CN109796590A - A kind of polyimide resin and transparent polyimide film - Google Patents
A kind of polyimide resin and transparent polyimide film Download PDFInfo
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- CN109796590A CN109796590A CN201711139163.8A CN201711139163A CN109796590A CN 109796590 A CN109796590 A CN 109796590A CN 201711139163 A CN201711139163 A CN 201711139163A CN 109796590 A CN109796590 A CN 109796590A
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- dianhydride
- polyimide resin
- structural unit
- phenyl ring
- polyimide film
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Abstract
In order to solve the problems, such as that existing polyimide resin dissolubility is poor, the present invention provides a kind of polyimide resins and a kind of transparent polyimide film.Polyimide resin and transparent polyimide film provided by the invention include structural unit (a) and (b), and in structural unit (a), A is the residue of dianhydride, and the residue of the dianhydride includes the dianhydride residue containing phenyl ring；In structural unit (a) and (b): R1, R2Each independently represent hydrogen atom, halogen atom, itrile group, nitro, alkyl, alkoxy or phenyl ring class substituent group.The synthon of the film includes dianhydride and diamines, and the dianhydride includes dianhydride and fluorine-containing dianhydride containing phenyl ring；The diamines is selected from fluorenediamine.Polyimide resin dissolubility provided by the invention is good, has the characteristics that transmitance is high, heat-resist by transparent polyimide film prepared by polyimide resin.
Description
Technical field
The present invention relates to polyimides, in particular to a kind of polyimide resin and transparent polyimide film.
Background technique
Polyimides is most important kind in the aromatic heterocyclic copolymer to grow up nearly half a century, and uses temperature
Highest a kind of high molecular material is spent, there is the very excellent synthesis such as high mechanical strength, high temperature resistant, chemical stabilization, creep resistant
Performance, Aeronautics and Astronautics, electrical, machinery, microelectronics, in terms of be widely used.
Recently as the development of new high-tech industry, flexible OLED, flexible thin-film solar cell, light guide, waveguide and liquid
Demand of the optical fields such as crystal display to the polyimides of high heat resistance, high light transmission is more more and more urgent, such as: computer control is aobvious
Show, liquid crystal display, the cover of the optical components such as electronic display, polarizer, the substrate of flexible solar battery, flexibility
The substrate of OLED, the cover board of flexibility OLED and plastic lens etc..But traditional polyimide film generally show it is faint yellow or
Dark brown greatly limits further application of the polyimides in photoelectric material, the main reason is that due to main polymer chain
In in the dianhydride residue that is alternately present the electron effect of the electron attraction and diamines residue of carbonyl and the intramolecular that generates and
Intermolecular electric charge transfer forms complex compound.Therefore it needs by changing molecular structure, exploitation can be used for flexible solar battery
Bottom plate, the thermostable transparent polyimide resin material in the fields such as Flexible Displays or illumination bottom plate.
As resin for optical material, polymethyl methacrylate or polycarbonate are used all the time, these resins are most
Pipe has the excellent transparency, but heat resistance is lower, thus with higher temperature carry out using with cannot obtain on the way
Using.In addition, polycarbonate has slightly higher heat resistance than polymethyl methacrylate, but it is being applied to optics with high accuracy
There is a problem of when in element birefringent high.
In addition, the general dissolubility of polyimide resin in a solvent is lower.Therefore, usually with its precursor polyamic acid
State is coated as solution, is then converted to polyimides by carrying out heat treatment at high temperature.But this processing
There are certain restrictions for method, and the part of especially quasi- configuration polyimides is easy due to heat by irreversible damage, this
In the case of there is a problem of cannot using etc.；In addition, usually with shrinking when being cooled down after high-temperature process, to have more greatly
Now because of the serious problems such as film stripping, crackle caused by the thermal stress that generates at this time.
The alicyclic ring knot that people are distorted by introducing flexible group, fluoro-containing group, space structure in molecular backbone in recent years
Structure etc. has made some progress in terms of improving polyimides dissolubility, such as application No. is CN 201410263703.3 (to announce
Day: on October 29th, 2014) Chinese patent in, it is noted that a kind of diffluent clear polyimides resin and its preparation side
Method introduces the alicyclic structure of space structure distortion specially in molecular backbone, has biggish free volume and steric hindrance,
The dissolubility of clear polyimides is improved, still, improves dissolution by way of introducing alicyclic ring in polyimide molecule main chain
Property will be greatly reduced the heat resistance of polyimides；Authorization Notice No. is CN 100569833C (authorized announcement date: in December, 2009
16 days) Chinese patent in refer to a kind of fluorine-containing thermoplastic polyimide polymer and preparation method thereof, specially in polyamides
Fluoro-containing group and flexible ether linkage are introduced in imines main chain, improve the dissolubility of polyimides, still, this method can be reduced seriously
The glass transition temperature of polyimides, influences subsequent use.
Summary of the invention
In order to solve the problems, such as that existing polyimide resin dissolubility is poor, the present invention provides a kind of polyimide resin and
A kind of transparent polyimide film.Polyimides provided by the invention in polyimides main chain by introducing the big side group list containing fluorenes
Member, structural unit containing F and backbone unit, can greatly improve the solubility property of polyimide resin in a solvent, by gathering
The transparent polyimide film of imide resin preparation has the characteristics that visible light transmittance is high, heat-resist.
In order to solve the above technical problem, the present invention provides following technical schemes:
The present invention provides a kind of polyimide resin, and the polyimide resin includes following structural units:
Wherein, in structural unit (a), A is the residue of dianhydride, and the residue of the dianhydride includes that the dianhydride containing phenyl ring is residual
Base；In structural unit (a) and (b): R1, R2Each independently represent hydrogen atom, halogen atom, itrile group, nitro, alkyl, alkoxy
Substituent group or phenyl ring.
Further, halogen atom is selected from one of fluorine, chlorine, bromine or iodine；The alkyl in methyl, ethyl one
Kind；The alkoxy is selected from methoxyl group；The phenyl ring is single phenyl ring.
Structure above (b) indicates fluorine-containing dianhydride.
Further, the dianhydride residue containing phenyl ring includes N number of phenyl ring, 3≤N≤6.
