CN106674027B - Diamine compound, polyimides, optical thin film and preparation method thereof - Google Patents
Diamine compound, polyimides, optical thin film and preparation method thereof Download PDFInfo
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- CN106674027B CN106674027B CN201611258200.2A CN201611258200A CN106674027B CN 106674027 B CN106674027 B CN 106674027B CN 201611258200 A CN201611258200 A CN 201611258200A CN 106674027 B CN106674027 B CN 106674027B
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- polyimides
- diamine compound
- polyamic acid
- tetrabasic carboxylic
- dicarboxylic anhydride
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- 0 CC1C(c(c(F)c(c(*C2C=CC(NCC(C3*)C(CNC)C3C(O)=O)=CC2)c2F)F)c2F)=CC=C(C)C1 Chemical compound CC1C(c(c(F)c(c(*C2C=CC(NCC(C3*)C(CNC)C3C(O)=O)=CC2)c2F)F)c2F)=CC=C(C)C1 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- 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
Abstract
It provides with good dissolubility, the optical thin film of higher optical transmittance.Polyamic acid is made using specific diamine compound and tetracarboxylic dianhydride；Polyamic acid dehydration closed-loop obtains polyimides, and transparent polyimide film is then further made.The film can be used for opto-electronic device, solar cell device, flexible display device, e-book, electronic tag or photoelectric sensor.
Description
Technical field
The invention belongs to optical material fields.It is sub- that the present invention relates to a kind of novel diamine compound, polyamic acid and polyamides
Amine, optical thin film and photoelectric device.More particularly, to novel diamine compound, the polyamic acid and polyamides that are made from it
Imines contains their optical thin film, the further photoelectric device and preparation method thereof containing the optical thin film.
Background technology
Polyimides is that molecular structure contains the pentacyclic a kind of high molecular material of acid imide, mainly passes through aromatic dianhydride
Compound is made with diamine compound by polycondensation method.This kind of compound is strong with excellent thermal stability, machinery due to it
Degree, dielectric properties, insulation characterisitic, and have the characteristics that toughness and flexibility outstanding, gradually it is applied to many fields, especially
It is to develop faster Flexible Displays industry in recent years.
With industrial expansions such as aerospace, solar energy, microelectronics, constantly to the heat resistance of polyimide material,
Dielectric properties and the transparency propose further requirement.Due to the aromatic conjugated property of the height of traditional polyimide molecule main chain
Transferance is complexed with charge in strand, Kapton usually has color, while photopermeability is poor, in visible region
Domain is almost opaque.
To improve the use characteristic of Kapton 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 (Mitsubishi's gas chemistry strains
Formula commercial firm) a kind of preparation method and preparation facilities of transparent polyimide film are disclosed, this method uses alicyclic dianhydride
1,2,4,5- hexamethylene tetracid dianhydride of compound is made with diamine compound polymerization technique, is directly prepared using the solution colourless
Bright Kapton, thickness obtained are that the light transmittance of 200 μm of films is 89.8%.Chinese patent application CN102634022A
A kind of colourless highly-transparent polyimide film and the preparation method and application thereof is disclosed, is polymerize from different diamines using fatty dianhydride
Obtain the good Kapton of the transparency.
Polyimides prepared by tradition causes to occur 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 group, strong electron-withdrawing group；Draw in diamine monomer
Enter cast structural, lipid structure etc..
However, required for heat resistance, dissolubility and the transparency, it is still unsatisfactory.
Invention content
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 with strong and containing fluorobenzene the diamines of fluorine-containing bridge, the polyimides being synthetically prepared with dianhydride is thin
Film has more excellent performance in heat resistance, dissolubility and transparency etc..
Based on this, one of the object of the invention is to overcome the deficiencies of the prior art and provide one kind being used for synthesis of polyimides list
The novel diamine compound of body, the diamine compound introduce strong containing fluorobenzene and fluorine-containing bridge.This can increase the molten of polyimides
Solution property and the permeability for improving Kapton.
