CN111269419A - Polyimide applicable to FOLED substrate and preparation method thereof - Google Patents

Polyimide applicable to FOLED substrate and preparation method thereof Download PDF

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CN111269419A
CN111269419A CN201911288090.8A CN201911288090A CN111269419A CN 111269419 A CN111269419 A CN 111269419A CN 201911288090 A CN201911288090 A CN 201911288090A CN 111269419 A CN111269419 A CN 111269419A
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monomer
polyimide
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xanthone
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刘亦武
谭井华
周栋
赵先清
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Hunan University of Technology
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    • 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
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
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Abstract

The invention discloses polyimide for an FOLED substrate and a preparation method thereof. Converting halogen atoms of dihalogenated xanthone into cyano groups, hydrolyzing to obtain dicarboxylic acid monomers, then performing acyl chlorination, grafting groups containing nitro groups through amide reaction, finally reducing to obtain diamine monomers, and polymerizing the prepared diamine monomers and dianhydride to obtain polyimide containing a xanthone structure. The polyimide containing the xanthone structure prepared by the invention has a plane rigid structure, contains more structures capable of generating hydrogen bonds, and has the advantages of tight stacking among molecular chains, small free volume and high barrier property.

Description

Polyimide applicable to FOLED substrate and preparation method thereof
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 and application thereof.
Background
In the middle of the 20 th century, with the development of high-tech fields such as aerospace, machinery, electronics, automobiles and the like, the requirements on the properties such as radiation resistance, thermal stability, modulus, strength, dielectric property and the like of materials are higher and higher, and polymer materials with main chains taking aromatic rings and heterocyclic rings as main structures are generated. Compared with other high molecular materials used at present, the service temperature of the polymer can be increased by more than 100 ℃. The successful development of the new materials becomes another big achievement in polymer science besides the Ziegler-Natta catalyst in the period. However, although there are dozens of aromatic hybrid polymers reported at the time, the number of them is really accepted by the industry. Among them, polyimide is one of the most spotlighted high-performance polymer materials because of its advantage in cost performance.
Aromatic Polyimide (PI) is a high-temperature resistant material with excellent performance, contains strong rigid benzene rings and imide rings, has excellent characteristics of high glass transition temperature (Tg), high strength, low Coefficient of Thermal Expansion (CTE) and the like, can well meet the high-temperature process requirement of the FOLED, and is one of the best choices of FOLED substrate materials or packaging materials. However, the barrier property of the traditional commercial polyimide film cannot meet the packaging requirement of the flexible display device. The existing method for improving the barrier property of polyimide generally adds layered nano particles, and effectively prolongs the diffusion path of water vapor in a base material through a flaky nano layer, thereby improving the barrier property of the polyimide. Such as modified sericite/polyimide composite film, the barrier property is greatly improved, and the water barrier transmittance (WVTR) reaches 0.0259 g/m2And day, the barrier effect is improved by 98.46 percent compared with that of a pure polyimide film. However, the polyimide composite film added with the inorganic nano material still cannot meet the packaging performance requirement of the FOLED. 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.
Disclosure of Invention
The invention aims to solve the technical problem of providing polyimide with high barrier property for an FOLED substrate aiming at the defects of thermal stability and barrier property of the existing FOLED substrate material.
The invention also provides a preparation method of the polyimide which can be used for the FOLED substrate.
