hydrate, refluxing for 24 hours, filtering the reaction solution by using a funnel, placing the filtrate in a refrigerator for 24 hours for crystallization, collecting an off-white solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain the product.
Example 2
This example provides the synthesis of N6- (5-aminopyridin-2-yl) -N2- (6-aminopyridin-3-yl) -9,10-dihydroacridine-2,6-diamine:
Figure BDA0002318591720000082
s1, synthesizing an intermediate 9,10-dihydroacridine-2,6-diamine:
adding 3.39g (0.01mol) of 2,6-dibromo-9,10-dihydroacridine, a proper amount of cuprous oxide, 50ml of NMP and 13ml of ammonia water (29%, 0.2mol) into a 200ml pressure resistant bottle, carrying out argon protection, carrying out reaction at 100 ℃, pouring the reaction liquid into ice water after the reaction is finished, extracting with dichloromethane, removing the solvent under reduced pressure, purifying the product by taking dichloromethane: n-hexane: 2: 1 (volume ratio) as a mobile phase silica gel as a stationary phase for column chromatography, collecting the product, carrying out spin drying, and drying at 80 ℃ for 24 hours in vacuum to obtain the intermediate. The intermediate has the following structure:
Figure BDA0002318591720000083
s2. Synthesis of intermediate N6- (5-nitropyridin-2-yl) -N2- (6-nitropyridin-3-yl) -9,10-dihydroacridine-2,6-diamine:
2.11g (0.01mol) of 9,10-dihydroacridine-2,6-diamine, 7.105g (0.05mol) of 2-fluoro-5-nitropyridine and 13.8g (0.1mol) of potassium carbonate were added to a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the reaction solution was poured into cold water after warming to 150 ℃ for 12 hours, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
Figure BDA0002318591720000091
s3. Synthesis of N6- (5-aminopyridin-2-yl) -N2- (6-aminopyridin-3-yl) -9,10-dihydroacridine-2,6-diamine:
4.55g (0.01mol) of N6- (5-nitropyridin-2-yl) -N2- (6-nitropyridin-3-yl) -9,10-dihydroacridine-2,6-diamine was added to a 500ml three-necked flask, 450ml of absolute ethanol was added, magnetic stirring was carried out and argon gas was introduced, after the oil bath was heated to 70 ℃, 0.1g of 10% wt palladium on carbon was added and 10ml of hydrazine hydrate was gradually added dropwise, after a reflux reaction for 24 hours, the reaction solution was filtered by a funnel, the filtrate was placed in a refrigerator for 24 hours to crystallize, after which an off-white solid was collected by suction filtration and dried in a vacuum oven at 80 ℃ for 24 hours to obtain a product.
Example 3
This example provides the synthesis of N1, N1' - (9,10-dihydroacridine-2,7-diyl) bis (bezene-1, 3-diamine):
Figure BDA0002318591720000092
s1 Synthesis of intermediate 9,10-dihydroacridine-2,6-diamine:
adding 3.41g (0.01mol) of 3,7-dibromo-10H-phenoxazine, a proper amount of cuprous oxide, 50ml of NMP and 13ml of ammonia water (29 percent and 0.2mol) into a 200ml pressure resistant bottle, reacting at 100 ℃, pouring the reaction liquid into ice water after the reaction is finished, extracting with dichloromethane, removing the solvent under reduced pressure, purifying the product by using dichloromethane/2: 1 (volume ratio) as a stationary phase and silica gel as a stationary phase for column chromatography, collecting the product, spin-drying, and drying at 80 ℃ for 24 hours in vacuum to obtain the intermediate. The intermediate has the following structure:
Figure BDA0002318591720000101
s2, synthesizing an intermediate N2, N7-bis (3-nitrophenyl) -9,10-dihydroacridine-2, 7-diamine:
2.11g (0.01mol) of 9,10-dihydroacridine-2,6-diamine, 7.50g (0.05mol) of m-fluoronitrobenzene and 13.8g (0.1mol) of potassium carbonate are added into a 250ml three-neck flask, 150ml of dimethyl sulfoxide is added, magnetic stirring is carried out, argon gas is introduced, the temperature is increased to 150 ℃ for reaction for 12 hours, then the reaction solution is poured into cold water, precipitates are filtered out, and hydrochloric acid and water are used for washing, thus obtaining the intermediate. The intermediate has the following structure:
Figure BDA0002318591720000102
s3, synthesizing N1, N1' - (9, 10-dihydroScriptine-2, 7-diyl) bis (bezene-1, 3-dimsine):
adding 4.53g (0.01mol) of N2, N7-bis (3-nitrophenyl) -9, 10-dihydroScriptine-2, 7-diSmine into a 500ml three-necked bottle, adding 450ml of absolute ethyl alcohol, magnetically stirring and introducing argon, heating in an oil bath to 70 ℃, adding 0.1g of 10 wt% palladium carbon, gradually dropwise adding 10ml of hydrazine hydrate, refluxing for 24 hours, filtering the reaction solution by using a funnel, placing the filtrate in a refrigerator for 24 hours for crystallization, collecting off-white solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain the product.