Further, dianhydride residue of the dianhydride residue containing phenyl ring selected from N=3 and the dianhydride including 3 N≤6 ﹤ are residual
One of base or at least two combination.
Further, the dianhydride residue containing phenyl ring is containing there are three phenyl ring or four phenyl ring or five phenyl ring or six
A phenyl ring.
The dianhydride residue containing phenyl ring is selected from following combinations:
The combination of dianhydride residue and another dianhydride residue including three phenyl ring including three phenyl ring, including three benzene
The combination of the dianhydride residue of ring and the dianhydride residue including four phenyl ring, dianhydride residue including three phenyl ring and including five benzene
The combination of the dianhydride residue of ring, the combination of dianhydride residue and the dianhydride residue including five phenyl ring including four phenyl ring, including
The combination of the dianhydride residue and another dianhydride residue including four phenyl ring of four phenyl ring.
Further, the weight average molecular weight of the polyimides is 5000~500,000.
Further, the molar ratio of the structural unit (a) and structural unit (b) is 1-9:1-9.
Further, the molar ratio of the structural unit (a) and structural unit (b) is 0.225-9:1.
Further, the molar ratio of the structural unit (a) and structural unit (b) is 1.45-9:1.
Further, the polyimide resin be soluble in n,N-Dimethylformamide, n,N-dimethylacetamide,
Sulfolane, metacresol, dimethyl sulfoxide, N-Methyl pyrrolidone, diphenyl sulphone (DPS), tetrahydrofuran, chloroform, acetone, gamma-butyrolacton,
In one of methanol or at least two combined solvents.
Further, the polyimide resin be soluble in one of tetrahydrofuran, chloroform, acetone or methanol or
In at least two combined low boiling point solvents.
Further, the glass transition temperature of the polyimides is 260 DEG C~340 DEG C.
Further, the glass transition temperature of the polyimides is 290 DEG C~340 DEG C.
Further, the glass transition temperature of the polyimides is 310 DEG C~340 DEG C.
Further, the glass transition temperature of the polyimides is measured by differential scanning calorimetry.
Further, the transparent polyimide film includes following structural units:
Wherein, in structural unit (a), A is the residue of dianhydride, and the residue of the dianhydride includes that the dianhydride containing phenyl ring is residual
Base；In structural unit (a) and (b): R1, R2Each independently represent hydrogen atom, halogen atom, itrile group, nitro, alkyl, alcoxyl
Base or phenyl ring class substituent group.
Further, the polyimides is random copolymer or alternate copolymer.
Further, the dianhydride residue containing phenyl ring includes N number of phenyl ring, 3≤N≤6.
The dianhydride residue containing phenyl ring is selected from the dianhydride residue including N=3 and the dianhydride residue including 3 N≤6 ﹤
It is a kind of or at least two combination.
Further, the dianhydride residue containing phenyl ring is containing there are three phenyl ring or four phenyl ring or five phenyl ring or six
A phenyl ring.
The residue of the dianhydride containing phenyl ring is selected from following combinations:
The combination of dianhydride residue and another dianhydride residue including three phenyl ring including three phenyl ring, including three benzene
The combination of the dianhydride residue of ring and the dianhydride residue including four phenyl ring, dianhydride residue including three phenyl ring and including five benzene
The combination of the dianhydride residue of ring, the combination of dianhydride residue and the dianhydride residue including five phenyl ring including four phenyl ring, including
The combination of the dianhydride residue and another dianhydride residue including four phenyl ring of four phenyl ring.
Further, the Kapton includes following structures:
Wherein, m, n are positive integer, 1≤m≤99,1≤n≤99.
Further, the value of m is preferably 10-50, and the value of n is preferably 10-50.
Further, the transparent polyimide film is white clear Kapton.
Further, the molar ratio of the structural unit (a) and structural unit (b) is 1-9:1-9.
Further, the molar ratio of the structural unit (a) and structural unit (b) is 0.225-9:1.
Further, the molar ratio of the structural unit (a) and structural unit (b) is 1.45-9:1.
Further, the A is selected from the combination of one of following structural unit or at least two:
Further, preferably, A is selected from the combination of one of following structural unit or at least two:
Further, the R1And R2It is respectively selected from the combination of one of following structural unit or at least two:
Further, preferably, R1And R2It is respectively selected from one or two kinds of combinations of following structural unit:
-H -F。
Further, the synthon of the film includes dianhydride and diamines, the dianhydride include dianhydride containing phenyl ring and
Fluorine-containing dianhydride；The diamines is selected from fluorenediamine.
Further, the diamines be selected from hydrogen atoms, halogen atom, itrile group, nitro, alkyl, alkoxy, phenyl ring fluorenes two
One of amine or at least two combination.
Further, halogen atom is selected from one of fluorine, chlorine, bromine or iodine；The alkyl in methyl, ethyl one
Kind；The alkoxy is selected from methoxyl group；The phenyl ring is single phenyl ring.
Further, the dianhydride containing phenyl ring is the long-chain dianhydride containing phenyl ring.
Further, the dianhydride containing phenyl ring includes N number of phenyl ring, 3≤N≤6.
Further, the dianhydride containing phenyl ring is selected from one in the dianhydride including N=3 and dianhydride including 3 N≤6 ﹤
Kind or at least two combination.
Further, the dianhydride containing phenyl ring preferably comprise the dianhydride of three phenyl ring or including four phenyl ring two
Acid anhydride.
Further, the dianhydride containing phenyl ring is preferably two ether dianhydride of bisphenol-A or 3,3- triphen diether tetracarboxylic acid dianhydride.
Further, the structural formula of the long-chain dianhydride containing phenyl ring is selected from one of following structural formula or at least two
Combination:
Further, the structural formula of the long-chain dianhydride containing phenyl ring is preferably
Further, the fluorine-containing dianhydride is 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids (6FDA).
Further, the structural formula of the diamines are as follows:
Wherein, R1And R2It is respectively selected from the combination of one of following structural unit or at least two:
- H ,-CH3,-OCH3,-CH2CH3,-NO2,-CN ,-F ,-Cl ,-Br ,-I,
Further, the diamines is preferably bis- (the fluoro- 4- aminophenyl of the 3-) fluorenes of 9,9-.