The purpose of the invention is realized by the following technical scheme:
a polyimide used for an FOLED substrate has a structural general formula as follows:
Figure RE-GDA0002478418880000021
Ar1any one selected from the following structural formulas:
Figure RE-GDA0002478418880000022
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 Ar2And Ar3Any one selected from the following structural formulas:
Figure RE-GDA0002478418880000031
further, X is selected from any one of the following structures:
Figure RE-GDA0002478418880000032
preferably, Ar is2Is composed of
Figure RE-GDA0002478418880000041
Ar3 is one or more of
Figure RE-GDA0002478418880000042
One or more of (a); x is
Figure RE-GDA0002478418880000043
The preparation method of the polyimide for the FOLED substrate comprises the following steps:
s1. reacting a xanthone monomer containing two halogen atom substitutions
Figure RE-GDA0002478418880000044
Figure RE-GDA0002478418880000045
Adding cyanide into a solvent 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 S1 into a solvent, adding alkali, and performing hydrolysis reaction under the atmosphere of protective gas to obtain a dicarboxylic acid monomer 4, a monomer 5 or a monomer 6;
s3, dissolving the monomer 4, the monomer 5 or the monomer 6 in the step S2 into a solvent, adding N, N-dimethylformamide as a catalyst, slowly dropwise adding thionyl chloride under an ice bath condition, and performing acyl chlorination reaction to obtain a diacid chloride monomer 7, a monomer 8 or a monomer 9;
s4, adding the monomer 7, the monomer 8 or the monomer 9 in the step S3 and Ar1 containing an amino group and a nitro group for substitution into a solvent, and performing amidation reaction under a protective gas atmosphere to obtain a dinitromonomer 10, a monomer 11 or a monomer 12;
s5, adding the monomer 10, the monomer 11 or the monomer 12 in the step S4 into a solvent, introducing protective gas, adding a reducing agent, and carrying out reduction reaction to obtain a xanthone-containing diamine monomer shown in the structural general formulas I-III;
s6, in an argon 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, the monomer 4, the monomer 5 and the monomer 6 in the step S2, the monomer 7, the monomer 8 and the monomer 9 in the step S3, and the monomer 10, the monomer 11 and the monomer 12 in the step S4 respectively have the following structural characteristics:
Figure RE-GDA0002478418880000051
further, the ratio of the two halogen atom-substituted xanthone monomers in S1 to the amount of cyano-containing species in the cyanide compound is 1: 2-8; preferably, the ratio of the amounts of the two halogen atom-substituted xanthone monomers in S1 to the amount of cyano species in the cyanide is 1: 5.
Further, the ratio of the amount of the monomer 1, the monomer 2 or the monomer 3 to the amount of the added alkali in the S2 is 1: 10-50; preferably, the mass ratio of the monomer 1, the monomer 2 or the monomer 3 to the added base in S2 is 1: 30-40.
Further, the molar ratio of the monomer 4, the monomer 5 or the monomer 6 to the thionyl chloride in S3 is 1: 2-4; preferably, the molar ratio of monomer 4, monomer 5 or monomer 6 to thionyl chloride in S3 is 1: 3.
Further, the mass ratio of the monomer 7, the monomer 8 or the monomer 9 to the substance containing an amino group-and nitro-substituted Ar1 monomer in S4 is 1: 2-1: 4; preferably, the mass ratio of the monomer 7, the monomer 8 or the monomer 9 to the substance containing an amino group-and a nitro group-substituted Ar1 monomer in S4 is 1: 2.5.
Further, the mass ratio of the monomer 10, the monomer 11 or the monomer 12 to the reducing agent in S5 is 1: 2-1: 32. Preferably, the mass ratio of the monomer 10, the monomer 11 or the monomer 12 to the reducing agent in S5 is 1: 15-25.
Further, the molar ratio of the diamine monomer containing the xanthone structure to the dianhydride containing the X structure in S6 is 1: 0.9-1.1.
Further, the protective gas in S1-S5 is one or more of nitrogen, helium, neon, argon, krypton, xenon and radon;
further, in S1, the cyanide is NaCN, KCN, Zn (CN)2And one or more of CuCN; preferably, the cyanide in S1 is CuCN.
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; preferably, the base of S2 is potassium hydroxide.
Further, the reducing agent in S5 is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder, and zinc powder; preferably, the reducing agent of S5 is hydrazine hydrate.