Example 4
This example provides the synthesis of N2, N2' - (9,10-dihydroacridine-2,6-diyl) bis (naphthalene-2, 6-diamine):
Figure BDA0002318591720000103
s1, synthesizing an intermediate N2, N6-bis (6-nitrilophen-2-yl) -9, 10-dihydroacridinine-2, 6-diamine:
2.11g (0.01mol) of 9,10-dihydroacridine-2,6-diamine, 9.56g (0.05mol) of 2-fluoro-6-nitro-naphthalene and 13.8g (0.1mol) of potassium carbonate are added into a 250ml three-neck flask, 150ml of dimethyl sulfoxide is added, magnetic stirring is carried out, argon gas is introduced, the temperature is increased to 150 ℃, reaction liquid is poured into cold water after 12 hours of reaction, precipitates are filtered out, and hydrochloric acid and water are used for washing, so as to obtain an intermediate. The intermediate has the following structure:
Figure BDA0002318591720000111
s2, synthesizing N2, N2' - (9,10-dihydroacridine-2,6-diyl) bis (naphthalene-2, 6-diamine):
adding 5.54g (0.01mol) of N2, N6-bis (6-nitroanthylalen-2-yl) -9,10-dihydroacridine-2,6-diamine into a 500ml three-neck flask, adding 450ml of absolute ethyl alcohol, magnetically stirring and introducing argon, heating the oil bath to 70 ℃, adding 0.1g of 10 wt% palladium carbon, gradually dropwise adding 10ml of hydrazine hydrate, refluxing for 24h, filtering the reaction solution by using a funnel, placing the filtrate in a refrigerator for 24h for crystallization, collecting off-white solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain a product 4.
Example 5
This example provides a synthesis of N1, N1' - (9,10-dihydroacridine-2,7-diyl) bis (N4- (4-aminophenyl) bezene-1, 4-diamine):
Figure BDA0002318591720000112
s1, synthesizing an intermediate N1, N1' - (9,10-dihydroacridine-2,7-diyl) bis (N4- (4-nitrophenyl) bezene-1, 4-diamine):
2.11g (0.01mol) of 9,10-dihydroacridine-2,7-diamine, 11.61g (0.05mol) of 4-fluoro-N- (4-nitrophenyl) aniline and 13.8g (0.1mol) of potassium carbonate are added into a 250ml three-necked flask, 150ml of dimethyl sulfoxide is added, magnetic stirring is carried out, argon is introduced, the temperature is increased to 150 ℃, reaction liquid is poured into cold water after 12 hours of reaction, precipitates are filtered out, and hydrochloric acid and water are used for washing, so as to obtain an intermediate. The intermediate has the following structure:
Figure BDA0002318591720000113
s2, synthesis of N1, N1' - (9,10-dihydroacridine-2,7-diyl) bis (N4- (4-aminophenyl) bezene-1, 4-diamine):
6.36g (0.01mol) of N1, N1' - (10H-phenoxazine-3,7-diyl) bis (N4- (4-nitrophenyl) benzene-1,4-diamine) is added into a 500ml three-necked flask, 450ml of absolute ethyl alcohol is added, magnetic stirring is carried out, argon is introduced, after the oil bath is heated to 70 ℃, 0.1g of 10% wt palladium carbon is added, 10ml of hydrazine hydrate is gradually added dropwise, after reflux reaction is carried out for 24 hours, the reaction liquid is filtered by a funnel, the filtrate is placed in a refrigerator for 24 hours for crystallization, after suction filtration, off-white solid is collected, and the product is dried in a vacuum drying oven at 80 ℃ for 24 hours to obtain the product.
