CN105906808A - Class I soluble polyimide containing tertiary butyl and multi-element aromatic ether structure and preparation method thereof - Google Patents
Class I soluble polyimide containing tertiary butyl and multi-element aromatic ether structure and preparation method thereof Download PDFInfo
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- CN105906808A CN105906808A CN201610270129.3A CN201610270129A CN105906808A CN 105906808 A CN105906808 A CN 105906808A CN 201610270129 A CN201610270129 A CN 201610270129A CN 105906808 A CN105906808 A CN 105906808A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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Abstract
The invention discloses a class I soluble polyimide containing tertiary butyl and multi-element aromatic ether structure and a preparation method thereof; the polyimide prepared by reacting diamine monomer and aromatic dianhydride monomer containing tertiary butyl and multi-element aromatic ether structure with a catalyst isoquinoline or quinoline in a phenol solution by one-step condensation polymerization. The prepared polyimide not only has good heat resistance, but also has excellent solubility (e.g., it is soluble to low boiling point solvents such as chloroform and tetrahydrofuran at room temperature); and the polyimide can be processed and shaped under normal temperature.
Description
Technical field
The present invention relates to polyimides technical field, be specifically related to a class containing the tert-butyl group and polynary aryl oxide structure soluble poly
Acid imide and preparation method thereof.
Background technology
Polyimides (Polyimide, PI) is the polymeric material on molecular backbone containing imide ring structure, due to tool
Have the combination property of excellence, Aeronautics and Astronautics, electrically, the every field such as machinery, chemical industry, microelectronics have answering widely
With.Traditional aroma type polyimides, owing to having the backbone structure of rigidity, is insoluble in most organic solvent, and fusing point is very
High even more than its decomposition temperature, therefore, it is difficult to process by conventional forming method.At present in commercial production, polyimides leads to
Synthesize frequently with " two-step method ", the intermediate polyamic acid of i.e. first synthesizing soluble, obtain through high temperature imidization again after machine-shaping
To corresponding polyimides goods.But intermediate polyamic acid is generally not sufficiently stable, it is difficult to preserve for a long time, and post processing is number
Tired.Therefore, exploitation can be processed by conventional method, and the polyimides of high-fire resistance and good mechanical properties can be kept to become have
Challenging research topic.
In order to improve the processing characteristics of polyimide, scientists has carried out numerous studies work, mainly from following several sides
The solubility of polyimides is set about improving in face: introduces fat segment, aliphatic ring structure, flexibly connect group, fluorine atom and big
Side base etc..Wherein, fat segment, aliphatic ring structure, flexibly connect the introducing of group, its glass transition problem (T can be causedg)
Reduce；The introducing of fluorine atom will cause polyimides cost to be substantially increased.And introduce big side base and not only can weaken polyimides and divide
Interaction between subchain, changes chain accumulation mode, increases substantially its dissolubility.Meanwhile, big side base also can hinder polyamides sub-
The rotation of amine molecule chain, improves its vitrification point and heat stability.
2005, Der-Jang Liaw etc. report a kind of biphenyl type diamine monomer containing big side base (1-naphthyl) and
Corresponding polyimides (Macromolecules, 2005,38,4024-4029), this polyimides has following repetitive structure list
Unit:
This contains naphthyl diamine monomer and 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acid, 3,3 ', 4,4 '-diphenylsulfone acid
Polyimides obtained by dianhydride dissolves in the highly polar aprotic solvent such as NMP, DMAc and DMF；And with 3,3 ', 4,4 '-two
Polyimides obtained by Benzophenone carboxylic acid dianhydride is only partially soluble in NMP, and fairly insoluble in DMAc, DMF.
As one of big side base, the tert-butyl group is the most often introduced in aromatic diamine monomers.Chinese invention patent
CN01112809.7 discloses a kind of based on the polyimides containing tert-butyl group aromatic diamine monomers, and it has following repetitive structure list
Unit:
The dissolubility that this quasi-polyimide is extremely excellent, dissolves in the low boiling point organic solvents such as chloroform.