The two of the object of the invention are to provide a kind of method for the novel diamine compound preparing the present invention.This method synthesis letter
It is single, easily operated, equipment cost is low and pollution-free.
The three of the object of the invention be to provide a kind of novel diamine compound using the present invention polyamic acid and polyamides it is sub-
Amine.
The four of the object of the invention are to provide a kind of optical thin film, which is formed by the polyimides of the present invention, resistance to
Hot, dissolubility and the transparency etc. have more excellent performance.
The five of the object of the invention are to provide a kind of photoelectric device, which is formed by the optical thin film of the present invention.It
There is important application value in fields such as photoelectron, solar cell substrate, flexible liquid crystals.
To achieve the above object, on the one hand, the present invention uses following technical proposal：
The diamine compound that the following general formula (I) indicates,
Wherein,
R1、R2With R be each independently selected from halogen, amino, hydroxyl, nitro, cyano, the alkyl of 1 to 12 carbon atom, 1 to
Alkylamino, 2 to 12 carbon atoms of the alkoxy of 12 carbon atoms, the aminoalkyl of 1 to 12 carbon atom, 1 to 12 carbon atom
Alkyl acyl, the alkyl amidos of 2 to 12 carbon atoms, 1 to 12 carbon atom alkoxyacyl, 1 to 12 carbon atom
Alkylthio, the alkylthio group of 1 to 12 carbon atom, the halogenated alkyl of 1 to 12 carbon atom, 1 to 12 carbon atom it is halogenated
Alkoxy, aryl or heteroaryl；
X is each independently selected from CF2O、OCF2、CHFO、OCHF、CF2And CHF；
N and m is each independently 0~4 integer；
Condition is, at least one R is selected from the halogenated of halogen, the halogenated alkyl of 1 to 12 carbon atom or 1 to 12 carbon atom
Alkoxy.
As expression R1、R2With the halogen of R, it is selected from fluorine, chlorine, bromine and iodine.
As expression R1、R2With alkyl halide (oxygen) base of R, one or more of alkyl CH is indicated2In H atom by halogen
Alkane (oxygen) base of element substitution.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, halogenated isopropyl alkane (oxygen) base, butyl halide (oxygen) base, halogenated iso-butane (oxygen)
Base, halogenated sec- butane (oxygen) base, halogenated tert- butane (oxygen) base, halogenated pentane (oxygen) base and halogenated hexane (oxygen) base.Further
Ground, such as the non-limiting examples of halogenated alkyl include chloro first (oxygen) base, 1- bromos second (oxygen) base, fluoro first (oxygen) base, two
Fluorine first (oxygen) base, fluoroform (oxygen) base, 1,1,1- trifluoro second (oxygen) base, etc..
In most situations, substituent group of the invention includes 1 to 12 carbon atom.By taking alkyl as an example, can be straight chain or
Branch, and can be substituted as noted herein.When the term of use " alkyl of 1 to 12 carbon atom ", etc.
It is same as C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11Or C12.Other substituent groups define similar, repeat no more.It is preferred that 1 to 12
The alkyl of a 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 branch, to including methyl, ethyl, n-propyl, isopropyl,
Butyl and its isomers (such as normal-butyl, isobutyl group and tertiary butyl), amyl and its isomers, hexyl and its isomers.