Further, the present invention also provides a kind of preparation method of transparent polyimide film, the method includes following
Step:
(1) it dissolves diamines: diamines and organic solvent being added in there-necked flask, stirs under nitrogen protection；
(2) polycondensation reaction: dianhydride and organic solvent is added after diamines dissolution, carries out polycondensation reaction；
(3) end capping reaction: end-capping reagent is added, is blocked, obtains polyamic acid solution；
(4) acetic anhydride and basic catalyst imidization reaction: are added in the polyamic acid solution that step (3) obtains
Mixed solution is stirred to react 2~24 hours, and cyclodehydration obtains polyimide solution；
(5) polyimide solution in step (4) is poured into precipitating reagent and is precipitated, sufficiently washed after collecting precipitating, it is dry,
Polyimide resin powder end is made；
(6) be coated on after dissolving at the polyimide resin powder end that step (5) obtains in organic solvent supporter (such as
Clean glass plate) on, transparent polyimide film is obtained by heating plate and oven drying and removal solvent.
Further, the organic solvent is polar non-solute or nonpolar solvent.
Further, the organic solvent be selected from n,N-Dimethylformamide, n,N-dimethylacetamide, sulfolane,
Metacresol, methyl sulfoxide, N-Methyl pyrrolidone, diphenyl sulphone (DPS), tetrahydrofuran, chloroform, acetone, gamma-butyrolacton, one in methanol
Kind or several combinations.
Further, the precipitating reagent is selected from the combination of one or both of ethyl alcohol, deionized water.
Further, the acetic anhydride is dehydrating agent.
Further, the basic catalyst is selected from the alkali gold of carbonate, bicarbonate, hydroxide, organic base, alcohol
Belong to the combination of one of salt, metal hydride, pyridine, isoquinolin, triethylamine or at least two.
Further, the preparation method of the Kapton further includes addition end-capping reagent progress after the completion of polycondensation reaction
Sealing end, the end-capping reagent are phthalic anhydride.
Further, the structural formula of phthalic anhydride are as follows:
Further, the feed ratio of the dianhydride monomer and diamine monomer is 96-100:96-100, and the ratio is to rub
That ratio.
Further, the feed ratio of the dianhydride monomer and diamine monomer is preferably 97-100:100.
Further, the feed ratio of the dianhydride monomer and diamine monomer is preferably 98-100:100.
Further, the feed ratio of the long-chain dianhydride in the dianhydride monomer containing phenyl ring and fluorine-containing dianhydride is 1-9:1-9,
The ratio is molar ratio.
Further, the feed ratio of the long-chain dianhydride in the dianhydride monomer containing phenyl ring and fluorine-containing dianhydride is 0.225-9:
1。
Further, the feed ratio of the long-chain dianhydride in the dianhydride monomer containing phenyl ring and fluorine-containing dianhydride is 1.45-9:
1。
Further, it is more right than dense when concentration of the polyimide resin in N-Methyl pyrrolidone is 0.5g/dL
Number viscosity is 0.3dL/g~1.2dL/g.
Further, it is more right than dense when concentration of the Kapton in N-Methyl pyrrolidone is 0.5g/dL
Number viscosity is 0.3dL/g~1.2dL/g.
Further, the logarithmic viscosity number is 0.5dL/g~0.8dL/g.
Further, for the logarithmic viscosity number by determination of ubbelohde viscometer, measuring temperature is 30 DEG C.
Further, average transmittance of transparent polyimide film when with a thickness of 15~25 μm, at 550nm
It is 86% or more.
Further, average transmittance of transparent polyimide film when with a thickness of 15~21 μm, at 550nm
It is 89.0% or more.
Further, the optical transmittance of the Kapton (with a thickness of 15~25 μm, wavelength is at 550nm) is logical
Cross ultra-violet and visible spectrophotometer measurement.
The present invention also provides a kind of preparation methods of polyimide resin, the described method comprises the following steps:
(1) in the reaction vessel, diamine monomer is added in nitrogen or the organic solvent of inert gas shielding, stirring makes
It is added dianhydride monomer and carries out polycondensation reaction after being completely dissolved, stirring obtains polyamic acid solution in 3~48 hours；
(2) mixed solution of acetic anhydride and basic catalyst, stirring are added in the polyamic acid solution that step (1) obtains
Reaction 2~24 hours, cyclodehydration obtains polyimide solution；
(3) polyimide solution in step (2) is poured into precipitating reagent and is precipitated, sufficiently washed after collecting precipitating, it is dry,
Polyimide resin powder end is made.
The present invention also provides the preparation methods of another polyimide resin, which comprises
(1) in the reaction vessel, dianhydride monomer, diamine monomer, organic solvent is added, mixes well；It is heated to reflux band water
Under the conditions of imidization reaction occurs；
(2) reaction product is poured into precipitating reagent after cooling, is filtered, sufficiently washed after collecting precipitating, dry, obtained polyamides
Imide resin powder；
Further, the preparation method of above two polyimide resin further includes squeezing out polyimide resin powder end to make
Grain prepares polyimide resin particle.
The present invention also provides the preparation method of another Kapton, the method also be may comprise steps of:
(a) resin dissolves: in organic solvent by the polyimide resin dissolution；
(b) remove solvent: the polyimide solution that step (a) is obtained is coated on supporter (such as clean glass plate)
On, transparent polyimide film is obtained by heating plate and oven drying and removal solvent.
In conclusion polyimide resin provided by the invention and Kapton have the advantages that
(1) due to using copolymerization by the way of prepare the transparent polyimide film, can significantly improve prepare this it is transparent gather
The solubility property of resin needed for imide membrane and the transmitance of the transparent polyimide film；
(2) molecular weight can be regulated and controled by end-capping reagent, convenient for preparing the polyimide resin of different solubility properties；
(3) introducing of structural unit containing F and the big side unit containing fluorenes, can greatly improve the saturating of transparent polyimide film
Cross rate；
(4) introducing of the big side unit containing fluorenes, can significantly improve the glass transition temperature of transparent polyimide film；
(5) introducing of backbone unit can significantly improve the dissolubility of polyimide resin and improve polymer and close
At when reactivity.