Example 6
This example provides for the synthesis of 4,4' - ((9, 10-dihydroacridinine-3, 6-diyl) bis (azanediyl)) bis (N- (4-aminophenyl) benzamide):
Figure BDA0002318591720000121
s1, synthesizing an intermediate 4,4' - ((9,10-dihydroacridine-3,6-diyl) bis (azanediyl)) bis (N- (4-nitrophenyl) benzamide):
2.11g (0.01mol) of 9,10-dihydroacridine-3,6-diamine, 13.01g (0.05mol) of 4-fluoro-N- (4-nitrophenyl) benzamide and 13.8g (0.1mol) of potassium carbonate were added to a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring and argon gas introduction were performed, the reaction solution was heated to 150 ℃ to react for 12 hours, and then poured into cold water, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
Figure BDA0002318591720000122
s2, synthesizing 4,4' - ((9,10-dihydroacridine-3,6-diyl) bis (azanediyl)) bis (N- (4-aminophenyl) benzamide):
6.92g (0.01mol) of 4,4' - ((9, 10-dihydroacridinine-3, 6-diyl) bis (azanediyl)) bis (N- (4-nitrophenyl) benzamide) is added into a 500ml three-necked flask, 450ml of absolute ethyl alcohol is added, the mixture is magnetically stirred and is introduced with argon, after the oil bath is heated to 70 ℃, 0.1g of 10 percent by weight of palladium carbon is added, 10ml of hydrazine hydrate is gradually added dropwise, after reflux reaction is carried out for 24 hours, the reaction liquid is filtered by a funnel, the filtrate is placed in a refrigerator for 24 hours for crystallization, after suction filtration, off-white solid is collected, and the off-white solid is dried in a vacuum drying oven at 80 ℃ for 24 hours, so that the product is obtained.
Example 7
This example provides a thermal imidization process to prepare polyimide, comprising the steps of:
dissolving diamine containing 9,10-dihydroacridine structure and dianhydride containing X structure in a polar aprotic solvent according to a molar ratio of 1: 0.95-1.05 in an argon protective atmosphere, stirring and reacting at-15-30 ℃ for 2-48 h to obtain homogeneous polyamic acid glue solution, then blade-coating the polyamic acid glue solution on a glass plate to form a thin layer with the thickness of 0.3-3 mm, then placing the glass plate in an oven, and heating, wherein the heating process is as follows: heating to 100 ℃ and keeping the temperature constant for 0.5-1 h, heating from 100 ℃ to 200 ℃ and keeping the temperature constant for 0.5-1 h, heating from 200 ℃ to 300 ℃ and keeping the temperature constant for 0.5-1 h, finally heating from 300 ℃ to 420 ℃ and keeping the temperature constant for 1.0-2.0 h, and cooling to obtain the high-planarity polyimide film containing the 9,10-dihydroacridine structure.
Example 8
This example provides a polyimide prepared by chemical imidization using the diamine monomer prepared in examples 1 to 4 and a pyromellitic dianhydride monomer:
dissolving diamine containing 9,10-dihydro acridine structure and dianhydride containing X structure in a molar ratio of 1: 0.95-1.05 in a polar aprotic solvent in an argon protective atmosphere, stirring and reacting for 2-48 h at-15-30 ℃ to obtain homogeneous polyamic acid glue solution, adding the polyamic acid glue solution into a mixed solution of pyridine and acetic anhydride, heating to 60-170 ℃, stirring for 0.5-6 h, cooling, pouring into methanol or acetone to obtain polyimide precipitate, filtering and drying to obtain polyimide powder, then dissolving the polyimide powder in N-methyl pyrrolidone, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, m-phenol or tetrahydrofuran, heating and dissolving, then coating the polyimide film on a glass plate in a scraping way, drying the glass plate in vacuum at 70-300 ℃, and cooling to obtain the polyimide film.