Summary of the invention
Based on above-mentioned technical background, the present invention uses one to contain the tert-butyl group and polynary aryl oxide structure diamine monomer and various business
Product aromatic dianhydride monomer is prepared for a series of new type polyimide resin containing big side base, and such polyimide resin is not only protected
Hold the heat resistance (T that traditional polyimides is goodg> 260 DEG C), it is also equipped with the dissolubility of excellence simultaneously, can be relatively low
Machine-shaping at temperature (room temperature～70 DEG C), and technique is simple, cost is relatively low.
Technical scheme is as follows:
Having synthesized a kind of novel containing the tert-butyl group with polynary aryl oxide structure diamine monomer (1), it has a following chemical constitution:
Solubility PI prepared based on diamine monomer 1 and various aromatic dianhydride has a following constitutional repeating unit:
Wherein: 10 < n < 1000, Ar refer to the chemical constitution of aromatic dianhydride.
In some specific embodiments of the present invention, described containing the tert-butyl group, polynary diether linkage structure soluble polyimide
One or more in following chemical structural units of aromatic dianhydride structure Ar in constitutional repeating unit:
The present invention also provides for the preparation method of a kind of above-mentioned soluble polyimide simultaneously, and this preparation method is molten with phenols
Agent, with a small amount of isoquinolin or quinoline as catalyst, by containing the tert-butyl group and polynary aryl oxide structure diamidogen and aromatic dianhydride by a step
Method polycondensation generate described in soluble polyimide, wherein said containing the tert-butyl group and polynary aryl oxide structure diamidogen and aromatic dianhydride
Mol ratio is 1:0.95～1.05.
Preferably, the preparation method of above-mentioned novel soluble polyimides comprises the steps:
A) under inert gas shielding, by phenol solvent, a small amount of isoquinolin or quinoline, containing the tert-butyl group and polynary aryl oxide structure
Diamidogen and aromatic dianhydride add in reactor, and at a temperature of room temperature～100 DEG C, reaction obtains polyamic acid solution；Catalyst content
For common catalytic amount, can be 1～5 in laboratory reacts, concrete consumption can be by those skilled in the art according to usual warp
Test and determine with common sense in the field；
B) by step A) gained polyamic acid solution be warming up to 120 DEG C～150 DEG C reaction 5～12h；Then heat to 180
DEG C～220 DEG C continue reaction and 12～24h obtain soluble polyimide solution；Wherein, polyamic acid solution be warming up to 120 DEG C～
The process of 150 DEG C of reactions 5～12h can be a temperature reaction process or temperature-programmed reaction process；
C) by step B) polyimides in gained polyimide solution is precipitated out, and separate and be dried.Wherein, precipitation side
Method can be: is diluted by gained polyimide solution and is poured slowly in alcohol precipitating agent, separates out threadiness polyimides, through taking out
Filter and be dried under vacuum to constant weight.Wherein, described precipitant can be methanol, ethanol etc..
The above-mentioned synthetic method containing the tert-butyl group and polynary aryl oxide structure diamine monomer is as follows:
With 2-tert-butyl group aniline as raw material, in the presence of sodium bicarbonate, water as solvent, with Iod R 5～6 hours under room temperature,
Obtain the 2-tert-butyl group-4-Iodoaniline；Then this 2-tert-butyl group-4-Iodoaniline is in the presence of triethylamine, and dichloromethane makees solvent, with
Generate N-(the 2-tert-butyl group-4-iodobenzene) acetamide after reacting 8h under chloroacetic chloride room temperature, with ethyl alcohol recrystallization, obtain pure N-(2-
The tert-butyl group-4-iodobenzene) acetamide；Then this N-(the 2-tert-butyl group-4-iodobenzene) acetamide makees catalyst, 1,10-phenanthroline with CuI
Make part, K3PO4In the presence of, protect with nitrogen, with 4,4 '-dihydroxy diphenyl ether generation coupling reaction, react under enclosed system
4,4 '-(the 3-tert-butyl group-4-acetylamino phenoxy group)-diphenyl ether are generated after 36h.By 4,4 ' after column chromatography purifies-(3-
The tert-butyl group-4-acetylamino phenoxy group)-diphenyl ether joins in the mixed solution of hydrochloric acid and ethanol, generates containing uncle after backflow 12h
Butyl and polynary aryl oxide structure diamine monomer 4,4 '-(the 3-tert-butyl group-4-amino-benzene oxygen)-diphenyl ether, use column chromatography equally
Method purifies.The details such as the design parameter do not mentioned in above description can be by those skilled in the art according to general knowledge or limited number of time
Experiment determines.In Figure of description, Fig. 1 is the proton nmr spectra that inventor synthesizes the diamine monomer 1 obtained, each characteristic peak
Corresponding chemical constitution is indicated the most in the drawings, shows that inventor has successfully prepared the new diamine monomer 1 of the present invention.