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 water;
further, the solvent in S3 is dichloromethane; the solvent in S4 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene and xylene;
further, the solvent in S5 is one or more selected from 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 is 50-170 ℃, and 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 140 ℃, the reaction time is 24 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in the S2, the drying temperature is 80 ℃, and the drying time is 24 h; in the S3, the reaction temperature is 75 ℃, the reaction time is 12 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in the S4, the reaction temperature is 100 ℃, the reaction time is 12 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in S5, 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 S6 is-15-30 ℃, and the stirring reaction time is 2-48 h.
Further, the thermal imidization step is: scraping and coating the polyamide acid glue solution on a glass plate into a thin layer with the thickness of 1-3 mm, then placing the glass plate in a vacuum oven, vacuumizing, and heating, wherein the heating process is as follows: and heating to 100 ℃, keeping the temperature for 0.5-1 h, heating from 100 ℃ to 200 ℃, keeping the temperature for 0.5-1 h, heating from 200 ℃ to 300 ℃, keeping the temperature for 0.5-1 h, heating from 300 ℃ to 420 ℃, keeping the temperature for 1.0-2.0 h, and cooling to obtain the high-planarity polyimide film containing xanthone 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 in vacuum at 70-200 ℃, and cooling to obtain the polyimide film.
The polyimide obtained by the method and used for the FOLED substrate is also applied to the fields of microelectronics, war industry, aerospace, packaging, protection and the like.
Compared with the prior art, the beneficial effects are:
according to the invention, through molecular structure design, a xanthone structure and an imide polar group are creatively introduced into a diamine monomer at the same time, so that the xanthone-containing diamine monomer with high planarity is prepared, and the xanthone-containing diamine monomer has high electron density and a good rigid structure. After the diamine monomer and the dianhydride monomer are polymerized, a plane rigid structure and a polar group are introduced into a polyimide main chain, the plane rigid structure is favorable for 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, so that the polyimide resin has excellent barrier property, higher glass transition temperature and thermal stability and lower thermal expansion coefficient. The polyimide prepared by the invention greatly improves the barrier capability from the intrinsic structure, obviously improves the barrier property compared with the commercial polyimide modified by inorganic nano-materials, and has the oxygen transmission rate lower than 0.01cc/m2(d) water vapor transmission rate of less than 0.01g/m2(d) a glass transition temperature of up to 400 ℃ and a low coefficient of thermal expansion。
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
The present embodiment provides
Synthesis of N3, N6-bis (4-aminophenyl) -9-oxo-9H-xanthene-3, 6-dicarboxamide:
Figure RE-GDA0002478418880000081
s1, synthesizing an intermediate 9-oxo-9H-xanthene-3, 6-dicarbonitrile:
3.54g (0.01mol) of 3,6-dibromo-9H-xanthen-9-one, 4.478g (0.05mol) of cuprous cyanide and 50ml of dried NMP were put in a 500ml three-necked flask, refluxed at 140 ℃ for 24 hours, and then H was added2O (180 mL), HCl (60mL) and FeCl3(4.19g,25.8mmol) were poured into the reaction and stirred for 1h, cooled to room temperature, filtered to give a brown precipitate, washed with water, the resulting solid redissolved in dichloromethane and washed with water, and the solvent was removed under reduced pressure to give the crude product as a brown solid, which was triturated with methanol to give the intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000082
s2, synthesizing an intermediate 9-oxo-9H-xanthene-3,6-dicarboxylic acid:
2.46g (0.01mol) of 9-oxo-9H-xanthene-3,6-dicarbonitrile, 20g of potassium hydroxide and 10ml of water are added into a 50ml three-necked flask, stirred magnetically and introduced with argon, heated slowly until the reaction is finished to form brown potassium dicarboxylate, and diluted with distilled water; then acidifying with concentrated hydrochloric acid, separating out solid, washing with water, dissolving the crude product in hot ethanol for recrystallization to obtain an intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000083
