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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- CN106674027A CN106674027A CN201611258200.2A CN201611258200A CN106674027A CN 106674027 A CN106674027 A CN 106674027A CN 201611258200 A CN201611258200 A CN 201611258200A CN 106674027 A CN106674027 A CN 106674027A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- G—PHYSICS
- G02—OPTICS
- 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 optical material field.The present invention relates to a kind of novel diamine compound, polyamic acid and polyamides are sub-
Amine, optical thin film and photoelectric device.More particularly, to novel diamine compound, the polyamic acid being made from it and polyamides
Imines, the further optical thin film containing them, photoelectric device containing the optical thin film and preparation method thereof.
Background technology
Polyimides are that molecular structure contains the pentacyclic family macromolecule material of acid imide, mainly by aromatic dianhydride
Compound is obtained with diamine compound by polycondensation method.This kind of compound has excellent heat stability, machinery strong due to it
Degree, dielectric properties, insulation characterisitic, and the features such as with prominent toughness and flexibility, many fields are gradually applied to, especially
It is to develop Flexible Displays industry faster in recent years.
With industrial expansions such as Aero-Space, solar energy, microelectronics, heat resistance continuous to polyimide material,
Dielectric properties and the transparency propose further requirement.Due to the highly aromatic conjugated property of traditional polyimide molecule main chain
With electric charge complexation transferance in strand, Kapton generally has color, while photopermeability is poor, in visible region
Domain is almost opaque.
To improve Kapton use characteristic in these areas, researcher has been carried out a series of exploration work
Make, part research work also achieves some effects.For example, Chinese patent application CN101674923A (Rhizoma Sparganii gas chemistry strain
Formula commercial firm) preparation method and preparation facilitiess of a kind of transparent polyimide film are disclosed, the method adopts alicyclic dianhydride
The hexamethylene tetracarboxylic dianhydride of compound 1,2,4,5- is obtained with diamine compound polymerization technique, is directly prepared using the solution colourless
Bright Kapton, it is 89.8% that obtained thickness is the light transmittance of 200 μm of thin film.Chinese patent application CN102634022A
A kind of colourless highly-transparent polyimide film and preparation method and application is disclosed, is polymerized from different diamidogen using fatty dianhydride
Obtain transparent Kapton well.
Polyimides prepared by tradition cause generation in polyimide molecule, between molecule due to larger conjugated degree
Electric charge transfer forms charge transfer complex (CTC) so that polyimide transparent is bad.The transparent of polyimides is improved at present
The approach of property mainly has：Using fluorochemical monomer；Introduce bulky group or side base, strong electron-withdrawing group；Draw in diamine monomer
Enter cast structural, lipid structure etc..
However, require for thermostability, dissolubility and the transparency, it is still unsatisfactory.
The content of the invention
According to background above, technical problem solved by the invention is how preferably to improve the heat-resisting of Kapton
Property, dissolubility and the transparency.
Inventor has found that, using having fluorine-containing bridge to be good for and the diamidogen containing fluorobenzene, the polyimides synthetically prepared with dianhydride are thin
Film, has relatively more excellent performance at aspects such as thermostability, dissolubility and the transparencys.
Based on this, one of the object of the invention is to overcome the deficiencies in the prior art, there is provided one kind is used for synthesis of polyimides list
The novel diamine compound of body, the diamine compound introduces strong containing fluorobenzene and fluorine-containing bridge.This can increase the molten of polyimides
Solution property and improve the permeability of Kapton.
The two of the object of the invention are to provide a kind of method of the novel diamine compound for preparing the present invention.The method synthesis letter
Single, easily operated, equipment cost is low and pollution-free.
The polyamic acid and polyamides that the three of the object of the invention are to provide a kind of novel diamine compound using the present invention is sub-
Amine.
The four of the object of the invention are to provide a kind of optical thin film, and the optical thin film is formed by the polyimides of the present invention, resistance to
The aspect such as hot, dissolubility and the transparency has relatively more excellent performance.
The five of the object of the invention are to provide a kind of photoelectric device, and the photoelectric device is formed by the optical thin film of the present invention.It
There is important using value in fields such as photoelectron, solar cell substrate, flexible liquid crystals.