Therefore, polyimide resin dissolubility provided by the invention is good, and the transparent polyamides by polyimide resin preparation is sub-
It is high, heat-resist that amine film has the characteristics that transmitance, and it is sub- that bright polyamides can be prepared to avoid polyimide acid solution coating
Amine film is shunk by irreversible damage due to heat and when being cooled down after high-temperature process, or is caused because of thermal stress
The serious problems such as film stripping, crackle.Transparent polyimide film provided by the invention is in flexible OLED, flexible thin-film solar
The optical fields such as battery, light guide, waveguide and liquid crystal display have a good application prospect.
Detailed description of the invention
Fig. 1 is the structural unit of polyimide resin provided by the invention.
Specific embodiment
Below in conjunction with specific embodiment, present invention is further described in detail, it is necessary to be pointed out that the present embodiment is only used
It is further detailed in the present invention, should not be understood as limiting the scope of the invention.Technology in the field is ripe
Some nonessential modifications and adaptations can be made according to the content of foregoing invention by practicing personnel.
Polyimide resin and transparent polyimide film provided by the invention the preparation method comprises the following steps:
The preparation method of polyimide resin provided by the invention:
(1) in the reaction vessel, it is mixed well after dianhydride monomer, diamine monomer, organic solvent being added, in basic catalyst
Condition heating is lower to occur polycondensation reaction, generates polyimides；
(2) reaction product in step (1) is cooling, it pours into precipitating reagent and is precipitated, filter, sufficiently washed after collecting precipitating
It washs, it is dry, polyimide resin powder end is made.
Another preparation method of polyimide resin provided by the invention:
(1) in the reaction vessel, diamine monomer is added in nitrogen or the organic solvent of inert gas shielding, stirring makes
It is added dianhydride monomer and carries out polycondensation reaction after being completely dissolved, stirring obtains polyamic acid solution in 3~48 hours；
(2) mixed solution of acetic anhydride and basic catalyst, stirring are added in the polyamic acid solution that step (1) obtains
Reaction 2~24 hours, cyclodehydration obtains polyimide solution；
(3) polyimide solution in step (2) is poured into precipitating reagent and is precipitated, sufficiently washed after collecting precipitating, it is dry,
Polyimide resin powder end is made.
Further, the preparation method of above-mentioned polyimide resin further includes by polyimide resin powder end extruding pelletization system
Standby polyimide resin particle.
The preparation method of transparent polyimide film provided by the invention the following steps are included:
(1) it dissolves diamines: diamines and organic solvent being added in there-necked flask, stirs under nitrogen protection；
(2) polycondensation reaction: dianhydride and organic solvent is added after diamines dissolution, carries out polycondensation reaction；
(3) end capping reaction: end-capping reagent is added, is blocked, obtains polyamic acid solution；
(4) acetic anhydride and basic catalyst imidization reaction: are added in the polyamic acid solution that step (3) obtains
Mixed solution is stirred to react 2~24 hours, and cyclodehydration obtains polyimide solution；
(5) polyimide solution in step (4) is poured into precipitating reagent and is precipitated, sufficiently washed after collecting precipitating, it is dry,
Polyimide resin powder end is made；
(6) be coated on after dissolving at the polyimide resin powder end that step (5) obtains in organic solvent supporter (such as
Clean glass plate) on, transparent polyimide film is obtained by heating plate and oven drying and removal solvent.
The polyimide resin and transparent polyimide film that the present invention is prepared carry out performance survey by the following method
Examination:
Logarithmic viscosity number: when concentration of the polyimide resin in N-Methyl pyrrolidone is 0.5g/dL, pass through Ubbelohde
Viscosimeter measures its logarithmic viscosity number at 30 DEG C.When the logarithmic viscosity number of resin is big, the mechanical property of material can be promoted,
But the excessive solubility property that will affect material.Logarithmic viscosity number is bigger, and molecular weight is bigger.
Glass transition temperature: it is measured by differential scanning calorimetry.Theoretically the glass transition temperature of resin is higher
It is better, but in general, glass transition temperature is high, then structural rigidity is stronger, need to increase the ratio of big pendant group, unfavorable
In the raising of polymer molecular weight.
Dissolubility: by the way that polyimide resin is made into 10% solid content from different organic solvents in teat glass
Solution, observe its dissolution situation under room temperature (25 DEG C) and under alcolhol burner heated condition.
Transmitance: the transmitance for the light that wavelength is 550nm is measured by ultra-violet and visible spectrophotometer.Transmitance is higher
It is better, advantageously reduce light loss when device uses.
Embodiment 1:
Bis- (the fluoro- 4- aminobenzenes of 3- of 19.2210g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 19.9908g (0.045mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 4,4'- (4,4'- hexafluoro isopropyls
Two phenoxy group of alkene) two anhydride phthalic acid 2.6025g (0.005mol) bisphenol-A diether dianhydride monomers, 360mL metacresol, 12 drop isoquinolin,
Under nitrogen protection, it reacts 2 hours for 120 DEG C；It then heats to 200 DEG C to react 10 hours, is cooled to 100 DEG C, 1.1850g is added
(0.008mol) phthalic anhydride, the reaction was continued 2 hours, is cooled to room temperature, and reaction solution is poured slowly into 2L ethyl alcohol and is precipitated,
Filtering, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 150 DEG C of vacuum drying ovens 8 hours dry, obtain white polyimides
Toner 38.39g, yield 91.8%；After the white polyimide resin powder end is dissolved in tetrahydrofuran, dry
Coating film forming on dry, clean glass plate, then the dry 30min in 50 DEG C of heating plate, does in 180 DEG C of vacuum drying oven
Dry 2h uses boiling water boiling after cooling taking-up, until the transparent polyimide film is removed on a glass, obtains with a thickness of 20 μm
Transparent polyimide film.The test result of transparent polyimide film performance is shown in Table 1.