s3, synthesizing an intermediate 9-oxo-9H-xanthene-3,6-dicarbonyl dichloride:
14.21g (0.05mol) of 9-oxo-9H-xanthene-3,6-dicarboxylic acid is added into a 250ml three-neck flask, 100ml of dehydrated dichloromethane is added, 17.846g (0.150 mol) of thionyl chloride is slowly dropped under the ice-bath condition, 3 to 4 drops of N, N-dimethylformamide are dropped as a catalyst, the mixture is magnetically stirred and argon is introduced, and the temperature is increased to 75 ℃ for reaction and reflux for 12 hours. The solvent and excess thionyl chloride were evaporated under reduced pressure to give a pale yellow solid intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000091
s4, synthesizing an intermediate N3, N6-bis (4-nitrophenyl) -9-oxo-9H-xanthene-3, 6-dicarboxamide:
13.812g (0.1mol) of 4-nitroaniline is dissolved in 150ml of a solution of N-methylpyrrolidone and pyridine at a ratio of 4:1, 6.42g (0.02mol) of 9-oxo-9H-xanthene-3,6-dicarbonyl dichloride is slowly added, the mixture is stirred for 2 hours at room temperature under an argon environment, then the temperature is increased to 100 ℃ for reaction for 12 hours, the reaction solution is poured into methanol after cooling, precipitates are filtered out, the precipitates are fully washed with the methanol, the precipitates are recrystallized in N, N-dimethylformamide and water, and the crystals are dried for 24 hours in a vacuum drying oven at a temperature of 80 ℃ to obtain an intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000092
(5) synthesis of N3, N6-bis (4-aminophenyl) -9-oxo-9H-xanthene-3, 6-dicarboxamide:
adding 5.24g (0.01mol) of N3, N6-bis (4-nitrophenyl) -9-oxo-9H-xanthene-3,6-dicarboxamide 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 2
The present embodiment provides
Synthesis of N2, N6-bis (5-aminophosphen-2-yl) -9-oxo-9H-xanthene-2, 6-dicarboxamide:
Figure RE-GDA0002478418880000101
s1, synthesizing an intermediate 9-oxo-9H-xanthene-2, 6-dicarbonitrile:
3.54g (0.01mol) of 2,6-dibromo-9H-xanthen-9-one, 4.478g (0.05mol) of cuprous cyanide and 50ml of dried NMP were put in a 500ml three-necked flask, refluxed at 140 ℃ for 24 hours, and then H was added2O (180 mL), HCl (60mL) and FeCl3(4.19g,25.8mmol) were poured into the reaction and stirred for 1h, cooled to room temperature, filtered to give a brown precipitate, washed with water, the resulting solid redissolved in dichloromethane and washed with water, and the solvent was removed under reduced pressure to give the crude product as a brown solid, which was triturated with methanol to give the intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000102
s2, synthesizing an intermediate 9-oxo-9H-xanthene-2,6-dicarboxylic acid:
2.46g (0.01mol) of 9-oxo-9H-xanthene-2,6-dicarbonitrile, 20g of potassium hydroxide and 10ml of water are added into a 50ml three-necked flask, stirred magnetically and introduced with argon, heated slowly until the reaction is finished to form brown potassium dicarboxylate, and diluted with distilled water; then acidifying with concentrated hydrochloric acid, separating out solid, washing with water, dissolving the crude product in hot ethanol for recrystallization to obtain an intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000103
s3, synthesizing an intermediate 9-oxo-9H-xanthene-2,6-dicarbonyl dichloride:
14.21g (0.05mol) of 9-oxo-9H-xanthene-2,6-dicarboxylic acid is added into a 250ml three-neck flask, 100ml of dehydrated dichloromethane is added, 17.846g (0.150 mol) of thionyl chloride is slowly dropped under the ice-bath condition, 3 to 4 drops of N, N-dimethylformamide are dropped as a catalyst, the mixture is magnetically stirred and argon is introduced, and the temperature is increased to 75 ℃ for reaction and reflux for 12 hours. The solvent and excess thionyl chloride were evaporated under reduced pressure to give a pale yellow solid intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000111
s4, synthesizing an intermediate N2, N6-bis (5-nitrothiophen-2-yl) -9-oxo-9H-xanthene-2, 6-dicarboxamide:
