CN106674027A - Diamine compound, polyimide, optical film and preparation method thereof - Google Patents
Diamine compound, polyimide, optical film and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
- C07C217/86—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom to an acyclic carbon atom of a hydrocarbon radical containing six-membered aromatic rings
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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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- G—PHYSICS
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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Abstract
The invention provides an optical film which is excellent in solubleness and higher in optical transmittance. A specific diamine compound and tetracarboxylic dianhydride are used to prepare a polyamide acid; the polyamide acid is subjected to dehydration and loop closing to obtain polyimide, and the polyimide is further prepared into the transparent polyimide film. The film can be applied to an optoelectronic device, a solar cell device, a flexible display device, an electronic book, an electronic label, or a photoelectric sensor.
Description
Technical Field
The invention belongs to the field of optical materials. The present invention relates to a novel diamine compound, polyamic acid and polyimide, an optical film, and a photoelectric device. More particularly, it relates to a novel diamine compound, polyamic acid and polyimide prepared therefrom, an optical film comprising the same, a photovoltaic device further comprising the optical film, and a method of preparing the same.
Background
Polyimide is a high molecular material with a molecular structure containing an imide five-membered ring, and is mainly prepared from an aromatic dianhydride compound and a diamine compound by a polycondensation method. The compound has the characteristics of excellent thermal stability, mechanical strength, dielectric property, insulating property, outstanding toughness, flexibility and the like, and is gradually applied to a plurality of fields, particularly to the flexible display industry which develops rapidly in recent years.
With the development of aerospace, solar, microelectronic and other industries, further requirements on the heat resistance, dielectric property and transparency of polyimide materials are continuously provided. Due to the high aromatic conjugation of the main chain of the traditional polyimide molecule and the charge complexing transfer effect in the molecular chain, the polyimide film is usually colored, has poor light transmittance and is almost opaque in a visible light region.
In order to improve the use characteristics of polyimide films in these fields, researchers have conducted a series of research works, and some research works have achieved some effects. For example, chinese patent application CN101674923A (mitsubishi gas chemical corporation) discloses a method and an apparatus for preparing a colorless transparent polyimide film, which is prepared by a polymerization process of an alicyclic dianhydride compound 1,2,4, 5-cyclohexanetetracarboxylic dianhydride and a diamine compound, and directly preparing a colorless transparent polyimide film using the solution, and the light transmittance of the prepared film having a thickness of 200 μm is 89.8%. Chinese patent application CN102634022A discloses a colorless and highly transparent polyimide film, a preparation method and application thereof, wherein the polyimide film with good transparency is obtained by polymerizing fatty dianhydride and different diamines.
The polyimide prepared conventionally has poor transparency because of large conjugation degree, which causes charge transfer to form a Charge Transfer Complex (CTC) in and between polyimide molecules. The current approaches to improve the transparency of polyimides are mainly: adopting fluorine-containing monomer; introducing bulky group or side group and strong electron-withdrawing group; a ring structure, an aliphatic structure, and the like are introduced into the diamine monomer.
However, the requirements for heat resistance, solubility and transparency are still unsatisfactory.
Disclosure of Invention
In light of the above background, the technical problem to be solved by the present invention is how to better improve the heat resistance, solubility and transparency of a polyimide film.
The inventors found that a polyimide film prepared by synthesizing a diamine having a fluorine-containing bridge and a fluorobenzene-containing diamine with a dianhydride has relatively excellent properties in heat resistance, solubility, transparency, and the like.
In view of the foregoing, it is an object of the present invention to overcome the disadvantages of the prior art and to provide a novel diamine compound for synthesizing a polyimide monomer, which introduces a fluorine-containing benzene and a fluorine-containing bridge. This can increase the solubility of the polyimide and improve the permeability of the polyimide film.
It is another object of the present invention to provide a process for preparing the novel diamine compound of the present invention. The method has the advantages of simple synthesis, easy operation, low equipment cost and no pollution.
It is still another object of the present invention to provide polyamic acids and polyimides using the novel diamine compounds of the present invention.
It is a fourth object of the present invention to provide an optical film which is formed from the polyimide of the present invention and has relatively excellent properties in terms of heat resistance, solubility, transparency, and the like.