Diamine compound according to the present 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 according to the present invention, wherein R is each independently selected from halogen, amino, hydroxyl, nitro, cyano, 1
To the alkyl of 12 carbon atoms, aminoalkyl, 1 to 12 carbon atom of the alkoxy of 1 to 12 carbon atom, 1 to 12 carbon atom
Alkylamino, the alkyl acyls of 2 to 12 carbon atoms, the alkyl amido of 2 to 12 carbon atoms, 1 to 12 carbon atom alkane
The alkyl halide of oxygroup acyl group, the alkylthio of 1 to 12 carbon atom, the alkylthio group of 1 to 12 carbon atom, 1 to 12 carbon atom
Halogenated alkoxy, aryl or the heteroaryl of base, 1 to 12 carbon atom；Also, at least one R is selected from halogen, 1 to 12 carbon original
The halogenated alkyl of son or the halogenated alkoxy of 1 to 12 carbon atom.Preferably, at least two R is selected from halogen, 1 to 12 carbon atom
Halogenated alkyl or 1 to 12 carbon atom halogenated alkoxy；It is highly preferred that at least three R is selected from halogen, 1 to 12 carbon atom
Halogenated alkyl or 1 to 12 carbon atom halogenated alkoxy；And most preferably, all R halogens, 1 to 12 carbon atom
The halogenated alkoxy of halogenated alkyl or 1 to 12 carbon atom.In a specific embodiment, R be each independently selected from fluorine,
The fluoro-alkyl of 1 to 12 carbon atom or the fluoroalkyl of 1 to 12 carbon atom.
Diamine compound according to the present invention, wherein n and m are respectively 0.
Diamine compound according to the present invention, wherein the compound is selected from following formula (II) compound
On the other hand, the present invention uses following technical proposal：
A method of it prepares according to diamine compound of the present invention, includes the following steps：
Make four substituted benzenes of formula (III)
The dinitro chemical combination for generating formula (IV) is reacted with substituted or unsubstituted nitrobenzene compound and other necessary reagents
Object；
So that the dinitro compound of formula (IV) is restored, the diamine compound of the present invention is made.
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 interfere reaction, it is not particularly limited.The 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 (DMSO), dimethylformamide, dimethylacetylamide etc..
In preparation method, the usage rate of four substituted benzenes and substituted or unsubstituted nitrobenzene compound of formula (III),
Relative to four substituted benzenes of 1 mole of formula (III), substituted or unsubstituted nitrobenzene compound is preferably 2~20 moles.
When the reduction of the dinitro compound of formula (IV), the reducing agents such as hydrogen, hydrazine, hydrochloric acid can be used in known catalyst
In the presence of carry out.As above-mentioned catalyst, can enumerate for example with group VIII metal, i.e., iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, indium,
The metals such as platinum, which are the metallic catalyst of active main body, specifically can enumerate Metal Supported in supported catalyst, above-mentioned gold
The complex catalyst of category.Above-mentioned reduction reaction can be that homogeneous system can also be heterogeneous system.
The dosage of catalyst can use ratio appropriate.Such as when catalyst is using above-mentioned group VIII metal as active main body
When, relative to 100 parts by weight dinitro compounds, it is preferable to use 0.0001~100 parts by weight, particularly preferably use 0.001~
20 parts by weight.In addition, as above-mentioned reduction reaction, zinc also can be used, tin, carbonization tin (II), vulcanized sodium, sodium bisulfide, connect two
The method of sodium sulfite, ammonium sulfide as reducing agent.Relative to the nitro of 1 mole of dinitro compound, reducing agent it is preferable to use
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
Object, and will not be rotten because of reduction reaction solvent, the alcohols such as methanol, ethyl alcohol, propyl alcohol, butanol can be enumerated；Ether, 1,
The ethers such as 2- dimethoxy-ethanes, tetrahydrofuran, dioxane, anisole.
In a specific embodiment, when preparing the diamine compound of formula (II), preparation method is as follows：
Using tetrahydrofuran as solvent under (1) 1,2,4,5- phenyl tetrafluoride low temperature, by reacting the examination of synthesis of phenyl lithium with butyl lithium
Agent；
(2) difluorodibromomethane of 2~3 equivalents is added under low temperature to above-mentioned reaction solution, is quenched after completion of the reaction with dilute hydrochloric acid
It goes out reaction, the concentrate of oily is obtained after processing；
(3) p-nitrophenol, room is added in the presence of non-protonic solvent, inorganic base in the grease that above step obtains
By series of processes after temperature reaction, yellow solid is obtained；
(4) above-mentioned solid is dissolved in toluene, ethyl alcohol or tetrahydrofuran, at Pd/C and hydrogen effect, is reduced to
Diamine compound.