14.415g (0.1mol) of 5-nitrothiophen-2-amine was dissolved in 150ml of a 4:1 solution of N-methylpyrrolidone and pyridine, 6.42g (0.02mol) of 9-oxo-9H-xanthone-2, 6-dicarbonyldichloride was slowly added thereto, and the mixture was stirred at room temperature under an argon atmosphere for 2 hours, then heated to 100 ℃ to react for 12 hours, cooled, poured into methanol, filtered to precipitate, sufficiently washed with methanol, recrystallized from N, N-dimethylformamide and water, and dried in a vacuum oven at 80 ℃ for 24 hours to obtain an intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000112
s5. synthesis
N2,N6-bis(5-aminothiophen-2-yl)-9-oxo-9H-xanthene-2,6-dicarboxamide：
Adding 5.36g (0.01mol) of N2, N6-bis (5-nitrothiophen-2-yl) -9-oxo-9H-xanthene-2,6-dicarboxamide into a 500ml three-neck flask, adding 450ml of absolute ethyl alcohol, magnetically stirring, 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 3
This example provides Synthesis
N2,N7-bis(7-aminodibenzo[b,d]furan-3-yl)-9-oxo-9H-xanthene-2,7-dicarboxami-de：
Figure RE-GDA0002478418880000121
S1, synthesizing an intermediate 9-oxo-9H-xanthene-2, 7-dicarbonitrile:
3.54g (0.01mol) of 2,7-dibromo-9H-xanthen-9-one, 4.478g (0.05mol) of cuprous cyanide and 50ml of dried NMP were put in a 500ml three-necked flask, refluxed at 140 ℃ for 24 hours, and then H was added2O (180 mL), HCl (60mL) and FeCl3(4.19g,25.8mmol) were poured into the reaction and stirred for 1h, cooled to room temperature, filtered to give a brown precipitate, washed with water, the resulting solid redissolved in dichloromethane and washed with water, and the solvent was removed under reduced pressure to give the crude product as a brown solid, which was triturated with methanol to give the intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000122
s2, synthesizing an intermediate 9-oxo-9H-xanthene-2,7-dicarboxylic acid:
2.46g (0.01mol) of 9-oxo-9H-xanthene-2,7-dicarbonitrile, 20g of potassium hydroxide and 10ml of water are added into a 50ml three-necked flask, stirred magnetically and introduced with argon, heated slowly until the reaction is finished to form brown potassium dicarboxylate, and diluted with distilled water; then acidifying with concentrated hydrochloric acid, separating out solid, washing with water, dissolving the crude product in hot ethanol for recrystallization to obtain an intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000123
s3, synthesizing an intermediate 9-oxo-9H-xanthene-2,7-dicarbonyl dichloride:
14.21g (0.05mol) of 9-oxo-9H-xanthene-2,7-dicarboxylic acid is added into a 250ml three-neck flask, 100ml of dehydrated dichloromethane is added, 17.846g (0.150 mol) of thionyl chloride is slowly dropped under the ice-bath condition, 3 to 4 drops of N, N-dimethylformamide are dropped as a catalyst, the mixture is magnetically stirred and argon is introduced, and the temperature is increased to 75 ℃ for reaction and reflux for 12 hours. The solvent and excess thionyl chloride were evaporated under reduced pressure to give a pale yellow solid intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000131
s4, synthesizing an intermediate N2, N7-bis (7-nitrodibenzo [ b, d ] furan-3-yl) -9-oxo-9H-xanthene-2, 7-dicarboxamide:
22.82g (0.1mol) of 7-nitrodibenzozo [ b, d ] furan-3-amine was dissolved in 150ml of a 4:1 solution of N-methylpyrrolidone and pyridine, 6.42g (0.02mol) of 9-oxo-9H-xanthene-2,7-dicarbonyl dichloride was slowly added, the mixture was stirred at room temperature for 2 hours under an argon atmosphere, then the temperature was raised to 100 ℃ to react for 12 hours, the reaction solution was poured into methanol after cooling, the precipitate was filtered off, sufficiently washed with methanol, recrystallized from N, N-dimethylformamide and water, and dried in a vacuum oven at 80 ℃ for 24 hours to obtain an intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000132
s5. synthesis
N2,N7-bis(7-aminodibenzo[b,d]furan-3-yl)-9-oxo-9H-xanthene-2,7-dicarboxami-de：
7.05g (0.01mol) of N2, N7-bis (7-nitrodibenzozo [ b, d ] furan-3-yl) -9-oxo-9H-xanthene-2,7-dicarboxamide was put into a 500ml three-necked flask, 450ml of absolute ethanol was added, magnetic stirring and argon gas introduction were carried out, after oil bath heating to 70 ℃, 0.1g of 10% wt palladium carbon was added, and 10ml of hydrazine hydrate was gradually added dropwise, after 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 suction filtration, an off-white solid was collected, and dried in a vacuum drying oven at 80 ℃ for 24 hours to obtain the product.