For achieving the above object, on the one hand, the present invention adopts following technical proposal：
The diamine compound that following logical formula (I)s are represented,
Wherein,
R1、R2With R be each independently selected from halogen, amino, hydroxyl, nitro, cyano group, the alkyl of 1 to 12 carbon atom, 1 to
The alkoxyl of 12 carbon atoms, the aminoalkyl of 1 to 12 carbon atom, alkylamino, 2 to 12 carbon atoms of 1 to 12 carbon atom
Alkyl acyl, the alkyl amido of 2 to 12 carbon atoms, alkoxyacyl, 1 to 12 carbon atom of 1 to 12 carbon atom
Alkylthio, the alkylthio group of 1 to 12 carbon atom, the haloalkyl of 1 to 12 carbon atom, the halo of 1 to 12 carbon atom
Alkoxyl, aryl or heteroaryl；
X is each independently selected from CF2O、OCF2、CHFO、OCHF、CF2And CHF；
N and m are each independently 0~4 integer；
Condition is, halos of at least one R selected from halogen, the haloalkyl of 1 to 12 carbon atom or 1 to 12 carbon atom
Alkoxyl.
As expression R1、R2With the halogen of R, selected from fluorine, chlorine, bromine and iodine.
As expression R1、R2With alkyl halide (oxygen) base of R, one or more CH in alkyl are represented2In H atom by halogen
Alkane (oxygen) base that element replaces.It is preferred that, alkyl halide (oxygen) base is C1-C10Alkyl halide (oxygen) base, C1-C8Alkyl halide (oxygen) base, C1-C6
Alkyl halide (oxygen) base, or C1-C4Alkyl halide (oxygen) base.The non-limiting examples of alkyl halide (oxygen) base include halide (oxygen) base,
Halothane (oxygen) base, halogenopropane (oxygen) base, halo isopropyl alkane (oxygen) base, butyl halide (oxygen) base, halo iso-butane (oxygen)
Base, halo sec- butane (oxygen) base, halo tert- butane (oxygen) base, halo pentane (oxygen) base, and halo hexane (oxygen) base.Further
Ground, the non-limiting examples of such as haloalkyl include chloro first (oxygen) base, 1- bromo second (oxygen) bases, fluoro first (oxygen) base, two
Fluorine first (oxygen) base, fluoroform (oxygen) base, 1,1,1- trifluoro second (oxygen) base, etc..
In most situations, the substituent group of the present invention includes 1 to 12 carbon atom.By taking alkyl as an example, its can be straight chain or
Side chain, and can be substituted as noted herein.When the term of " alkyl of 1 to 12 carbon atom " is used, etc.
It is same as C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11Or C12.Other substituent group definition are similar, repeat no more.It is preferred that, 1 to 12
The alkyl of individual carbon atom is C1-C10Alkyl, C1-C8Alkyl, C1-C6Alkyl, or C1-C4Alkyl.Further, for example, C1-C6Alkane
Base includes all straight chains with 1 to 6 carbon atom, the alkyl of side chain, so as to include methyl, ethyl, n-pro-pyl, isopropyl,
Butyl and its isomer (such as normal-butyl, isobutyl group and the tert-butyl group), amyl group and its isomer, hexyl and its isomer.