It is a fifth object of the present invention to provide a photovoltaic device formed of the optical film of the present invention. The method has important application value in the fields of photoelectron, solar cell substrate, flexible liquid crystal display and the like.
In order to achieve the above object, in one aspect, the present invention adopts the following technical solutions:
a diamine compound represented by the following general formula (I),
wherein,
R1、R2and each R is independently selected from the group consisting of halogen, amino, hydroxyl, nitro, cyano, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, aminoalkyl of 1 to 12 carbon atoms, alkylamino of 1 to 12 carbon atoms, alkanoyl of 2 to 12 carbon atoms, alkylamido of 2 to 12 carbon atoms, alkoxyacyl of 1 to 12 carbon atoms, thioalkyl of 1 to 12 carbon atoms, alkylthio of 1 to 12 carbon atoms, haloalkyl of 1 to 12 carbon atoms, haloalkoxy of 1 to 12 carbon atoms, aryl or heteroaryl;
each X is independently selected from CF2O、OCF2、CHFO、OCHF、CF2And CHF;
n and m are each independently an integer of 0 to 4;
with the proviso that at least one R is selected from halogen, haloalkyl of 1 to 12 carbon atoms, or haloalkoxy of 1 to 12 carbon atoms.
As a representation of R1、R2And halogen of R selected from fluorine, chlorine, bromine and iodine.
As a representation of R1、R2And haloalkoxy (oxy) of R represents one or more CH in alkyl2An alkyl (oxy) group in which the H atom is substituted with a halogen. Preferably, the haloalkane (oxy) group is C1-C10Alkyl (oxy) halide, C1-C8Alkyl (oxy) halide, C1-C6Alkyl (oxy) halide, or C1-C4Alkyl (oxy) halide group. Non-limiting examples of the haloalkanyl (oxy) group include a methyl (oxy) halide group, an ethyl (oxy) halide group, a propane (oxy) halide group, an isopropanyl (oxy) halide group, a butane (oxy) halide group, an isobutane (oxy) halide group, a sec-butane (oxy) halide group, a tert-butane (oxy) halide group, a pentane (oxy) halide group, and a hexane (oxy) halide group. Further, for example, non-limiting examples of the haloalkyl group include a chloromethyloxy group, a 1-bromoethoxy (oxy) group, a fluoromethoxy (oxy) group, a difluoromethoxy (oxy) group, a trifluoromethyl (oxy) group, a 1,1, 1-trifluoroethyl (oxy) group, and the like.
In most cases, the substituents of the present invention contain 1 to 12 carbon atoms. In the case of alkyl, it may be straight or branched chain and may be substituted as indicated herein. When the term "alkyl of 1 to 12 carbon atoms" is used, it is equivalent to C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11Or C12. Other substituents are defined similarly and are not described in detail. Preferably of 1 to 12 carbon atomsAlkyl is C1-C10Alkyl radical, C1-C8Alkyl radical, C1-C6Alkyl, or C1-C4An alkyl group. Further, for example, C1-C6Alkyl includes all straight chain, branched alkyl groups having 1 to 6 carbon atoms, thereby including methyl, ethyl, n-propyl, isopropyl, butyl and isomers thereof (e.g., n-butyl, isobutyl and tert-butyl), pentyl and isomers thereof, hexyl and isomers thereof.