Chemical equation is as follows：
Another aspect, the present invention use following technical proposal：
A kind of polyamic acid is obtained with tetrabasic carboxylic acid dicarboxylic anhydride by polycondensation reaction by the diamine compound of the present invention.
In another aspect, the present invention uses following technical proposal：
A kind of polyimides is gathered with tetrabasic carboxylic acid dicarboxylic anhydride by polycondensation reaction by the diamine compound of the present invention first
Amic acid；Then polyamic acid dehydration closed-loop obtains.
Can be Alicyclic tetracarboxylic acid dicarboxylic anhydride as the tetrabasic carboxylic acid dicarboxylic anhydride that the present invention uses.Butane four can be enumerated
Carboxylic diacid acid anhydride, 1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, 1,2- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride,
1,3- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, bis- chloro- 1,2,3,4- cyclobutane tetrabasic carboxylic acid dicarboxylic anhydrides of 1,3-, 1,
2,3,4- tetramethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, 1,2,3,4- pentamethylene tetrabasic carboxylic acids dicarboxylic anhydride, 1,2,4,5- rings
Hexane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5- norbornane tetrabasic carboxylic acids dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydrides,
2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, tri- carboxyl norbornane -2- acetic acid dianhydrides of 3,5,6-, 2,3,4,5- tetrahydrofurans four
Carboxylic diacid acid anhydride, 1,3,3a, 4,5,9b- hexahydros -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furans -1,
3- diketone, 1,3,3a, 4,5,9b- hexahydro -5- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furans -
1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -5- ethyls -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furan
Mutter -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -7- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c] -
Furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -7- ethyls -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-
C]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,
2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- ethyls -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene
[1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -5,8- dimethyl -5- (tetrahydrochysene -2,5- dioxo -3- furans
Base)-naphthalene [1,2-c]-furans -1,3- diketone, 5- (2,5- dioxotetrahydros fural) -3- methyl -3- cyclohexene -1,2-
Dicarboxylic acid dianhydride, bicyclic [2,2,2]-octyl- 7- alkene -2,3,5,6- tetrabasic carboxylic acids dicarboxylic anhydride, 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 uses, aromatic tetracarboxylic acid's dicarboxylic anhydride can also be.Pyromellitic acid dianhydride,
3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydrides, 1,4,5,8- naphthalene tetracarboxylic acids
Dicarboxylic anhydride, 2,3,6,7- naphthalene tetracarboxylic acids dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-dimethyl
Diphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetrabasic carboxylic acid dicarboxylic anhydrides, 1,2,3,4- furans tetrabasic carboxylic acid two
Acid anhydrides, 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 isopropylidenes two
Phthalandione dianhydride, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydrides, 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), propylene glycol-two (are dehydrated inclined benzene
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- hydroxyphenyls) propane-two (dehydration trimellitate).
They can be with a kind of independent or 2 kinds or combination of the above use.
Polyimides according to the present invention, wherein the polyimides preferably has following formula (V) structure：
Wherein, R is quadrivalent organic radical；Polymerization degree n is in 5 to 500 ranges.
Polyimides according to the present invention, wherein preferably, 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 by making diamine compound be made with tetrabasic carboxylic acid diacid anhydride reactant.Tetrabasic carboxylic acid dicarboxylic anhydride with
The usage rate of diamine compound makes the acid of tetrabasic carboxylic acid dicarboxylic anhydride preferably with respect to amino contained in 1 equivalent diamine compound
Anhydride group is the ratio of 0.2~2 equivalent, the more preferably 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
It is carried out under 180~200 DEG C of temperature condition.