Embodiment 2:
Bis- (the fluoro- 4- aminobenzenes of 3- of 19.2210g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 200mL n,N-dimethylacetamide, stirring at normal temperature adds after diamine monomer all dissolution under nitrogen protection
Enter 2.2212g (0.005mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 23.4221g (0.045mol) bisphenol-A diether
Normal-temperature reaction 24 hours, the mixed solution of acetic anhydride and triethylamine was added in dianhydride monomer, 50mL n,N-dimethylacetamide
30ml (wherein 22mL acetic anhydride, 8mL triethylamine) continues normal-temperature reaction 12 hours, reaction solution is poured slowly into 2L deionized water
Middle precipitation, filtering, gained filter cake is boiled with ethyl alcohol to be washed 3 times, be placed in 140 DEG C of vacuum drying ovens 6 hours dry, it is poly- to obtain white
Imide resin powder 40.96g, yield 91.3%；By the white polyimide resin powder end in N-Methyl pyrrolidone
After dissolution, then the coating film forming on drying, clean glass plate dries 30min, at 260 DEG C in 80 DEG C of heating plate
Dry 1h in vacuum drying oven, uses boiling water boiling after cooling taking-up, until the transparent polyimide film is removed on a glass, obtains
To the transparent polyimide film with a thickness of 22 μm.The test result of transparent polyimide film performance is shown in Table 1.
Embodiment 3:
Bis- (the fluoro- 4- aminobenzenes of 3- of 19.2210g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 12.8830g (0.029mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 10.4098g (0.020mol)
Bisphenol-A diether dianhydride monomer, 355mL metacresol, 10 drop isoquinolin, under nitrogen protection, 140 DEG C are reacted 2 hours；Then it heats up
It is reacted 8 hours to 200 DEG C, is cooled to 100 DEG C, 0.5925g (0.004mol) phthalic anhydride is added, the reaction was continued 5 hours,
Be cooled to room temperature, reaction solution be poured slowly into 3L ethyl alcohol and is precipitated, filter, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed on
It is 4 hours dry in 120 DEG C of vacuum drying ovens, obtain white polyimide resin powder end 38.46g, yield 90.4%；By the white
After polyimide resin powder end is dissolved in n,N-dimethylacetamide, the coating film forming on drying, clean glass plate, then
The dry 30min in 80 DEG C of heating plate, the dry 2h in 290 DEG C of vacuum drying oven, uses boiling water boiling after cooling taking-up, until will
The transparent polyimide film is removed on a glass, obtains the transparent polyimide film with a thickness of 21 μm.Transparent polyamides is sub-
The test result of amine film performance is shown in Table 1.
Embodiment 4:
Bis- (the fluoro- 4- aminobenzenes of 3- of 19.2210g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 220mL n,N-dimethylacetamide, stirring at normal temperature adds after diamine monomer all dissolution under nitrogen protection
Enter 8.2184g (0.0185mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 15.6147g (0.030mol) bisphenol-A diether
Normal-temperature reaction 24 hours, the mixed solution 30ml of acetic anhydride and pyridine was added in dianhydride monomer, 20mL n,N-dimethylacetamide
(wherein 22mL acetic anhydride, 8mL pyridine) continues normal-temperature reaction 12 hours, reaction solution is poured slowly into 3L deionized water and is precipitated,
Filtering, gained filter cake is boiled with ethyl alcohol to be washed 3 times, be placed in 120 DEG C of vacuum drying ovens 10 hours dry, obtain white polyimides
Toner 40.96g, yield 91.3%；The white polyimide resin powder end is dissolved in DMAC N,N' dimethyl acetamide
Afterwards, the coating film forming on drying, clean glass plate, then dries 30min, in 280 DEG C of vacuum in 80 DEG C of heating plate
Dry 1h in baking oven, uses boiling water boiling after cooling taking-up, until the transparent polyimide film is removed on a glass, obtains thickness
The transparent polyimide film that degree is 19 μm.The test result of transparent polyimide film performance is shown in Table 1.
Embodiment 5:
Bis- (4- aminophenyl) the fluorenes lists of 17.4220g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Body, 200mL n,N-dimethylacetamide, stirring at normal temperature is added after diamine monomer all dissolution under nitrogen protection
17.5475g (0.0395mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 4.0232g (0.010mol) 3,3- triphen two
Normal-temperature reaction 12 hours, the mixing of acetic anhydride and pyridine was added in ether tetracarboxylic acid dianhydride monomer, 20mL n,N-dimethylacetamide
Solution 30ml (wherein 22mL acetic anhydride, 8mL pyridine) continues normal-temperature reaction 6 hours, reaction solution is poured slowly into 2L deionized water
Middle precipitation, filtering, gained filter cake is boiled with ethyl alcohol to be washed 3 times, be placed in 120 DEG C of vacuum drying ovens 10 hours dry, obtain white
Polyimide resin powder end 35.60g, yield 91.3%；After the white polyimide resin powder end is dissolved in acetone,
It dries, coating film forming on clean glass plate, then the dry 20min in 50 DEG C of heating plate, in 160 DEG C of vacuum drying oven
Dry 1h uses boiling water boiling after cooling taking-up, until the transparent polyimide film is removed on a glass, obtains with a thickness of 19
μm transparent polyimide film.The test result of transparent polyimide film performance is shown in Table 1.
Embodiment 6:
Bis- (4- aminophenyl) the fluorenes lists of 17.4220g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Body, 180mL n,N-dimethylacetamide, stirring at normal temperature is added after diamine monomer all dissolution under nitrogen protection
3.9982g (0.009mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 16.0928g (0.040mol) 3,3- triphen diether
Tetracarboxylic acid dianhydride monomer, 20mL n,N-dimethylacetamide, normal-temperature reaction 12 hours, the mixing that acetic anhydride and pyridine is added was molten
Liquid 30ml (wherein 22mL acetic anhydride, 8mL pyridine) continues normal-temperature reaction 10 hours, reaction solution is poured slowly into 2L deionized water
Middle precipitation, filtering, gained filter cake is boiled with ethyl alcohol to be washed 3 times, be placed in 120 DEG C of vacuum drying ovens 10 hours dry, obtain white
Polyimide resin powder end 34.51g, yield 92.0%；After the white polyimide resin powder end is dissolved in acetone,
It dries, coating film forming on clean glass plate, then the dry 20min in 50 DEG C of heating plate, in 180 DEG C of vacuum drying oven
Dry 2h uses boiling water boiling after cooling taking-up, until the transparent polyimide film is removed on a glass, obtains with a thickness of 22
μm transparent polyimide film.The test result of transparent polyimide film performance is shown in Table 1.