Diamine compound according to the invention, wherein X is each independently selected from CF2O、OCF2、CHFO、OCHF、CF2And CHF. Preferably, each X is independently selected from CF based on synthetic convenience2O、OCF2CHFO and OCHF; and, most preferably, each X is independently selected from CF2O and OCF2。
The diamine compound according to the present invention, wherein each R is independently selected from halogen, amino, hydroxyl, nitro, cyano, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, aminoalkyl of 1 to 12 carbon atoms, alkylamino of 1 to 12 carbon atoms, alkanoyl of 2 to 12 carbon atoms, alkylamido of 2 to 12 carbon atoms, alkoxyacyl of 1 to 12 carbon atoms, thioalkyl of 1 to 12 carbon atoms, alkylthio of 1 to 12 carbon atoms, haloalkyl of 1 to 12 carbon atoms, haloalkoxy of 1 to 12 carbon atoms, aryl or heteroaryl; and, at least one R is selected from halogen, haloalkyl of 1 to 12 carbon atoms, or haloalkoxy of 1 to 12 carbon atoms. Preferably, at least 2R are selected from halogen, haloalkyl of 1 to 12 carbon atoms, or haloalkoxy of 1 to 12 carbon atoms; more preferably, at least 3R are selected from halogen, haloalkyl of 1 to 12 carbon atoms, or haloalkoxy of 1 to 12 carbon atoms; and, most preferably, all R halogens, haloalkyl groups of 1 to 12 carbon atoms, or haloalkoxy groups of 1 to 12 carbon atoms. In a specific embodiment, each R is independently selected from fluorine, fluoroalkyl of 1 to 12 carbon atoms, or fluoroalkoxy of 1 to 12 carbon atoms.
The diamine compound according to the present invention, wherein n and m are each 0.
The diamine compound according to the present invention, wherein the compound is selected from the group consisting of compounds of the following formula (II)
On the other hand, the invention adopts the following technical scheme:
a method for producing a diamine compound according to the present invention, comprising the steps of:
reacting a tetra-substituted benzene of formula (III)
With a substituted or unsubstituted nitrobenzene compound and other necessary reagents to produce a dinitro compound of formula (IV);
the diamine compound of the present invention is produced by reducing the dinitro compound of the formula (IV).
In the synthesis reaction of the diamine compound, a solvent may be used as necessary. The solvent is not particularly limited as long as it can dissolve the specific diamine compound and does not interfere with the reaction. Examples thereof include aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and dimethyl sulfoxide, dimethylformamide, dimethylacetamide and the like.
In the preparation method, the ratio of the tetra-substituted benzene of the formula (III) to the substituted or unsubstituted nitrobenzene compound is preferably 2 to 20 moles of the substituted or unsubstituted nitrobenzene compound to 1 mole of the tetra-substituted benzene of the formula (III).
When the dinitro compound of the formula (IV) is reduced, it can be carried out with a reducing agent such as hydrogen, hydrazine, hydrochloric acid or the like in the presence of a known catalyst. Examples of the catalyst include a metal catalyst mainly composed of a group VIII metal, i.e., a metal such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, indium, or platinum, and specifically, a catalyst in which a metal is supported on a carrier, and a complex catalyst of the above metals. The reduction reaction may be a homogeneous system or a heterogeneous system.
The amount of the catalyst may be used in an appropriate ratio. For example, when the catalyst mainly contains the above-mentioned group VIII metal as an active component, the amount of the catalyst is preferably 0.0001 to 100 parts by weight, particularly preferably 0.001 to 20 parts by weight, based on 100 parts by weight of the dinitro compound. In addition, as the reduction reaction, a method using zinc, tin (II) carbide, sodium sulfide, sodium hydrogen sulfide, sodium hydrosulfite, or ammonium sulfide as a reducing agent can be used. The reducing agent is preferably used in an amount of 0.001 to 10 moles per 1 mole of the nitro group of the dinitro compound.
The solvent used in the reduction reaction is preferably a solvent which can dissolve the dinitro compound and the diamine compound at the same time and does not change the quality by the reduction reaction, and examples thereof include alcohols such as methanol, ethanol, propanol, and butanol; ethers such as diethyl ether, 1, 2-dimethoxyethane, tetrahydrofuran, dioxane and anisole.
In a specific embodiment, when the diamine compound of formula (II) is prepared, the preparation method is as follows:
(1)1,2,4, 5-tetrafluorobenzene is used as a solvent at low temperature, and reacts with butyl lithium to synthesize a phenyllithium reagent;
(2) adding 2-3 equivalents of difluorodibromomethane into the reaction solution at low temperature, quenching the reaction with dilute hydrochloric acid after the reaction is finished, and treating to obtain an oily concentrate;
(3) adding p-nitrophenol into the oily substance obtained in the above steps in the presence of an aprotic solvent and an inorganic base, reacting at room temperature, and performing series treatment to obtain a yellow solid;
(4) the solid is dissolved in toluene, ethanol or tetrahydrofuran, and is reduced into diamine compound under the action of Pd/C and hydrogen.