As organic solvent, as long as the polyamic acid of synthesis can be dissolved or be disperseed, it is not particularly limited.It can be with
Illustrate such as n-methyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), γ-fourth
The aprotic polar solvents such as lactone, tetramethylurea, hexamethyl phosphorous acid triamide；Between sylvan, dimethlbenzene, phenol, halogenated
The phenol solvents such as phenol.
In addition, in the range of not making the polyamic acid of generation be precipitated, 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, ethyl alcohol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4- butanediols, triethylene glycol, ethylene glycol list can be enumerated
Methyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, methyl acetate, ethyl acetate,
Butyl acetate, methoxy methyl propionate, ethoxyl ethyl propionate, diethy-aceto oxalate, diethyl malonate, ether, ethylene glycol first
Ether, ethylene glycol ethyl ether, 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 acetic acid esters, tetrahydrofuran, dichloromethane, 1,2- dichloroethanes, 1,4- dichloroetane, trichloroethanes, chlorine
Benzene, o-dichlorohenzene, hexane, heptane, octane, benzene,toluene,xylene etc..
As described above, obtaining the reaction solution of dissolving polyamic acid.Then, which is distributed to a large amount of bad molten
In agent, precipitate is obtained.Then, precipitate is filtered, washed, dried, obtain polyamic acid.
Then, in organic solvent by polyamic acid dissolving, the film on cleaning substrate, then gradually drying, finally dries
It is dry, it is cooling, obtain Kapton.
In a specific embodiment, preparation method is as follows：
(1) diamines of equivalent and dianhydride are added in metacresol solvent, are heated up under nitrogen or argon gas protection
It to 180~200 DEG C, heats 8~15 hours, then cools to room temperature, disperseed with methanol solvate, filter, wash, it is dry,
Obtain polyamic acid (performed polymer)；
(2) polyamic acid is dissolved in organic solvent, then the film on clean substrate, then gradually drying, finally
It is dried 120 minutes at 200~300 DEG C, it is cooling, obtain Kapton.
Chemical equation is as follows：
Wherein, R is quadrivalent organic radical；Polymerization degree n is in 5 to 500 ranges.
Another aspect, the present invention use 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, polyamic acid and/or polyimides containing the present invention.
Last aspect, the present invention use following technical proposal：
A kind of photoelectric device, the optical thin film containing the present invention.
Photoelectric device according to the present invention, wherein the photoelectric device be 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 present invention provides a kind of simplicity, and industrialized fluorinated polyimide synthetic method may be implemented；Synthesis is simple,
Contain 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, increase the dissolubility of polyimides, press down
The formation for having made intramolecular and intermolecular CTC increases material flexibility and transparency, and hot property is excellent, aobvious in flexible and transparent
There is preferable application prospect in the example such as fields OLED.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after having read present disclosure, those skilled in the art
The present invention can be made various changes or modifications, such equivalent forms are equally fallen within defined by the application the appended claims
Range.
It will be helpful to understand the present invention by following embodiments, but cannot limit the scope of the invention.
Embodiment 1：The preparation of diamines (chemical formula 1)：
1,30g (0.2mol) 1,2,4,5- phenyl tetrafluoride is added in 1L there-necked flasks, 600ml tetrahydrofurans install stirring, cold
Bath, dropwise addition and nitrogen protection device, start stirring, are cooled to -75 DEG C under nitrogen protection, and 220ml butyl lithium solutions are added dropwise
(0.44mol, 2mol/L), after being added dropwise, -70 DEG C of holding is 30 minutes stirred below, then proceedes to that difluorodibromomethane is added dropwise
Solution (0.52mol contains 110g difluorodibromomethanes) is kept for -60 DEG C hereinafter, be added dropwise, continues stirring 30 minutes, then
It is hydrolyzed, and then is post-processed with 10% dilute hydrochloric acid, obtain rufous grease 70g, yield 86% need not be into one
Step processing, directly carries out next step reaction；
2, it is added in 1L there-necked flasks and walks brown oil 50g, 500ml dimethylformamide obtained, 1g potassium iodide,
30g p-nitrophenols are heated to 90 DEG C, after reacting 2 hours, stop heating and ice water is added into reaction system after cooling, until
Product is precipitated, and filtering after washing, is crystallized with ethyl alcohol, obtains yellow solid 31g, yield 60%, purity 97%.