The following examples are prepared by polymerizing the diamines prepared in examples 1-6, respectively, with the dianhydrides shown below, each of which is commercially available on the commercial scale from the reagent of Aladdin, by the thermal imide method or the chemical imide method, and the specific dianhydride structure is as follows:
examples 9 to 14 Pyromellitic dianhydride
Examples 15 to 20 Biphenyltetracarboxylic acid dianhydride
Examples 21 to 26 1,4,5, 8-naphthalenetetracarboxylic acidAnhydrides of
Examples 27 to 32 4,4' -Biphenyl Ether dianhydride
Examples 33 to 38 4,4' - (Hexafluoroisopropylene) diphthalic anhydride
Examples 39 to 44 3,3', 4' -benzophenone tetracarboxylic dianhydride
The polyimide with the 9,10-dihydroacridine structure prepared in the examples 9-44 is tested for barrier property, glass transition temperature, thermal stability and thermal expansion coefficient, the tests of the polyimide with the same kind prepared by thermal imidization and chemical imidization are averaged, and the test results are shown in tables 1-6:
the barrier property is detected according to GB/T1038-2000 differential pressure method for testing gas permeability of plastic films and sheets and GB/T19789-2005 coulometer detection method for testing oxygen permeability of plastic films and sheets of packaging materials, and the thermal expansion coefficient and the proud transition temperature are detected according to GB/T36800.2-2018 thermo-mechanical analysis method for plastics.
TABLE 1
Figure BDA0002318591720000141
TABLE 2
Figure BDA0002318591720000151
TABLE 3
Figure BDA0002318591720000152
TABLE 4
Figure BDA0002318591720000153
TABLE 5
Figure BDA0002318591720000161
TABLE 6
Figure BDA0002318591720000162
As shown in tables 1-6, the diamine monomer containing the polar group and having high planarity is prepared by simultaneously introducing the 9,10-dihydroacridine structure and the polar group into the diamine monomer, and has high electron density and good rigid structure. A plane rigid structure and a polar group are introduced into a polyimide main chain, the plane rigid structure is beneficial to regular stacking of molecular chains and induces polymer crystallization, and the polar group can enhance the hydrogen bond effect of molecular chain bonds and promote the tight stacking of the molecular chains. The synergy of the effects can ensure that molecular chains are regularly arranged and tightly stacked, and the barrier property of the polyimide is obviously improved, so that the polyimide has excellent barrier property, higher glass transition temperature and thermal stability and lower thermal expansion coefficient.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A polyimide containing a 9,10-dihydroacridine structure is characterized by having a structural formula as follows:
Figure FDA0002318591710000011
Ar1any one selected from the following structural formulas:
Figure FDA0002318591710000012
wherein y is 1-10000; n is 0-6, m is 0-6, and n and m in the same structural formula are not 0 at the same time.
2. The polyimide having a 9,10-dihydroacridine structure according to claim 1, wherein Ar is Ar2And Ar3Any one selected from the following structural formulas:
Figure FDA0002318591710000021
x is selected from any one of the following structures:
Figure 3
3. the polyimide having a 9,10-dihydroacridine structure according to claim 1 or 2, characterized in that it is prepared by the steps comprising: in an inert gas protective atmosphere, dissolving a diamine monomer containing a 9,10-dihydroacridine structure and a dianhydride monomer containing an X structure in a molar ratio of 1: 0.95-1.05 in a polar aprotic solvent, stirring and reacting for 2-48 h at-15-30 ℃ to obtain a homogeneous polyamic acid glue solution, and then performing thermal imidization or chemical imidization dehydration on the polyamic acid glue solution to obtain polyimide.