The chemical reaction formula is as follows:
in another aspect, the invention adopts the following technical scheme:
a polyamic acid is obtained by the polycondensation reaction of the diamine compound and tetracarboxylic dianhydride.
In another aspect, the invention adopts the following technical scheme:
a polyimide, get polyamic acid through condensation polymerization reaction of diamine compound and tetracarboxylic acid dianhydride of the invention at first; then dehydrating and ring-closing polyamic acid to obtain the polyamic acid.
The tetracarboxylic acid dianhydride used in the present invention may be an alicyclic tetracarboxylic acid dianhydride. Mention may be made, for example, of butanetetracarboxylic dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 3-dichloro-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 1,2,4, 5-norbornane tetracarboxylic dianhydride, 3 ', 4,4 ' -dicyclohexyltetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4 ' -dicarboxyhydric dianhydride, 3,5, 6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4, 5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalen [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-5-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalen [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-5-ethyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-7-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-7-ethyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-8-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-8-ethyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-5, 8-dimethyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 5- (2, 5-dioxotetrahydrofurylidene) -3-methyl-3-cyclohexene-1, 2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2, 4-dione-6-spiro-3 ' - (tetrahydrofuran-2 ', 5 ' -dione).
The tetracarboxylic acid dianhydride used in the present invention may be an aromatic tetracarboxylic acid dianhydride. Pyromellitic dianhydride, 3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride, 3 ', 4,4 ' -diphenylsulfonetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 3 ', 4,4 ' -diphenylethertetracarboxylic dianhydride, 3 ', 4,4 ' -dimethyldiphenylsilanetetracarboxylic dianhydride, 3 ', 4,4 ' -tetraphenylsilanetetracarboxylic dianhydride, 1,2,3, 4-furantetracarboxylic dianhydride, 4,4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl propane dianhydride, 3,3 ', 4,4 ' -perfluoroisopropylidene diphthalic dianhydride, 3 ', 4,4 ' -biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4 ' -diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4 ' -diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1, 4-butanediol-bis (anhydrotrimellitate), 1, 6-hexanediol-bis (anhydrotrimellitate), 1, 8-octanediol-bis (anhydrotrimellitate), 2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate).
They may be used 1 kind alone or 2 or more kinds in combination.
The polyimide according to the present invention, wherein the polyimide preferably has the following structure of formula (V):
wherein R is a tetravalent organic group; the degree of polymerization n is in the range of 5 to 500.
The polyimide according to the present invention, wherein, preferably, the tetracarboxylic dianhydride is selected from at least one of the following compounds:
the polyamic acid of the present invention is obtained by reacting a diamine compound with tetracarboxylic acid dianhydride. The ratio of the tetracarboxylic acid dianhydride to the diamine compound is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents, of the acid anhydride group of the tetracarboxylic acid dianhydride to 1 equivalent of the amino group contained in the diamine compound.
The synthesis reaction of the polyamic acid is carried out in an organic solvent at a temperature of 100 to 250 ℃, preferably 150 to 220 ℃, and more preferably 180 to 200 ℃.
The organic solvent is not particularly limited as long as it can dissolve or disperse the synthesized polyamic acid. Examples thereof include aprotic polar solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, tetramethylurea, hexamethylphosphorous triamide and the like; phenol solvents such as m-methylphenol, xylenol, phenol, and halogenated phenol.
In addition, the organic solvent may be used in combination with a polyamic acid poor solvent such as alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons, as long as the formed polyamic acid is not precipitated. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, methylene chloride, 1, 2-dichloroethane, 1, 4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol methyl lactate, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, 1, 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and the like.
As described above, a reaction solution in which the polyamic acid was dissolved was obtained. Then, the reaction solution was dispersed in a large amount of a poor solvent to obtain precipitates. Then, the precipitate was filtered, washed, and dried to obtain polyamic acid.
And then dissolving the polyamide acid in an organic solvent, coating a film on a clean substrate, gradually drying, and finally drying and cooling to obtain the polyimide film.