Embodiment 7:
Bis- (the fluoro- 4- aminobenzenes of 3- of 19.2210g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 15.5484g (0.035mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 6.0348g (0.015mol) 4,
4- triphen diether tetracarboxylic acid dianhydride monomer, 340mL metacresol, 10 drop isoquinolin, under nitrogen protection, 120 DEG C are reacted 2 hours；
It then heats to 200 DEG C to react 10 hours, is cooled to 100 DEG C, 0.2963g (0.002mol) phthalic anhydride is added, continue
Reaction 2 hours, is cooled to room temperature, reaction solution is poured slowly into 2L ethyl alcohol and is precipitated, and filters, and gained filter cake is boiled with ethyl alcohol to be washed 2 times,
Be placed in 180 DEG C of vacuum drying ovens 8 hours dry, obtain white polyimide resin powder end 37.3g, yield 91.5%；
After the white polyimide resin powder end is dissolved in n,N-dimethylacetamide, it is coated on drying, clean glass plate
It forms a film, then the dry 30min in 100 DEG C of heating plate, the dry 2h in 280 DEG C of vacuum drying oven uses boiling after cooling taking-up
Boiling obtains the transparent polyimide film with a thickness of 20 μm until the transparent polyimide film is removed on a glass.
The test result of transparent polyimide film performance is shown in Table 1.
Embodiment 8:
Bis- (the fluoro- 4- aminobenzenes of 3- of 19.2210g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 6.2194g (0.014mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 14.0812g (0.035mol) 4,
4- triphen diether tetracarboxylic acid dianhydride monomer, 320mL metacresol, 10 drop isoquinolin, under nitrogen protection, 120 DEG C are reacted 4 hours；
It then heats to 190 DEG C to react 10 hours, is cooled to 100 DEG C, 0.5926g (0.004mol) phthalic anhydride is added, continue
Reaction 2 hours, is cooled to room temperature, reaction solution is poured slowly into 3L ethyl alcohol and is precipitated, and filters, and gained filter cake is boiled with ethyl alcohol to be washed 2 times,
Be placed in 150 DEG C of vacuum drying ovens 8 hours dry, obtain white polyimide resin powder end 36.4g, yield 92.0%；
After the white polyimide resin powder end is dissolved in n,N-dimethylacetamide, it is coated on drying, clean glass plate
Film forming, then the dry 40min in 70 DEG C of heating plate, the dry 2h in 280 DEG C of vacuum drying oven use boiling water after cooling taking-up
It boils, until the transparent polyimide film is removed on a glass, obtains the transparent polyimide film with a thickness of 20 μm.Thoroughly
The test result of bright Kapton performance is shown in Table 1.
Embodiment 9:
Bis- (3- methyl -4- the aminobenzenes of 20.2275g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 220mL n,N-dimethylacetamide, stirring at normal temperature adds after diamine monomer all dissolution under nitrogen protection
Enter 2.2212g (0.005mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 22.3811g (0.043mol) bisphenol-A diether
Normal-temperature reaction 24 hours, the mixed solution of acetic anhydride and triethylamine was added in dianhydride monomer, 50mL n,N-dimethylacetamide
30ml (wherein 22mL acetic anhydride, 8mL triethylamine) continues normal-temperature reaction 12 hours, reaction solution is poured slowly into 2L deionized water
Middle precipitation, filtering, gained filter cake is boiled with ethyl alcohol to be washed 3 times, be placed in 140 DEG C of vacuum drying ovens 6 hours dry, it is poly- to obtain white
Imide resin powder 40.93g, yield 91.3%；By the white polyimide resin powder end in N-Methyl pyrrolidone
After dissolution, then the coating film forming on drying, clean glass plate dries 30min, at 260 DEG C in 80 DEG C of heating plate
Dry 1h in vacuum drying oven, uses boiling water boiling after cooling taking-up, until the transparent polyimide film is removed on a glass, obtains
To the transparent polyimide film with a thickness of 22 μm.The test result of transparent polyimide film performance is shown in Table 1.
Embodiment 10:
Bis- (3- cyanogen -4- the aminobenzenes of 22.4240g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 11.1060g (0.025mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 15.7108g (0.025mol)
4,4'- (4,4'- hexafluoro isopropyl alkene, two phenoxy group) two phthalandione anhydride monomers, 380mL metacresol, 12 drop isoquinolin, in nitrogen protection
Under, 100 DEG C are reacted 2 hours；It then heats to 190 DEG C to react 10 hours, is cooled to 100 DEG C, be added 1.1850g (0.008mol)
Phthalic anhydride, the reaction was continued 2 hours, is cooled to room temperature, and reaction solution is poured slowly into 3L ethyl alcohol and is precipitated, filtering, gained
Filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 140 DEG C of vacuum drying ovens 8 hours dry, obtain white polyimide resin powder end
45.11g, yield 91.6%；After the white polyimide resin powder end is dissolved in tetrahydrofuran, in drying, clean
Coating film forming on glass plate, then the dry 20min in 80 DEG C of heating plate, the drying 2h in 250 DEG C of vacuum drying oven, cooling
Boiling water boiling is used after taking-up, until the transparent polyimide film is removed on a glass, is obtained transparent poly- with a thickness of 22 μm
Imide membrane.The test result of transparent polyimide film performance is shown in Table 1.
Embodiment 11:
Bis- (3- methyl -4- the aminobenzenes of 20.2275g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 200mL n,N-dimethylacetamide, stirring at normal temperature adds after diamine monomer all dissolution under nitrogen protection
Enter 11.1060g (0.025mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 12.6605g (0.025mol) 4,4'- (4,
Bis- phenoxy group ketone of 4'-) two phthalandione anhydride monomers, 20mL n,N-dimethylacetamide, normal-temperature reaction 12 hours, be added acetic anhydride with
The mixed solution 30ml (wherein 22mL acetic anhydride, 8mL pyridine) of pyridine continues normal-temperature reaction 10 hours, reaction solution is slowly fallen
Enter and be precipitated in 2L deionized water, filtered, gained filter cake is boiled with ethyl alcohol to be washed 3 times, to be placed in 120 DEG C of vacuum drying ovens dry 10 small
When, obtain white polyimide resin powder end 40.47g, yield 92.0%；By the white polyimide resin powder end in tetrahydro
After dissolving in furans, then the coating film forming on drying, clean glass plate dries 20min in 50 DEG C of heating plate,
Dry 2h in 180 DEG C of vacuum drying oven, uses boiling water boiling after cooling taking-up, until on a glass by the transparent polyimide film
It removes, obtains the transparent polyimide film with a thickness of 21 μm.The test result of transparent polyimide film performance is shown in Table 1.