Diamine compound of the invention, wherein, X is each independently selected from CF2O、OCF2、CHFO、OCHF、CF2With
CHF.Convenience based on synthesis, it is preferable that X is each independently selected from CF2O、OCF2, CHFO and OCHF；And, most preferably,
X is each independently selected from CF2O and OCF2。
Diamine compound of the invention, wherein, R be each independently selected from halogen, amino, hydroxyl, nitro, cyano group, 1
Alkyl to 12 carbon atoms, the alkoxyl of 1 to 12 carbon atom, aminoalkyl, 1 to 12 carbon atom of 1 to 12 carbon atom
Alkylamino, the alkyl acyl of 2 to 12 carbon atoms, the alkyl amido of 2 to 12 carbon atoms, the alkane of 1 to 12 carbon atom
Epoxide acyl group, the alkylthio of 1 to 12 carbon atom, the alkylthio group of 1 to 12 carbon atom, the alkyl halide of 1 to 12 carbon atom
Base, the halogenated alkoxy of 1 to 12 carbon atom, aryl or heteroaryl；Also, at least one R is selected from halogen, 1 to 12 carbon original
The haloalkyl of son or the halogenated alkoxy of 1 to 12 carbon atom.Preferably, at least 2 R are selected from halogen, 1 to 12 carbon atom
Haloalkyl or 1 to 12 carbon atom halogenated alkoxy；It is highly preferred that at least 3 R are selected from halogen, 1 to 12 carbon atom
Haloalkyl or 1 to 12 carbon atom halogenated alkoxy；And, most preferably, all R halogens, 1 to 12 carbon atom
The halogenated alkoxy of haloalkyl or 1 to 12 carbon atom.In a specific embodiment, R be each independently selected from fluorine,
The fluoroalkyl of the fluoro-alkyl of 1 to 12 carbon atom or 1 to 12 carbon atom.
Diamine compound of the invention, wherein, n and m are respectively 0.
Diamine compound of the invention, wherein, the compound is selected from following formula (II) compound
On the other hand, the present invention adopts following technical proposal：
A kind of method prepared according to diamine compound of the present invention, comprises the steps：
Make four substituted benzenes of formula (III)
With the dinitro chemical combination that substituted or unsubstituted nitrobenzene compound and other necessary reagent reactings generate formula (IV)
Thing；
The dinitro compound for making formula (IV) is reduced, and the diamine compound of the present invention is obtained.
In the synthetic reaction of diamine compound, solvent can be used as needed.As above-mentioned solvent, as long as can make
Specific diamine compound dissolves, and will not hinder reaction, and it is not particularly limited.Such as fragrance such as benzene, toluene can be enumerated
Race's hydro carbons；The ethers such as ether, tetrahydrofuran, dioxane；The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；And,
Dimethyl sulfoxide, dimethylformamide, dimethyl acetylamide etc..
In preparation method, four substituted benzenes of formula (III) and the usage rate of substituted or unsubstituted nitrobenzene compound,
Relative to four substituted benzenes of 1 mole of formula (III), substituted or unsubstituted nitrobenzene compound is preferably 2~20 moles.
When the dinitro compound of formula (IV) is reduced, can be with reducing agents such as hydrogen, hydrazine, hydrochloric acid in known catalyst
In the presence of carry out.As above-mentioned catalyst, can enumerate for example with group VIII metal, i.e. ferrum, cobalt, nickel, ruthenium, rhodium, palladium, osmium, indium,
The metals such as platinum are the metallic catalyst of active main body, specifically, can enumerate metal load in supported catalyst, above-mentioned gold
The complex catalyst of category.It can also be heterogeneous system that above-mentioned reduction reaction can be homogeneous system.
The consumption of catalyst can use appropriate ratio.For example when catalyst is with above-mentioned group VIII metal as active main body
When, relative to 100 weight portion dinitro compounds, 0.0001~100 weight portion is preferably used, particularly preferably using 0.001~
20 weight portions.Additionally, as above-mentioned reduction reaction, it is also possible to use zinc, stannum, carbonization stannum (II), sodium sulfide, sodium bisulfide, company two
The method of sodium sulfite, ammonium sulfide as reducing agent.Relative to the nitro of 1 mole of dinitro compound, reducing agent is preferably used
0.001~10 mole.
As the solvent used in above-mentioned reduction reaction, it is preferably able to dissolve dinitro compound and two amine compounds simultaneously
Thing, and will not be rotten because of reduction reaction solvent, such as alcohols such as methanol, ethanol, propanol, butanol can be enumerated；Ether, 1,
The ethers such as 2- dimethoxy-ethanes, tetrahydrofuran, dioxane, methoxybenzene.