3, step dinitro compound obtained, 200ml toluene, 100ml ethyl alcohol, 1g 5% on 30g are added in 1L autoclaves
Pd/C, normal temperature and pressure adds hydrogen 5 hours, by gas-chromatography monitor reaction it is qualified after, carry out the processing of next step, filter, it is dense
Contracting is used in combination 100ml isopropanols to crystallize, and obtains pink solid powder, 24g, gas chromatographic purity 99%, yield are obtained after dry
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：
1, the preparation of polyamic acid (structural formula is as follows)：
Operation：In 1L there-necked flasks, diamines 20g and 8.5g cyclobutanetetracarboxylic dianhydride is added, 500g metacresols add
Heat after reacting 8 hours, is cooled to 60 DEG C or so, anti-liquid is distributed in methanol under stiring to 150 DEG C, suction strainer after cooling, and
It is washed with methanol.It is dry, obtain 25g stringy solids.
2, the preparation of Kapton：
Stringy solids made from upper step are dissolved in 5% N-Methyl pyrrolidone, 5% solution is made into, with 0.45 μ
The filter membrane of m is filtered, to remove mechanical admixture.Then polymer solution is coated on clean glass substrate, 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 obtained thickness is about 20 μm or so transparent
Kapton.
Film is tested：Glass transition temperature is 320 DEG C, and heat decomposition temperature is 500 DEG C, is in 450nm transmitances
96%.
Embodiment 3：With embodiment 2, the difference is that dianhydride used is：
It is tested after film, 300 DEG C of glass transition temperature, the transmitance 90% at 450nm transmitances 88%, 400nm.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., be all included in the scope of protection of the present invention.
Claims (5)
1. a kind of polyamic acid, which is characterized in that obtained by polycondensation reaction with tetrabasic carboxylic acid dicarboxylic anhydride by diamine compound；Its
In,
The diamine compound is selected from following formula (II) compound：
The tetrabasic carboxylic acid dicarboxylic anhydride is selected from at least one of following compounds：
2. a kind of polyimides, which is characterized in that obtained first by polycondensation reaction with tetrabasic carboxylic acid dicarboxylic anhydride by diamine compound
Polyamic acid；Then polyamic acid dehydration closed-loop obtains；Wherein,
The diamine compound is selected from following formula (II) compound：
The tetrabasic carboxylic acid dicarboxylic anhydride is selected from at least one of following compounds：
3. polyimides according to claim 2, wherein the polyimides has following formula (V) structure：
Wherein, R is the quadrivalent organic radical that the tetrabasic carboxylic acid dicarboxylic anhydride is formed；Polymerization degree n is in 5 to 500 ranges.
4. a kind of optical thin film, which is characterized in that it is any by polyamic acid described in claim 1 and/or claim 2-3
Polyimides described in is prepared, alternatively, it contains polyamic acid described in claim 1 and/or claim 2-3 appoints
Polyimides described in one.
5. a kind of photoelectric device, which is characterized in that contain the optical thin film described in claim 4.
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| CN108530308B (en) * | 2018-06-06 | 2020-10-16 | 江苏创拓新材料有限公司 | Polyfluoro-substituted diamine compound and preparation method thereof |
| KR102577116B1 (en) | 2018-12-18 | 2023-09-11 | 주식회사 엘지화학 | Diamine compound, polyimide precursor and polyimide film prepared by using same |
| CN112430323B (en) * | 2020-11-26 | 2021-05-11 | 深圳瑞华泰薄膜科技股份有限公司 | Transparent polyimide film with excellent performance and preparation method thereof |
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