Embodiment 12:
Bis- (3- methoxyl group -4- the amino of 23.4270g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Phenyl) fluorenes monomer, 220mL n,N-dimethylacetamide, stirring at normal temperature under nitrogen protection, after diamine monomer all dissolution,
11.1060g (0.025mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 13.5618g (0.025mol) 4,4'- is added
Normal-temperature reaction 10 hours, acetic anhydride was added in (4,4'- bis- phenoxy group sulfone) two phthalandione anhydride monomers, 20mL n,N-dimethylacetamide
With the mixed solution 30ml (wherein 22mL acetic anhydride, 8mL pyridine) of pyridine, continues normal-temperature reaction 8 hours, reaction solution is slowly fallen
Enter and be precipitated in 3L deionized water, filtered, gained filter cake is boiled with ethyl alcohol to be washed 3 times, to be placed in 150 DEG C of vacuum drying ovens dry 10 small
When, obtain white polyimide resin powder end 44.00g, yield 91.5%；By the white polyimide resin powder end in first
After being dissolved in the mixed solution of alcohol/tetrahydrofuran (1:1), the coating film forming on drying, clean glass plate, then at 50 DEG C
Dry 20min in heating plate, the dry 2h in 150 DEG C of vacuum drying oven, uses boiling water boiling after cooling taking-up, until this is transparent poly-
Imide membrane is removed on a glass, obtains the transparent polyimide film with a thickness of 20 μm.Transparent polyimide film
The test result of energy is shown in Table 1.
Embodiment 13:
Bis- (the fluoro- 4- aminobenzenes of 3- of 18.4522g (0.048mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 200mL n,N-dimethylacetamide, stirring at normal temperature adds after diamine monomer all dissolution under nitrogen protection
Enter 2.2212g (0.005mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 23.4221g (0.045mol) bisphenol-A diether
Normal-temperature reaction 18 hours, the mixed solution of acetic anhydride and triethylamine was added in dianhydride monomer, 30mL n,N-dimethylacetamide
30ml (wherein 22mL acetic anhydride, 8mL triethylamine) continues normal-temperature reaction 12 hours, reaction solution is poured slowly into 2L deionized water
Middle precipitation, filtering, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 160 DEG C of vacuum drying ovens 6 hours dry, it is poly- to obtain white
Imide resin powder 40.35g, yield 91.5%；By the white polyimide resin powder end in N-Methyl pyrrolidone
After dissolution, then the coating film forming on drying, clean glass plate dries 30min, at 262 DEG C in 80 DEG C of heating plate
Dry 1h in vacuum drying oven, uses boiling water boiling after cooling taking-up, until the transparent polyimide film is removed on a glass, obtains
To the transparent polyimide film with a thickness of 20 μm.The test result of transparent polyimide film performance is shown in Table 1.
Comparative example 1:
Bis- (the fluoro- 4- aminobenzenes of 3- of 19.2210g (0.050mol) 9,9- are added in the 500mL there-necked flask of dried and clean
Base) fluorenes monomer, 22.2120g (0.050mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 330mL metacresol, 10 drop it is different
Quinoline, under nitrogen protection, 120 DEG C are reacted 2 hours；It then heats to 200 DEG C to react 10 hours, is cooled to 100 DEG C, be added
0.2963g (0.002mol) phthalic anhydride, the reaction was continued 2 hours, is cooled to room temperature, and reaction solution is poured slowly into 2L ethyl alcohol
Middle precipitation, filtering, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 180 DEG C of vacuum drying ovens 8 hours dry, it is poly- to obtain white
Imide resin powder 37.5g, yield 90.5%；By the white polyimide resin powder end in DMAC N,N' dimethyl acetamide
After dissolution, then the coating film forming on drying, clean glass plate dries 30min, at 280 DEG C in 100 DEG C of heating plate
Dry 2h in vacuum drying oven, discovery film is gone to sticks and staves after cooling taking-up.
Comparative example 2:
16.0130g (0.050mol) 4,4 '-diamino -2,2 '-bis- three is added in the 500mL there-necked flask of dried and clean
Methyl fluoride biphenyl monomer, 200mL n,N-dimethylacetamide, stirring at normal temperature, all dissolves to diamine monomer under nitrogen protection
Afterwards, addition 22.2120g (0.050mol) 4,4'- (hexafluoro isopropyl alkene) two phthalandione anhydride monomers, 20mL n,N-dimethylacetamide,
Normal-temperature reaction 12 hours, the mixed solution 30ml (wherein 22mL acetic anhydride, 8mL pyridine) of acetic anhydride and pyridine is added, continues normal
Temperature reaction 10 hours, reaction solution is poured slowly into 2L deionized water and is precipitated, and is filtered, and gained filter cake is boiled with ethyl alcohol washes 3 times, later
Drying 10 hours in 120 DEG C of vacuum drying ovens are placed in, white polyimide resin powder end 35.2g, yield 92.0% are obtained；It should
After white polyimide resin powder end is dissolved in n,N-dimethylacetamide, the coating film forming on drying, clean glass plate,
Then the dry 20min in 80 DEG C of heating plate, the dry 2h in 280 DEG C of vacuum drying oven, uses boiling water boiling after cooling taking-up, directly
The transparent polyimide film is removed on a glass extremely, obtains the transparent polyimide film with a thickness of 21 μm.It is transparent poly-
The test result of imide membrane performance is shown in Table 1.
The polyimide resin powder end that embodiment 1- embodiment 13 and comparative example 1-2 obtain is weighed into 1.0g respectively, is added
Into test tube, then it is separately added into the n,N-dimethylacetamide of 10.0g, N-Methyl pyrrolidone, tetrahydrofuran, chlorine in test tube
Imitative, acetone, methanol, methanol and tetrahydrofuran 1:1 mixed solution, observes its dissolution feelings at normal temperature and under heated condition
Condition.The dissolubility test result at polyimide resin powder end is shown in Table 2.
