CN111072506A - Diamine containing anthrone structure and polyimide prepared by using same - Google Patents

Diamine containing anthrone structure and polyimide prepared by using same Download PDF

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CN111072506A
CN111072506A CN201911288070.0A CN201911288070A CN111072506A CN 111072506 A CN111072506 A CN 111072506A CN 201911288070 A CN201911288070 A CN 201911288070A CN 111072506 A CN111072506 A CN 111072506A
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monomer
polyimide
anthrone
diamine
anthrone structure
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刘亦武
谭井华
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Hunan University of Technology
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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    • 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
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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    • 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
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes

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Abstract

The invention discloses diamine containing an anthrone structure and polyimide prepared by utilizing the diamine. The invention uses the anthrone intermediate containing two halogen atom substitutions to react with ammonia water, and converts the halogen atom into amino; grafting a nitro-containing group through an Ullmann coupling reaction, reducing to obtain a diamine monomer containing an anthrone structure, and polymerizing the prepared diamine monomer and dianhydride to obtain polyimide containing the anthrone structure. The invention creatively introduces the plane rigid structure and the polar group of the anthrone into the polyimide main chain, the plane rigid structure is beneficial to regular stacking of molecular chains and induces the crystallization of polymers, 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

Diamine containing anthrone structure and polyimide prepared by using same
Technical Field
The invention relates to the technical field of material science, in particular to polyimide capable of being used for an FOLED substrate and a preparation method thereof.
Background
Polyimide is one of organic polymer materials with the best comprehensive performance, has extremely strong heat resistance, good mechanical property and dimensional stability, and becomes one of the most attractive high-performance polymer materials due to the advantages of the performance. Aromatic Polyimide (PI) is a high temperature resistant material with excellent performance, contains strong rigid benzene rings and imide rings, has excellent characteristics such as high glass transition temperature (Tg), high strength, low Coefficient of Thermal Expansion (CTE), and the like, and is widely applied to structural materials or used as functional materials.
The currently reported polyimide generally has the defects of poor barrier property and easy water and oxygen permeation. The existing polyimide is generally modified by adding a nano inorganic substance, and the diffusion path of water vapor and oxygen molecules in a base material is effectively prolonged through a flaky nano layer, so that the barrier property of the polyimide is improved. In addition, the barrier property of the polyimide film is improved by a compact film layer coated on the polyimide film, and even the barrier property of the polyimide film cannot be improved any more after the coating is stripped. Or other films with high barrier property and polyimide are bonded to form a multilayer composite film, the preparation process is complex, and the difference between the film and the polyimide in the aspects of strength, heat resistance and the like is large, so that the waste of the polyimide property is caused. The existing mode is that the barrier property of the additive to the polyimide is improved, which can increase some application limits of the additive, and the most fundamental mode for improving the polyimide is that the free volume is greatly reduced by the structural design of molecules from the structure of the polyimide, so that the barrier property of the polyimide is effectively improved. Therefore, preparing a polyimide with a high packing density and only a small volume is the most effective method for improving the barrier properties.
Disclosure of Invention
The invention aims to solve the technical problem of providing diamine containing an anthrone structure and polyimide with high barrier property prepared by the diamine aiming at the defect of barrier property of the existing polyimide.
The invention also provides a preparation method of the polyimide for the FOLED substrate.
The purpose of the invention is realized by the following technical scheme:
diamine containing an anthrone structure, which has a structural formula shown as the following:
Figure BDA0002318592790000021
wherein Ar is1Any one selected from the following structural formulas:
Figure BDA0002318592790000022
ar is2And Ar3Any one selected from the following structural formulas:
Figure BDA0002318592790000031
wherein n is 0-6, m is 0-6, and n and m in the same structural formula are not 0 at the same time.
Preferably, Ar is2Is composed of
Figure BDA0002318592790000032
Ar3 is one or more of
Figure BDA0002318592790000033
One or more of (a).
The diamine containing the anthrone structure is used for preparing polyimide, and the structural general formula is as follows:
Figure BDA0002318592790000034
wherein y is 1-10000, and X is any one of the following structures:
Figure BDA0002318592790000041
the preparation method of the polyimide containing the anthrone structure comprises the following steps:
s1, preparing an anthrone monomer containing two halogen atom substitutions
Figure BDA0002318592790000042
Figure BDA0002318592790000043
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 xanthone structure;
s4, in a protective atmosphere, dissolving diamine monomers containing xanthone structures and dianhydride containing X structures in a strong-polarity aprotic solvent in proportion, stirring for reaction 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;
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 BDA0002318592790000051
further, the mass ratio of the monomer 1, the monomer 2 or the monomer 3 to the substance containing a halogen atom and a nitro-substituted Ar1 monomer in S2 is 1: 2-8. Preferably, the ratio of the amount of monomer 1, monomer 2 or monomer 3 to the amount of substance containing one halogen atom and one nitro-substituted Ar1 monomer in S2 is 1: 5.