In one embodiment, the preparation method is as follows:
(1) adding equivalent amount of diamine and dianhydride into m-cresol solvent under the protection of nitrogen or argon, heating to 180-200 ℃, heating for 8-15 hours, cooling to room temperature, dispersing with methanol solvent, filtering, washing, and drying to obtain polyamide acid (prepolymer);
(2) dissolving polyamic acid in an organic solvent, coating on a clean substrate, gradually drying, finally drying at 200-300 ℃ for 120 minutes, and cooling to obtain the polyimide film.
The chemical reaction formula is as follows:
wherein R is a tetravalent organic group; the degree of polymerization n is in the range of 5 to 500.
In another aspect, the invention adopts the following technical scheme:
an optical film is prepared from the polyamic acid and/or polyimide of the invention.
Still further alternatively, an optical film comprising the polyamic acid and/or the polyimide according to the present invention.
In the last aspect, the invention adopts the following technical scheme:
an opto-electronic device comprising the optical film of the present invention.
An optoelectronic device according to the present invention, wherein the optoelectronic device is selected from an optoelectronic device, a solar cell device, a flexible display device (e.g. OLED and LCD), an electronic book, an electronic label or a photosensor.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a simple and convenient fluorine-containing polyimide synthesis method which can realize industrialization; the synthesis is simple, and the structure containing the tetrafluorophenyl bis-difluoromethoxy bridge bond is adopted;
(2) the polyimide has a molecular structure containing fluorine phenyl and a fluorine bridge, so that the solubility of the polyimide is increased, the formation of intramolecular and intermolecular CTC is inhibited, the flexibility and transparency of the material are increased, the thermal property is excellent, and the polyimide has a good application prospect in the field of flexible transparent display such as OLED.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications can be made by those skilled in the art after reading the contents of the present invention, and those equivalents also fall within the scope of the invention defined by the appended claims.
The following examples will aid understanding of the present invention, but are not intended to limit the scope of the present invention.
Example 1: preparation of diamine (chemical formula 1):
1. adding 30g (0.2mol) of 1,2,4, 5-tetrafluorobenzene and 600ml of tetrahydrofuran into a 1L three-necked bottle, installing and stirring, cooling the mixture to-75 ℃ in a cold bath way, dropwise adding and protecting a nitrogen device, starting stirring, reducing the temperature to-75 ℃ in the nitrogen protection way, dropwise adding 220ml of butyl lithium solution (0.44mol, 2mol/L), keeping the temperature below-70 ℃ for stirring for 30 minutes after the dropwise adding is finished, then continuously dropwise adding difluorodibromomethane solution (0.52mol, containing 110g of difluorodibromomethane), keeping the temperature below-60 ℃, keeping the temperature to be below-60 ℃, continuously stirring for 30 minutes after the dropwise adding is finished, then hydrolyzing with 10% diluted hydrochloric acid, and further carrying out post-treatment to obtain 70g of a red brown oily substance, wherein the yield is 86%, and the next-step reaction is directly carried out without;
2. 50g of brown oily matter prepared in the previous step, 500ml of dimethylformamide, 1g of potassium iodide and 30g of p-nitrophenol are added into a 1L three-necked bottle, the mixture is heated to 90 ℃, after the reaction is carried out for 2 hours, the heating is stopped, ice water is added into the reaction system after the cooling, the product is separated out, the filtration and the washing are carried out, and the crystallization is carried out by using ethanol, so that 31g of yellow solid is obtained, the yield is 60 percent, and the purity is 97 percent.
3. 30g of the dinitro compound prepared in the previous step, 200ml of toluene, 100ml of ethanol and 1g of 5% Pd/C are added into a 1L autoclave, hydrogenation is carried out for 5 hours at normal temperature and normal pressure, the next step of treatment, filtration and concentration are carried out after the reaction is qualified through gas chromatography monitoring, 100ml of isopropanol is used for crystallization to obtain pink solid powder, 24g of pink solid powder is obtained after drying, the purity of the gas chromatography is 99%, the yield is 90%, and MS confirms that the structure (molecular weight M +464) is correct.