4. The polyimide having a 9,10-dihydroacridine structure according to claim 3, wherein the thermal imidization step is: scraping the polyamide acid glue solution on a glass plate to form a thin layer with the thickness of 0.3-3 mm, then placing the glass plate in an oven, and heating, wherein the heating process is as follows: and (3) raising the temperature to 100 ℃ and keeping the temperature constant for 0.5-1 h, raising the temperature from 100 ℃ to 200 ℃ and keeping the temperature constant for 0.5-1 h, raising the temperature from 200 ℃ to 300 ℃ and keeping the temperature constant for 0.5-1 h, raising the temperature from 300 ℃ to 420 ℃ and keeping the temperature constant for 1.0-2.0 h, and cooling to obtain the high-planarity polyimide film containing the 9,10-dihydroacridine structure.
5. The polyimide having a 9,10-dihydroacridine structure according to claim 3, wherein the chemical imidization step is: adding the polyamic acid glue solution into a mixed solution of pyridine and acetic anhydride, heating to 60-170 ℃, stirring for 0.5-6 h, cooling, pouring into methanol or acetone to obtain polyimide precipitate, filtering and drying to obtain polyimide powder, dissolving the polyimide powder in N-methyl pyrrolidone, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, m-phenol or tetrahydrofuran, heating and dissolving, coating the polyimide powder on a glass plate in a scraping manner, drying at 70-300 ℃, and cooling to obtain the polyimide film.
6. The polyimide having a 9,10-dihydroacridine structure according to claim 3, wherein the diamine monomer having a 9,10-dihydroacridine structure is prepared by a method comprising:
s1, 9,10-dihydroacridine monomer substituted by two halogen atoms
Figure FDA0002318591710000031
Figure FDA0002318591710000032
Reacting with ammonia water under a protective atmosphere to obtain a monomer 1, a monomer 2 or a monomer 3;
s2, adding the monomer 1, the monomer 2 or the monomer 3 in the step S1, an Ar1 monomer containing a halogen atom and a nitro substituent into a solvent, adding alkali in a protective gas atmosphere, and performing Ullmann coupling reaction to obtain a monomer 4, a monomer 5 or a monomer 6 containing two nitro groups;
s3, adding the monomer 4, the monomer 5 or the monomer 6 in the step S2 into a solvent, adding a reducing agent, and carrying out reduction reaction in an atmosphere of protective gas to obtain a diamine monomer containing a 9,10-dihydroacridine structure and shown in a structural general formula I, II or III;
the monomer 1, the monomer 2 and the monomer 3 in the step S1, and the monomer 4, the monomer 5 and the monomer 6 in the step S2 respectively have the following structural characteristics:
Figure FDA0002318591710000041
7. the polyimide having a 9,10-dihydroacridine structure according to claim 6, wherein monomer 1, monomer 2 or monomer 3 in S2 is reacted with Ar having a halogen atom and a nitro group substitution1The mass ratio of the monomers is 1: 2-4, and the mass ratio of the added alkali to the monomers 1, 2 or 3 is 1: 0.5-2; the mass ratio of the monomer 4, the monomer 5 or the monomer 6 to the reducing agent in S3 is 1: 2-32.
8. The polyimide having a 9,10-dihydroacridine structure according to claim 6, wherein the protective gas in S1-S3 is one or more of nitrogen, helium, neon, argon, krypton, xenon and radon; the alkali in S2 is one or more of sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium fluoride, n-butyl lithium, potassium tert-butoxide, sodium tert-butoxide and hexamethyldisilazane lithium; in S3, the reducing agent is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder and zinc powder; the solvent in S1 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene and xylene; the solvent in S2 is one or more of dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, toluene, xylene, acetone, acetonitrile and diphenyl ether; the solvent in S3 is one or more of ethanol, methanol, N-propanol, tert-butanol, tert-amyl alcohol, ethanol, hexanol, tetrahydrofuran, 1,4 dioxane, dimethyl sulfoxide, N-dimethylformamide, ethyl acetate and toluene.