Example 4
The present embodiment provides
Synthesis of N2, N6-bis (4- ((4-aminophenyl) amino) phenyl) -9-oxo-9H-xanthone-2, 6-dicarb-oxamide:
Figure RE-GDA0002478418880000141
s1, synthesizing an intermediate N2, N6-bis (4- ((4-nitrophenyl) amino) phenyl) -9-oxo-9H-xanthene-2, 6-dicarboxamide:
22.92g (0.1mol) of N1- (4-nitrophenyl) bezene-1, 4-diamine is dissolved in 150ml of a 4:1 solution of N-methylpyrrolidone and pyridine, 6.42g (0.02mol) of 9-oxo-9H-xanthene-2,6-dicarbonyl dichloride is slowly added, the mixture is stirred at room temperature for 2 hours under an argon atmosphere, then the temperature is raised to 100 ℃ for reaction for 12 hours, the reaction solution is poured into methanol after cooling, the precipitate is filtered off, the precipitate is sufficiently washed with methanol, the precipitate is recrystallized from N, N-dimethylformamide and water, and the precipitate is dried in a vacuum drying oven at 80 ℃ for 24 hours to obtain an intermediate. The intermediate has the following structure:
Figure RE-GDA0002478418880000142
s2. synthesis
N2,N6-bis(4-((4-aminophenyl)amino)phenyl)-9-oxo-9H-xanthene-2,6-dicarboxa-mid e：
Adding 7.07g (0.01mol) of N2, N7-bis (4- ((4-nitrophenyl) amino) phenyl) -10H-phenoxazine-2,7-dicarboxamide 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 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 to crystallize, collecting off-white solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24H to obtain the product.
Example 5
This example provides the preparation of a polyimide by a thermal imidization process, comprising the steps of:
dissolving diamine containing xanthone structures and dianhydride containing X structures in a strong 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, 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 ℃, keeping the temperature constant for 0.5-1 h, heating from 100 ℃ to 200 ℃, keeping the temperature constant for 0.5-1 h, heating from 200 ℃ to 300 ℃, keeping the temperature constant for 0.5-1 h, heating from 300 ℃ to 420 ℃, keeping the temperature constant for 1.0-2.0 h, and cooling to obtain the high-planarity polyimide film containing the xanthone structure.