In a specific embodiment, when the diamine compound of formula (II) is prepared, preparation method is as follows：
With tetrahydrofuran as solvent under (1) 1,2,4,5- phenyl tetrafluoride low temperature, by the way that phenyl lithium examination is synthesized with butyl lithium
Agent；
(2) difluorodibromomethane of 2~3 equivalents is added to above-mentioned reactant liquor under low temperature, is quenched with dilute hydrochloric acid after completion of the reaction
Go out reaction, the concentrate of oily is obtained after process；
(3) grease that above step is obtained adds paranitrophenol, room in the presence of non-protonic solvent, inorganic base
Through series of processes after temperature reaction, yellow solid is obtained；
(4) above-mentioned solid dissolving under Pd/C and hydrogen effect, is reduced in toluene, ethanol or tetrahydrofuran
Diamine compound.
Chemical equation is as follows：
Another aspect, the present invention adopts following technical proposal：
A kind of polyamic acid, is obtained with tetrabasic carboxylic acid dicarboxylic anhydride by the diamine compound of the present invention by polycondensation reaction.
Another further aspect, the present invention adopts following technical proposal：
A kind of polyimides, are gathered first with tetrabasic carboxylic acid dicarboxylic anhydride by the diamine compound of the present invention by polycondensation reaction
Amic acid；Then polyamic acid dehydration closed-loop is obtained.
Can be Alicyclic tetracarboxylic acid dicarboxylic anhydride as the tetrabasic carboxylic acid dicarboxylic anhydride that the present invention is used.Butane four can be enumerated
Carboxylic diacid acid anhydride, 1,2,3,4- Tetramethylene. tetrabasic carboxylic acid dicarboxylic anhydrides, 1,2- dimethyl -1,2,3,4- Tetramethylene. tetrabasic carboxylic acid dicarboxylic anhydrides,
1,3- dimethyl -1,2,3,4- Tetramethylene. tetrabasic carboxylic acid dicarboxylic anhydrides, the chloro- 1,2,3,4- Tetramethylene. tetrabasic carboxylic acid dicarboxylic anhydrides of 1,3- bis-, 1,
2,3,4- tetramethyl -1,2,3,4- Tetramethylene. tetrabasic carboxylic acid dicarboxylic anhydrides, 1,2,3,4- Pentamethylene. tetrabasic carboxylic acid dicarboxylic anhydrides, 1,2,4,5- rings
Hexane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5- norbornane tetrabasic carboxylic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride,
2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides, the carboxyl norbornane -2- acetic acid dianhydrides of 3,5,6- tri-, 2,3,4,5- tetrahydrofurans four
Carboxylic diacid acid anhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furan -1,
3- diketone, 1,3,3a, 4,5,9b- hexahydro -5- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furan -
1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -5- ethyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furan
Mutter -1,3- diketone, 1,3,3a, and 4,5,9b- hexahydro -7- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c] -
Furan -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -7- ethyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-
C]-furan -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,
2-c]-furan -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- ethyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene
[1,2-c]-furan -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -5,8- dimethyl -5- (tetrahydrochysene -2,5- dioxo -3- furan
Base)-naphthalene [1,2-c]-furan -1,3- diketone, 5- (2,5- dioxotetrahydro furals) -3- methyl -3- cyclohexene -1,2-
Dicarboxylic acid dianhydride, bicyclic [2,2,2]-octyl- 7- alkene -2,3,5,6- tetrabasic carboxylic acid dicarboxylic anhydrides, 3- oxabicyclos [3.2.1] octane -2,
4- diketone -6- spiral shells -3 '-(tetrahydrofuran -2 ', 5 '-diketone).