The performance test results of the transparent polyimide film of table 1 embodiment 1-13 and comparative example 1-2 preparation
The solubility property test result at the polyimide resin powder end of table 2 embodiment 1-13 and comparative example 1-2 preparation
Note: ++ it indicates to dissolve under room temperature ,+indicate to dissolve under heated condition ,+- indicates part under heated condition
Dissolution ,-indicate not dissolving under heated condition.
The testing result shown in the table 1 and table 2 it can be concluded that, polyimide resin provided in the present invention and transparent polyamides
The comprehensive performance of imines film is preferable.Wherein, the polyimide resin and transparent polyamides that embodiment 1 and embodiment 3-8 are provided are sub-
The comprehensive performance of amine film is preferable, and polyimide resin fiberglass transition temperature is at least 290 DEG C, transparent polyimide film
The optical transmittance of (with a thickness of 15-25 μm, wavelength 550nm) is at least 87.2%, and polyimide resin powder end is in low boiling point
It can be dissolved in solvent.Particularly, the polyimide resin and clear polyimides that embodiment 1,3,5 and embodiment 7 provide are thin
The comprehensive performance of film is best, and polyimide resin fiberglass transition temperature is at least 310 DEG C, transparent polyimide film (thickness
Be 15-21 μm, wavelength 550nm) optical transmittance be at least 89.2%, polyimide resin powder end is in low boiling point solvent
It can dissolve.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.It is all
The equivalent changes and modifications that content is done according to the present invention are encompassed by the scope of the patents of the invention.
Claims (10)
1. a kind of polyimide resin, which is characterized in that the polyimide resin includes following structural units:
Wherein, in structural unit (a), A is the residue of dianhydride, and the residue of the dianhydride includes the dianhydride residue containing phenyl ring；?
In structural unit (a) and (b): R1, R2Hydrogen atom, halogen atom, itrile group, nitro, alkyl, alkoxy is each independently represented to replace
Base or phenyl ring.
2. polyimide resin according to claim 1, which is characterized in that the structural unit (a) and structural unit (b)
Molar ratio be 1-9:1-9.
3. polyimide resin according to claim 1, which is characterized in that the polyimide resin is soluble in N,
Dinethylformamide, DMAC N,N' dimethyl acetamide, sulfolane, metacresol, dimethyl sulfoxide, N-Methyl pyrrolidone, hexichol
In one of sulfone, tetrahydrofuran, chloroform, acetone, gamma-butyrolacton, methanol or at least two combined solvents.
4. polyimide resin according to claim 1, which is characterized in that the polyimide resin is in N- methylpyrrole
When concentration in alkanone is 0.5g/dL, logarithmic viscosity number is 0.3dL/g~1.2dL/g.
5. a kind of transparent polyimide film, which is characterized in that the transparent polyimide film includes following structural units:
Wherein, in structural unit (a), A is the residue of dianhydride, and the residue of the dianhydride includes the dianhydride residue containing phenyl ring；?
In structural unit (a) and (b): R1, R2Each independently represent hydrogen atom, halogen atom, itrile group, nitro, alkyl, alkoxy or benzene
Ring.
6. transparent polyimide film according to claim 5, which is characterized in that the structural unit (a) and structure list
The molar ratio of first (b) is 1-9: 1-9.
7. transparent polyimide film according to claim 5, which is characterized in that the A is selected from following structural unit
One of or at least two combination:
8. transparent polyimide film according to claim 5, which is characterized in that the R1And R2It is respectively selected from following
One of structural unit or at least two combination:
-- H ,-CH3,-OCH3,-CH2CH3,-NO2,-CN ,-F ,-Cl ,-Br, -- l
9. transparent polyimide film according to claim 5, which is characterized in that the synthon of the film includes two
Acid anhydride and diamines, the dianhydride include dianhydride and fluorine-containing dianhydride containing phenyl ring；The diamines is selected from fluorenediamine.
10. transparent polyimide film according to claim 9, which is characterized in that the dianhydride monomer and diamine monomer
Feed ratio be 96-100: 96-100, the ratio be molar ratio.
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| CN110628061A (en) * | 2019-10-15 | 2019-12-31 | 李南文 | Polyimide film, optical film, image display device and preparation method thereof |
| CN111019130A (en) * | 2019-12-03 | 2020-04-17 | 武汉华星光电半导体显示技术有限公司 | Polyimide, preparation method of polyimide film and display device |
| CN111421898A (en) * | 2020-04-01 | 2020-07-17 | 南京南大波平电子信息有限公司 | Preparation method of light flexible high-temperature-resistant honeycomb core material |
| CN111647270A (en) * | 2020-05-29 | 2020-09-11 | 浙江中科玖源新材料有限公司 | Insulating polyimide film and preparation method thereof |
| CN112300423A (en) * | 2020-09-27 | 2021-02-02 | 浙江中科玖源新材料有限公司 | Preparation method of colorless transparent polyimide film |
| CN112778140A (en) * | 2020-12-29 | 2021-05-11 | 宁波博雅聚力新材料科技有限公司 | Fluorene-containing diamine monomer, polyimide film, preparation method and application thereof |
| CN113527731A (en) * | 2021-06-29 | 2021-10-22 | 宁波长阳科技股份有限公司 | Preparation method of transparent polyimide film |
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| CN111647270A (en) * | 2020-05-29 | 2020-09-11 | 浙江中科玖源新材料有限公司 | Insulating polyimide film and preparation method thereof |
| CN112300423A (en) * | 2020-09-27 | 2021-02-02 | 浙江中科玖源新材料有限公司 | Preparation method of colorless transparent polyimide film |
| CN112778140A (en) * | 2020-12-29 | 2021-05-11 | 宁波博雅聚力新材料科技有限公司 | Fluorene-containing diamine monomer, polyimide film, preparation method and application thereof |
| CN113527731A (en) * | 2021-06-29 | 2021-10-22 | 宁波长阳科技股份有限公司 | Preparation method of transparent polyimide film |
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