9. The polyimide having a 9,10-dihydroacridine structure according to claim 6, wherein the reaction temperature in S1-S3 is 50 ℃ to 170 ℃, the reaction time is 10-48 hours, the drying temperature is 40 ℃ to 120 ℃, and the drying time is 6-30 hours.
10. The polyimide containing a 9,10-dihydroacridine structure as claimed in any one of claims 1 to 9, wherein the polyimide is applied to microelectronics, military industry, aerospace, packaging and protection, and electronic device packaging.
CN201911288076.8A 2019-12-15 2019-12-15 Polyimide containing 9,10-dihydroacridine structure and preparation method and application thereof Withdrawn CN111040158A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911288076.8A CN111040158A (en) 2019-12-15 2019-12-15 Polyimide containing 9,10-dihydroacridine structure and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911288076.8A CN111040158A (en) 2019-12-15 2019-12-15 Polyimide containing 9,10-dihydroacridine structure and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN111040158A true CN111040158A (en) 2020-04-21

Family

ID=70236410

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911288076.8A Withdrawn CN111040158A (en) 2019-12-15 2019-12-15 Polyimide containing 9,10-dihydroacridine structure and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111040158A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114790162A (en) * 2022-05-19 2022-07-26 江苏森禾化工科技有限公司 Low-fogging degree environment-friendly plasticizer

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114790162A (en) * 2022-05-19 2022-07-26 江苏森禾化工科技有限公司 Low-fogging degree environment-friendly plasticizer
CN114790162B (en) * 2022-05-19 2024-02-20 江苏森禾化工科技有限公司 Low-atomization environment-friendly plasticizer

Similar Documents

Publication Publication Date Title
CN111763182A (en) Diamine containing phenothiazine and amide structures and polyimide thereof
CN108864454B (en) High-transparency and high-flexibility polyimide film for electronic device and preparation method
CN111072960B (en) Polyimide with high barrier property and preparation method and application thereof
TW201525025A (en) Polyimide precursor composition, method of manufacturing polyimide, polyimide, polyimide film, and substrate
CN101787129A (en) Soluble and high-temperature resistant aromatic polyimide and preparation method thereof
CN111040159A (en) High-barrier polyimide containing high-planarity structure and preparation method and application thereof
JP2016502560A (en) Novel polyamideimide with low thermal expansion coefficient
JP2016035073A (en) Polyimide precursor and polyimide
CN111253576A (en) Antibacterial material and preparation method and application thereof
Wang et al. Synthesis and characterization of an aromatic diamine and its polyimides containing asymmetric large side groups
CN110198926A (en) Diamine compound and the polyimide compound and molding for using it
CN113583443A (en) Transparent polyimide applied to flexible photoelectric field and preparation method thereof
CN110938305B (en) Polyimide barrier film material and preparation method and application thereof
Zhang et al. Preparation and properties of heat-sealable polyimide films with comparable coefficient of thermal expansion and good adhesion to copper matrix
CN112979582A (en) Preparation method of diamine containing phenothiazine structure and synthetic polyimide
CN111040158A (en) Polyimide containing 9,10-dihydroacridine structure and preparation method and application thereof
Huang et al. Synthesis and characterization of novel highly soluble and optical transparent polyimides containing tert-butyl and morpholinyl moieties
CN111072585A (en) Diamine containing phenoxazine and amide structures and polyimide thereof
CN111072975A (en) Polyimide for FOLED substrate and preparation method thereof
CN111116538A (en) Diamine with antibacterial effect and preparation method thereof
CN108503832A (en) A kind of polyimides and its preparation method and application containing fluorenes or Fluorenone structure
CN111303424A (en) Transparent high polymer material composition and application thereof
CN111072964A (en) Polyimide precursor composition and preparation method and application thereof
CN111040160A (en) Thioxanthone polyimide and preparation method thereof
CN112390950B (en) Polyimide, polyimide film and preparation method of polyimide film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20200421

WW01 Invention patent application withdrawn after publication