As the tetrabasic carboxylic acid dicarboxylic anhydride that the present invention is used, aromatic tetracarboxylic acid's dicarboxylic anhydride is can also be.Pyromellitic acid dianhydride,
3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-sulfobenzide. tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8- naphthalene tetracarboxylic acids
Dicarboxylic anhydride, 2,3,6,7- naphthalene tetracarboxylic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dimethyl
Diphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4- furan tetrabasic carboxylic acid two
Anhydride, 4,4 '-two (3,4- di carboxyl phenyloxies) diphenylsulfide dicarboxylic anhydrides, 4,4 '-two (3,4- di carboxyl phenyloxies) hexichol
Base sulfone dicarboxylic anhydride, 4,4 '-two (3,4- di carboxyl phenyloxies) diphenyl propane dicarboxylic anhydrides, 3,3 ', 4,4 '-perfluor isopropylidene two
Phthalandione dianhydride, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, two (phthalandione) phosphniline oxide dicarboxylic anhydrides, p-phenylene-two (three
Phenyl phthalandione) dianhydride,-phenylene-two (triphenyl phthalandione) dianhydride, two (triphenyl phthalandione) -4,4 '-diphenyl ether dianhydrides, two
(triphenyl phthalandione) -4,4 '-diphenyl methane dianhydride, ethylene glycol-two (dehydration trimellitate), (the inclined benzene of dehydration of Propylene Glycol-two
Three acid esters), 1,4- butanediols-two (dehydration trimellitate), 1,6-HD-two (dehydration trimellitate), 1,8- pungent two
Alcohol-two (dehydration trimellitate), 2,2- bis- (4- hydroxyphenyl) propane-two (dehydration trimellitate).
They can be with a kind individually or 2 kinds or more are applied in combination.
Polyimides of the invention, wherein, the polyimides preferably have following formula V structure：
Wherein, R is quadrivalent organic radical；Polymerization degree n is in the range of 5 to 500.
Polyimides of the invention, wherein it is preferred to, the tetrabasic carboxylic acid dicarboxylic anhydride is selected from following compounds at least
It is a kind of：
The polyamic acid of the present invention is obtained by making diamine compound with tetrabasic carboxylic acid diacid anhydride reactant.Tetrabasic carboxylic acid dicarboxylic anhydride with
The usage rate of diamine compound, preferably with respect to amino contained in 1 equivalent diamine compound, makes the acid of tetrabasic carboxylic acid dicarboxylic anhydride
Anhydride group is the ratio of 0.2~2 equivalent, more preferably the ratio of 0.3~1.2 equivalent.
The synthetic reaction of polyamic acid, in organic solvent in 100~250 DEG C, be preferable over 150~220 DEG C, more preferably in
Carry out under 180~200 DEG C of temperature conditionss.
As organic solvent, as long as the polyamic acid for synthesizing can be dissolved or be disperseed, it is not particularly limited.Can be with
Illustrate such as METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-fourth
The aprotic polar solvents such as lactone, tetramethylurea, hexamethyl phosphorous acid Disnalon (Ferrer).；Between sylvan, xylenols, phenol, halo
The phenol solvents such as phenol.
Additionally, in the range of the polyamic acid for not making generation is separated out, can also be used in combination in above-mentioned organic solvent poly-
Amic acid poor solvent alcohols, ketone, esters, ethers, halogenated hydrocarbon, hydro carbons etc..As the specific example of this poor solvent,
Such as methanol, ethanol, isopropanol, Hexalin, ethylene glycol, Propylene Glycol, 1,4- butanediols, 2,2'-ethylenedioxybis(ethanol)., ethylene glycol list can be enumerated
Methyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, methyl acetate, ethyl acetate,
Butyl acetate, methoxy methyl propionate, ethoxyl ethyl propionate, ethyl oxalate, diethyl malonate, ether, ethylene glycol first
Ether, ethylene glycol, ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ethers
Ether acetic acid ester, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid
Ester, diethylene glycol monoethyl ether acetass, tetrahydrofuran, dichloromethane, 1,2- dichloroethanes, 1,4- dichloroetane, trichloroethane, chlorine
Benzene, o-dichlorohenzene, hexane, heptane, octane, benzene,toluene,xylene etc..
As described above, obtaining dissolving the reaction solution of polyamic acid.Then, the reaction solution is distributed to a large amount of bad molten
In agent, precipitate is obtained.Then, precipitate filtered, washed, be dried, obtain polyamic acid.
Subsequently, polyamic acid is dissolved in organic solvent, then the film on cleaning substrate gradually dries, most after bake
Dry, cooling obtains Kapton.