The polyimide prepared by the method of example 7 was prepared by reacting the high-plane diamines of xanthone structure prepared in examples 1 to 4 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 according to examples 1 to 4 were classified into polyimide nos. 1 to 24, and the barrier property, glass transition temperature, thermal stability and thermal expansion coefficient and antibacterial property of the polyimide were measured, and p-phenylenediamine and polyimide synthesized with pyromellitic dianhydride were selected as a blank control group having antibacterial property of 6mrn, and the results of the measurements 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 RE-GDA0002478418880000151
Figure RE-GDA0002478418880000161
As shown in Table 1, the present invention introduces xanthone structure and polar group into diamine monomer simultaneously to prepare 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. A polyimide for an FOLED substrate is characterized in that the structural general formula of the polyimide is as follows:
Figure FDA0002318592720000011
Ar1any one selected from the following structural formulas:
Figure FDA0002318592720000012
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 for the FOLED substrate according to claim 1, wherein Ar is selected from the group consisting of2And Ar3Any one selected from the following structural formulasOne of them is:
Figure FDA0002318592720000021
x is selected from any one of the following structures:
Figure FDA0002318592720000022
3. the method for preparing the polyimide for the FOLED substrate according to claim 1 or 2, wherein the preparation step comprises:
s1. reacting a xanthone monomer containing two halogen atom substitutions
Figure RE-FDA0002478418870000031
Figure RE-FDA0002478418870000032
Adding cyanide into a solvent 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 S1 into a solvent, adding alkali, and performing hydrolysis reaction under the atmosphere of protective gas to obtain a dicarboxylic acid monomer 4, a monomer 5 or a monomer 6;
s3, dissolving the monomer 4, the monomer 5 or the monomer 6 in the step S2 into a solvent, adding N, N-dimethylformamide as a catalyst, slowly dropwise adding thionyl chloride under an ice bath condition, and performing acyl chlorination reaction to obtain a diacid chloride monomer 7, a monomer 8 or a monomer 9;
s4, adding the monomer 7, the monomer 8 or the monomer 9 in the step S3 and Ar1 containing an amino group and a nitro group for substitution into a solvent, and performing amidation reaction under a protective gas atmosphere to obtain a dinitromonomer 10, a monomer 11 or a monomer 12;
s5, adding the monomer 10, the monomer 11 or the monomer 12 in the step S4 into a solvent, introducing protective gas, adding a reducing agent, and carrying out reduction reaction to obtain a xanthone-containing diamine monomer shown in the structural general formulas I-III;
s6, 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, the monomer 4, the monomer 5 and the monomer 6 in the step S2, the monomer 7, the monomer 8 and the monomer 9 in the step S3, and the monomer 10, the monomer 11 and the monomer 12 in the step S4 respectively have the following structural characteristics:
Figure RE-FDA0002478418870000041
4. the method of claim 3, wherein the ratio of the amounts of the two halogen atom-substituted xanthone monomers in S1 to the amount of cyano group-containing substance in cyanide is 1:2 to 8; the mass ratio of the monomer 1, the monomer 2 or the monomer 3 to the added alkali in S2 is 1: 10-50; the molar ratio of the monomer 4, the monomer 5 or the monomer 6 to the thionyl chloride in S3 is 1: 2-4; the monomer 7, the monomer 8 or the monomer 9 in S4 and Ar substituted by one amino group and one nitro group1The mass ratio of the monomers is 1: 2-1: 4; the mass ratio of the monomer 10, the monomer 11 or the monomer 12 to the reducing agent in S5 is 1: 2-1: 32.
5. The method for preparing polyimide usable for an FOLED substrate according to claim 3, wherein the molar ratio of the diamine monomer containing a xanthone structure to the dianhydride containing an X structure in S6 is 1: 0.9-1.1.
6. The method as claimed in claim 3, wherein the protective gas from S1 to S5 is one or more selected from nitrogen, helium, neon, argon, krypton, xenon, and radon.
7. According toThe method for preparing polyimide for FOLED substrate as claimed in claim 3, wherein the cyanide compound S1 is NaCN, KCN, Zn (CN)2And one or more of CuCN; the reducing agent is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder and zinc powder; s2, the alkali 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.
8. The method for preparing polyimide applicable to the FOLED substrate according to claim 3, wherein 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 water; the solvent of step S3 is dichloromethane; the solvent in S4 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene and xylene; the solvent in S5 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 preparation method of the polyimide applicable to the FOLED substrate according to claim 3, wherein the reaction temperature is 50-170 ℃, and the reaction time is 10-48 h; the drying temperature is 40-120 ℃, and the drying time is 6-30 h.
10. The method for preparing polyimide for the FOLED substrate according to claim 3, wherein the stirring reaction in S4 is carried out at-15 to 30 ℃ for 2 to 48 hours.
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