Example 2: preparing a transparent polyimide film:
the structural formula is as follows:
1. preparation of polyamic acid (structural formula:
the operation is as follows: in a 1L three-necked flask, 20g of diamine, 8.5g of cyclobutanetetracarboxylic dianhydride and 500g of m-cresol are added, the mixture is heated to 150 ℃ and reacted for 8 hours, then the reaction solution is cooled to about 60 ℃, the reaction solution is dispersed into methanol under stirring, and the methanol is sucked and filtered after cooling and is washed by the methanol. Drying gave 25g of a filamentous solid.
2. Preparing a polyimide film:
dissolving the filamentous solid in 5% N-methylpyrrolidone to obtain 5% solution, and filtering with 0.45 μm filter membrane to remove mechanical impurities. Then coating the polymer solution on a clean glass substrate, drying for 1 hour at 50 ℃,1 hour at 100 ℃, finally drying for 2 hours at 200 ℃, cooling to room temperature, and demoulding to obtain the transparent polyimide film with the thickness of about 20 mu m.
The films were tested: the glass transition temperature was 320 ℃, the thermal decomposition temperature was 500 ℃ and the transmittance at 450nm was 96%.
Example 3: the difference from example 2 is that the dianhydride used is:
after film making, the glass transition temperature is 300 ℃, the transmittance at 450nm is 88 percent, and the transmittance at 400nm is 90 percent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A diamine compound represented by the following general formula (I),
wherein,
R1、R2and each R is independently selected from the group consisting of halogen, amino, hydroxy, nitro, cyano, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, aminoalkyl of 1 to 12 carbon atoms, alkylamino of 1 to 12 carbon atoms, 2An alkanoyl group of up to 12 carbon atoms, an alkylamido group of 2 to 12 carbon atoms, an alkoxyacyl group of 1 to 12 carbon atoms, a thioalkyl group of 1 to 12 carbon atoms, an alkylthio group of 1 to 12 carbon atoms, a haloalkyl group of 1 to 12 carbon atoms, a haloalkoxy group of 1 to 12 carbon atoms, an aryl or heteroaryl group;
each X is independently selected from CF2O、OCF2、CHFO、OCHF、CF2And CHF, preferably X is each independently selected from CF2O and OCF2；
n and m are each independently an integer of 0 to 4, preferably n and m are each 0;
with the proviso that at least one R is selected from halogen, haloalkyl of 1 to 12 carbon atoms, or haloalkoxy of 1 to 12 carbon atoms.
2. Diamine compound according to claim 1, wherein each R is independently selected from fluorine, fluoroalkyl of 1 to 12 carbon atoms or fluoroalkoxy of 1 to 12 carbon atoms.
3. Diamine compound according to claim 1 or 2, wherein the compound is selected from the following compounds of formula (II)
4. A process for preparing a diamine compound as defined in any one of claims 1 to 3, comprising the steps of:
reacting a tetra-substituted benzene of formula (III)
With a substituted or unsubstituted nitrobenzene compound and other necessary reagents to produce a dinitro compound of formula (IV);
reducing the dinitro compound of the formula (IV) to produce the diamine compound according to any one of claims 1 to 3.
5. A polyamic acid obtained by polycondensation of the diamine compound according to any one of claims 1 to 3 and a tetracarboxylic acid dianhydride.
6. A polyimide which is characterized by first obtaining a polyamic acid by a polycondensation reaction of a diamine compound according to any one of claims 1 to 3 and a tetracarboxylic acid dianhydride; then dehydrating and ring-closing polyamic acid to obtain the polyamic acid.
7. The polyimide according to claim 6, wherein the polyimide has the following structure of formula (V):
wherein R is a tetravalent organic group; the degree of polymerization n is in the range of 5 to 500.
8. A polyimide according to claim 6 or 7, wherein the tetracarboxylic dianhydride is selected from at least one of the following compounds:
9. an optical film produced from the polyamic acid according to claim 5 and/or the polyimide according to any one of claims 6 to 8, or comprising the polyamic acid according to claim 5 and/or the polyimide according to any one of claims 6 to 8.
10. An opto-electronic device comprising the optical film according to claim 9.
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