In a specific embodiment, preparation method is as follows：
(1) diamidogen and dianhydride of equivalent in being added to metacresol solvent, are heated up under nitrogen or argon protection
To 180~200 DEG C, heat 8~15 hours, be subsequently cooled to room temperature, disperseed with methanol solvate, filter, washing is dried,
Obtain polyamic acid (performed polymer)；
(2) polyamic acid is dissolved in organic solvent, then the film on clean substrate, then gradually dries, finally
Dry 120 minutes at 200~300 DEG C, cooling obtains Kapton.
Chemical equation is as follows：
Wherein, R is quadrivalent organic radical；Polymerization degree n is in the range of 5 to 500.
Another aspect, the present invention adopts following technical proposal：
A kind of optical thin film, is prepared by the polyamic acid and/or polyimides of the present invention.
Again or, a kind of optical thin film, the polyamic acid containing the present invention and/or polyimides.
Last aspect, the present invention adopts following technical proposal：
A kind of photoelectric device, the optical thin film containing the present invention.
Photoelectric device of the invention, wherein, the photoelectric device selected from opto-electronic device, solar cell device,
Flexible display device (such as OLED and LCD), e-book, electronic tag or photoelectric sensor.
Compared with prior art, the present invention has following advantage：
(1) the invention provides a kind of simplicity can realize industrialized fluorinated polyimide synthetic method；Synthesis is simple,
Containing the strong structure of the double difluoromethoxy bridges of tetrafluoro phenyl；
(2) have in polyimide molecule structure and be good for containing fluorophenyl and fluorine-containing bridge, increased the dissolubility of polyimides, press down
The formation of intramolecular and intermolecular CTC is made, material flexibility and transparency has been increased, hot property is excellent, it is aobvious in flexible and transparent
There is preferable application prospect in example such as OLED fields.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright rather than restriction the scope of the present invention.In addition, it is to be understood that after present disclosure has been read, those skilled in the art
The present invention can be made various changes or modifications, these equivalent form of values equally fall within what the application appended claims were limited
Scope.
Will be helpful to understand the present invention by following embodiments, but the scope of the present invention can not be limited.
Embodiment 1：The preparation of diamidogen (chemical formula 1)：
1st, 30g (0.2mol) 1,2,4,5- phenyl tetrafluoride is added in 1L there-necked flasks, 600ml tetrahydrofurans install stirring, cold
Bath, Deca and nitrogen protection device, start stirring, -75 DEG C are cooled under nitrogen protection, Deca 220ml butyl lithium solution
(0.44mol, 2mol/L), after completion of dropping, -70 DEG C of holding is stirred below 30 minutes, then proceedes to Deca difluorodibromomethane
Solution (0.52mol, containing 110g difluorodibromomethanes), is kept for less than -60 DEG C, and completion of dropping continues stirring 30 minutes, then
It is hydrolyzed with 10% dilute hydrochloric acid, and then carries out post processing, obtains rufous grease 70g, yield 86%, it is not necessary to enter
Step process, directly carries out next step reaction；
2nd, add in 1L there-necked flasks and walk obtained brown oil 50g, 500ml dimethylformamides, 1g potassium iodide,
30g paranitrophenols, are heated to 90 DEG C, after reacting 2 hours, stop heating, after cooling, frozen water are added in reaction system, extremely
Product is separated out, and is filtered, and after washing, is crystallized with ethanol, obtains yellow solid 31g, yield 60%, purity 97%.
3rd, the obtained dinitro compound of step, 200ml toluene, 100ml ethanol, 1g 5% on 30g are added in 1L autoclaves
Pd/C, normal temperature and pressure be hydrogenated with 5 hours, by gas chromatogram monitoring reaction it is qualified after, carry out the process of next step, filter, it is dense
Contracting, and crystallized with 100ml isopropanols, pink solid powder is obtained, 24g, gas chromatographic purity 99%, yield are obtained after being dried
90%, MS confirm that (molecular weight M+464) structure is correct.
Embodiment 2：It is prepared by transparent polyimide film：
Structural formula is as follows：
1st, the preparation (structural formula is as follows) of polyamic acid：
Operation：In 1L there-necked flasks, addition diamidogen 20g, and 8.5g cyclobutanetetracarboxylic dianhydrides, 500g metacresols, plus
Heat after reacting 8 hours, is cooled to 60 DEG C or so to 150 DEG C, anti-liquid is distributed under agitation in methanol, suction strainer after cooling, and
Washed with methanol.It is dried, obtains 25g stringy solids.