Further, the amount ratio of the added alkali to the monomer 1, the monomer 2 or the monomer 3 in S2 is 1: 0.5-2; preferably, the ratio of base added to the mass of monomer 1, monomer 2 or monomer 3 in S2 is 1: 1.
Further, the ratio of the amount of the monomer 4, the monomer 5, or the monomer 6 to the amount of the reducing agent in S3 is 1:2 to 32. Preferably, the amount of the substance of the monomer 4, the monomer 5 or the monomer 6 to the reducing agent in S3 is 1: 20.
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 hexamethyldisilazane-based aminolithium;
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;
further, the solvent in S2 is one or more of dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, 1,4 dioxane, toluene, xylene, acetone, acetonitrile, and diphenyl ether;
further, 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.
Further, the stirring reaction temperature in the S4 is-15-30 ℃, and the stirring reaction time is 2-48 h.
The obtained polyimide containing the anthrone structure can be applied to the fields of microelectronics, military industry, aerospace, packaging and protection, electronic packaging and the like.
Compared with the prior art, the beneficial effects are:
the invention designs and synthesizes an angle through a molecular structure, creatively introduces an anthrone 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 anthrone 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 containing the anthrone structure has high planarity and strong rigidity, and contains polar groups, and the prepared polyimide has regular molecular chain arrangement, strong intermolecular force and tight molecular chain stacking, so that the polyimide has excellent barrier property, higher glass transition temperature and thermal stability and lower thermal expansion coefficient.
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 2,7-bis ((4-aminophenyl) amino) anthracenone-9 (10H) -one:
Figure BDA0002318592790000061
s1, synthesizing an intermediate 2,7-diaminoanthracen-9(10H) -one:
adding 3.52g (0.01mol) of 2, 7-dibromoantrhracene-9 (10H) -one, 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 taking dichloromethane and n-hexane as mobile phase silica gel as stationary phase as column chromatography, collecting the product, spin-drying, and drying at 80 ℃ for 24 hours in vacuum to obtain an intermediate I. The intermediate has the following structure:
Figure BDA0002318592790000071
s2, synthesizing an intermediate 2,7-bis ((4-nitrophenyl) amino) anthracen-9(10H) -one:
2.24g (0.01mol) of 2, 7-diaminoanthracacen-9 (10H) -one, 7.50g (0.05mol) of p-fluoronitrobenzene and 13.8g (0.1mol) of potassium carbonate were put into a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the temperature was raised to 150 ℃ to react for 12 hours, then the reaction solution was poured into cold water, and the precipitate was filtered off and washed with hydrochloric acid and water to obtain intermediate II. The intermediate II has the following structure:
Figure BDA0002318592790000072
s3, synthesizing 2,7-bis ((4-aminophenyl) amino) anthracen-9(10H) -one:
adding 4.66g (0.01mol) of 2,7-bis ((4-nitrophenyl) amino) anthracen-9(10H) -one 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 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 the product.