2nd, the preparation of Kapton：
Stringy solids obtained in upper step are dissolved in 5% N-Methyl pyrrolidone, 5% solution is made into, 0.45 μ is used
The filter membrane of m is filtered, to remove mechanical admixture.Then polymer solution is coated on the glass substrate of cleaning, 50 DEG C of drying 1
Hour, 100 DEG C 1 hour, last 200 DEG C dry 2 hours, are cooled to room temperature, demoulding, and prepared thickness is for about 20 μm or so transparent
Kapton.
Thin film is tested：Vitrification point is 320 DEG C, and heat decomposition temperature is 500 DEG C, is in 450nm transmitances
96%.
Embodiment 3：With embodiment 2, difference is that dianhydride used is：
Test after masking, 300 DEG C of vitrification point, in 450nm transmitances 88%, transmitance 90% at 400nm.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., be all contained within protection scope of the present invention.
Claims (10)
1. the diamine compound that following logical formula (I)s are represented,
Wherein,
R1、R2With R be each independently selected from halogen, amino, hydroxyl, nitro, cyano group, the alkyl of 1 to 12 carbon atom, 1 to 12
The alkoxyl of carbon atom, the aminoalkyl of 1 to 12 carbon atom, the alkylamino of 1 to 12 carbon atom, the alkane of 2 to 12 carbon atoms
Base acyl group, the alkyl amido of 2 to 12 carbon atoms, the alkoxyacyl of 1 to 12 carbon atom, the sulfur of 1 to 12 carbon atom
Substituted alkyl, the alkylthio group of 1 to 12 carbon atom, the haloalkyl of 1 to 12 carbon atom, the haloalkoxy of 1 to 12 carbon atom
Base, aryl or heteroaryl；
X is each independently selected from CF2O、OCF2、CHFO、OCHF、CF2And CHF, preferred X are each independently selected from CF2O and OCF2；
N and m are each independently 0~4 integer, and preferred n and m are respectively 0；
Condition is, haloalkoxies of at least one R selected from halogen, the haloalkyl of 1 to 12 carbon atom or 1 to 12 carbon atom
Base.
2. diamine compound according to claim 1, wherein, R is each independently selected from the fluorine of fluorine, 1 to 12 carbon atom
The fluoroalkyl of substituted alkyl or 1 to 12 carbon atom.
3. diamine compound according to claim 1 and 2, wherein, the compound is selected from following formula (II) compound
4. a kind of method for preparing diamine compound described in any one of claim 1-3, comprises the steps：
Make four substituted benzenes of formula (III)
With the dinitro compound that substituted or unsubstituted nitrobenzene compound and other necessary reagent reactings generate formula (IV)；
The dinitro compound for making formula (IV) is reduced, and the diamine compound described in any one of claim 1-3 is obtained.
5. a kind of polyamic acid, it is characterised in that the diamine compound by described in any one of claim 1-3 and tetracarboxylic acid acid diacid
Acid anhydride is obtained by polycondensation reaction.
6. a kind of polyimides, it is characterised in that the diamine compound and tetrabasic carboxylic acid first by described in any one of claim 1-3
Dicarboxylic anhydride obtains polyamic acid by polycondensation reaction；Then polyamic acid dehydration closed-loop is obtained.
7. polyimides according to claim 6, wherein, the polyimides have following formula V structure：
Wherein, R is quadrivalent organic radical；Polymerization degree n is in the range of 5 to 500.
8. polyimides according to claim 6 or 7, wherein, the tetrabasic carboxylic acid dicarboxylic anhydride selected from following compounds extremely
Few one kind：
9. a kind of optical thin film, it is characterised in that it is arbitrary by the polyamic acid and/or claim 6-8 described in claim 5
Polyimides described in are prepared, or, it contains the polyamic acid and/or claim 6-8 described in claim 5 appoints
Polyimides described in one.
10. a kind of photoelectric device, it is characterised in that containing the optical thin film described in claim 9.
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