Example 2
The present embodiment provides
Synthesis of 2- ((5-aminopyridin-2-yl) amino) -6- ((6-aminopyridin-3-yl) amino) anthracen-9(10H) -one:
Figure BDA0002318592790000073
s1, synthesizing an intermediate 2,6-diaminoanthracen-9(10H) -one:
adding 3.52g (0.01mol) of 2, 6-dibromoantrhracene-9 (10H) -one, 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 taking dichloromethane which is 2: 1 (volume ratio) as mobile phase silica gel as stationary phase as column chromatography, collecting the product, spin-drying, and drying in vacuum at 80 ℃ for 24 hours to obtain the intermediate. The intermediate has the following structure:
Figure BDA0002318592790000081
s2, synthesizing an intermediate
2-((5-nitropyridin-2-yl)amino)-6-((6-nitropyridin-3-yl)amino)anthracen-9(10H)-one：
2.24g (0.01mol) of 2,6-diaminoanthracen-9(10H) -one, 7.105g (0.05mol) of 2-fluoro-5-nitropyridine and 13.8g (0.1mol) of potassium carbonate were charged into 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 BDA0002318592790000082
s3. synthesis
2-((5-aminopyridin-2-yl)amino)-6-((6-aminopyridin-3-yl)amino)anthracen-9(10-H)-one:
4.68g (0.01mol)
Adding 2- ((5-nitropyridin-2-yl) amino) -6- ((6-nitropyridin-3-yl) amino) anthracen-9(10H) -one into a 500ml three-neck flask, adding 450ml of absolute ethyl alcohol, magnetically stirring and introducing argon, heating 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 liquid 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 3
This example provides the synthesis of 3,6-bis ((3-aminophenyl) amino) anthracenone-9 (10H) -one:
Figure BDA0002318592790000091
s1, synthesizing an intermediate 2,6-diaminoanthracen-9(10H) -one:
adding 3.52g (0.01mol) of 2, 6-dibromoantrhracene-9 (10H) -one, 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 taking dichloromethane and n-hexane as mobile phase silica gel as stationary phase as 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 BDA0002318592790000092
s2, synthesizing an intermediate 3,6-bis ((3-nitrophenyl) amino) anthracen-9(10H) -one:
2.24g (0.01mol) of 2, 6-diaminoanthracacen-9 (10H) -one, 7.50g (0.05mol) of m-fluoronitrobenzene and 13.8g (0.1mol) of potassium carbonate were charged in a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the temperature was raised to 150 ℃ to react for 12 hours, then the reaction solution was poured into cold water, and the precipitate was filtered off and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
Figure BDA0002318592790000093
(3) synthesis of 3,6-bis ((3-aminophenyl) amino) anthracen-9(10H) -one:
adding 4.66g (0.01mol) of 3,6-bis ((3-nitrophenyl) amino) anthracen-9(10H) -one 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 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 the product.
Example 4
This example provides the synthesis of 2,6-bis ((6-aminophthalen-2-yl) amino) anthracenone-9 (10H) -one:
Figure BDA0002318592790000101
s2. Synthesis of intermediate 2,6-bis ((6-nitriloalken-2-yl) amino) anthracen-9(10H) -one:
2.24g (0.01mol) of 2,6-diaminoanthracen-9(10H) -one, 9.56g (0.05mol) of 2-fluoro-6-nitroanthlene 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 BDA0002318592790000102
s2. Synthesis of 2,6-bis ((6-aminonaphthalene-2-yl) amino) anthracen-9(10H) -one:
adding 5.67g (0.01mol) of 2,6-bis ((6-nitrilophen-2-yl) amino) anthracen-9(10H) -one 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 liquid 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 5
The present embodiment provides
Synthesis of 3,6-bis ((4- ((4-aminophenyl) amino) phenyl) amino) anthracen-9(10H) -one:
Figure BDA0002318592790000103
s1, synthesizing an intermediate
3,6-bis((4-((4-nitrophenyl)amino)phenyl)amino)anthracen-9(10H)-one：
2.24g (0.01mol) of 3, 6-diaminoanthracacen-9 (10H) -one, 11.61g (0.05mol) of 4-fluoro-N- (4-nitrophenyl) aniline and 13.8g (0.1mol) of potassium carbonate were put into a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was conducted while introducing argon gas, the reaction solution was poured into cold water after warming to 150 ℃ for reaction 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 BDA0002318592790000111
s2. synthesis
3,6-bis((4-((4-aminophenyl)amino)phenyl)amino)anthracen-9(10H)-one：
Mixing 6.67g (0.01mol)
N1, N1' - (10H-phenoxazine-3,7-diyl) bis (N4- (4-nitrophenyl) benzene-1,4-diamine) are added into a 500ml three-neck flask, 450ml of absolute ethyl alcohol is added, magnetic stirring is carried out, argon is introduced, after the oil bath is heated to 70 ℃, 10% wt of palladium carbon 0.1g is added, 10ml of hydrazine hydrate is gradually dripped, after 24 hours of reflux reaction, reaction liquid is filtered by a funnel, filtrate is placed in a refrigerator for 24 hours to crystallize, 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 to obtain the product.
Example 6
The present embodiment provides
Synthesis of 4,4' - ((9-oxo-9H-dihydroanthracene-2,7-diyl) bis (azanediyl)) bis (N- (4-aminophenyl) benzamide):
Figure BDA0002318592790000112
s1, synthesizing intermediate 4,4' - ((9-oxo-9H-dihydroanthrene-2, 7-diyl) bis (azanediyl)) bis (N- (4-nitrophenyl) benzamide):
2.24g (0.01mol) of 2, 7-diaminoanthracenone-9 (10H) -one, 13.01g (0.05mol) of 4-fluoro-N- (4-nitrophenyl) benzamide and 13.8g (0.1mol) of potassium carbonate were put in a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was conducted while introducing argon gas, 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 BDA0002318592790000121
s2. synthesis
4,4'-((9-oxo-9H-dihydroanthracene-2,7-diyl)bis(azanediyl))bis(N-(4-aminophenyl)benzamide)：
7.05g (0.01mol)
Adding 4,4' - ((9-oxo-9,10-dihydroanthracene-2,7-diyl) bis (azanediyl)) bis (N- (4-nitrophenyl) be-nzamide) into a 500ml three-necked bottle, 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 dripping 10ml of hydrazine hydrate, refluxing for 24 hours, filtering the reaction liquid 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 7
This example provides the preparation of polyimide by thermal imidization, using the following specific steps:
in an argon protective atmosphere, dissolving diamine containing an anthrone structure and dianhydride containing an X structure in a strong polar aprotic solvent according to a molar ratio of 1: 0.95-1.05, stirring and reacting at-15-30 ℃ for 2-48 h to obtain a homogeneous polyamic acid glue solution, scraping and coating the polyamic acid glue solution on a glass plate to form a thin layer with the thickness of 1-3 mm, then placing the glass plate in a vacuum oven, vacuumizing, heating, and performing the heating process: 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 anthrone structure.
Polyimide was prepared by the method of example 7 using the high-plane diamines of the anthrone structure prepared in examples 1 to 6, with pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, 4 '-diphenyl ether dianhydride, 1,4,5, 8-naphthalene tetracarboxylic anhydride, 4' - (hexafluoroisopropylene) diphthalic anhydride and 3,3', 4' -benzophenonetetracarboxylic dianhydride, respectively, and the diamines prepared in examples 1 to 6 were classified into polyimide nos. 1 to 36, and the barrier properties, glass transition temperature, thermal stability and thermal expansion coefficient of the polyimide were measured, and the results are shown in table 1:
wherein the dianhydrides are all commercially available on the commercial scale from the reagent Aladdin. 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 BDA0002318592790000131
Figure BDA0002318592790000141
As shown in Table 1, the present invention introduces the anthrone structure and the polar group into the diamine monomer simultaneously to prepare the polar group-containing diamine monomer with high planarity, 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. The diamine containing the anthrone structure is characterized by having the following structural general formula:
Figure FDA0002318592780000011
Ar1any one selected from the following structural formulas:
Figure FDA0002318592780000012
wherein 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 anthrone structure-containing diamine according to claim 1, wherein Ar is Ar2And Ar3Any one selected from the following structural formulas:
Figure FDA0002318592780000021
3. the diamine containing an anthrone structure according to claim 1 or 2, wherein the polyimide prepared from the diamine has the following general structural formula:
Figure FDA0002318592780000022
wherein, y is 1-10000, and X is any one of the following structures:
Figure FDA0002318592780000031
4. the anthrone structure-containing polyimide according to claim 3, wherein the polyimide is prepared by the steps comprising:
s1, preparing an anthrone monomer containing two halogen atom substitutions
Figure FDA0002318592780000032
Figure FDA0002318592780000033
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 an anthrone structure;
s4, in a protective atmosphere, dissolving a diamine monomer containing an anthrone structure and dianhydride containing an X structure in a strong-polarity aprotic solvent according to an equal molar ratio, stirring for reaction 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;
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 FDA0002318592780000041
5. the anthrone structure-containing polyimide according to claim 4, wherein the amount ratio of the monomer 1, the monomer 2 or the monomer 3 to the substance containing a halogen atom and a nitro group-substituted Ar1 monomer in S2 is 1:2 to 4, and the amount ratio of the base to the substance containing the monomer 1, the monomer 2 or the monomer 3 is 1: 0.5 to 2.
6. The polyimide having an anthrone structure according to claim 4, wherein the amount ratio of the monomer 4, the monomer 5 or the monomer 6 to the reducing agent in S3 is 1:2 to 32.
7. The polyimide with an anthrone structure according to claim 4, 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; the reducing agent in S3 is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder and zinc powder.
8. The polyimide containing an anthrone structure according to claim 4, wherein the solvent in S1 is one or more selected from 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 an anthrone structure according to claim 4, wherein the reaction temperature of S1 to S3 is 50 ℃ to 170 ℃ and the reaction time is 10 to 48 hours, and the drying temperature is 40 ℃ to 120 ℃ and the drying time is 6 to 30 hours.
10. The polyimide prepared according to claims 4-9 is used in microelectronics, military industry, aerospace, packaging and protection, and electronic packaging.
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