In some specific embodiments of the present invention, described aromatic dianhydride is selected from 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid two
Acid anhydride, 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acid, Bisphenol A Type Diether Dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ',
4,4 '-benzophenone tetracarboxylic dianhydride, 1,2,4,5-equal benzene tertacarbonic acid dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid acid anhydride, 3,3,4,4-hexichol
One or both in base sulfone tetrabasic carboxylic acid dicarboxylic anhydride.
In some currently preferred embodiments of the present invention, in above-mentioned preparation method, step A) in polyamic acid solution containing solid
Amount is 5wt%～20wt%.
Present invention simultaneously provides a kind of above-mentioned novel soluble polyimides for the method preparing polyimides goods, general
Described polyimides at room temperature～70 DEG C, be dissolved in N,N-dimethylacetamide (DMAc), DMF (DMF),
N-Methyl pyrrolidone (NMP), chloroform, oxolane, metacresol polar organic solvent be configured to solution, casting film or
Directly application.
In above-mentioned application process preferably, the solid content of described polyimide solution is 0.5wt%～10wt%.
Compared with prior art, beneficial effects of the present invention is as follows:
First, the present invention has prepared novel soluble polyimides by suitable preparation method (one-step method)；
Second, gained novel soluble polyimides of the present invention not only has good thermostability (Tg> 260 DEG C), simultaneously
It is also equipped with good dissolubility, can machine-shaping at relatively low temperature (room temperature～70 DEG C).
Certainly, the arbitrary product implementing the present invention it is not absolutely required to reach all the above advantage simultaneously.
Accompanying drawing explanation
The proton nmr spectra of the diamine monomer 1 of Fig. 1 present invention synthesis；
The infrared spectrum of the polyimides of Fig. 2 embodiment of the present invention one synthesis；
The infrared spectrum of the polyimides of Fig. 3 embodiment of the present invention two synthesis；
The infrared spectrum of the polyimides of Fig. 4 embodiment of the present invention three synthesis.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright, rather than limit protection scope of the present invention.Those skilled in the art are according to changing that the present invention makes in actual applications
Enter and adjust, still falling within protection scope of the present invention.
In the present invention, it is not particularly limited for preparing the aromatic dianhydride monomer of novel soluble polyimides, Ren Hehe
Suitable commercialization aromatic dianhydride is used equally to prepare the novel soluble polyimides of the present invention, and described aromatic dianhydride monomer can
Think but be not limited in following example 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), 3,3 ', the 4,4 '-diphenyl ether mentioned
In tetracarboxylic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acid (6FDA) and Bisphenol A Type Diether Dianhydride (BPADA)
One or both.
Raw material in following example, catalyst and aromatic dianhydride monomer are commercially available, and diamine monomer (1) is by inventor first
Synthesis, its preparation method at Summary it is stated that.
In following example, the performance test methods of each embodiment gained sample is as follows:
Its molecular weight and molecular weight distribution are being furnished with the PE Series 200 GPC instrument of differential refractive index detector (RI)
On carry out detecting that (flow velocity 1.0mL/min, with polystyrene (PS) for mark for test condition: employing DMF is eluent, column temperature 25 DEG C
Sample)；
Its glass transition temperature (Tg) use TA Q2000 differential scanning calorimeter (DSC) be measured (test condition:
Under nitrogen atmosphere, heating rate is 20 DEG C/min, and temperature range is 40 DEG C～430 DEG C, and test result is after eliminating thermal history
Secondary temperature elevation curve obtains；
Its heat stability use TA Q5000IR thermogravimetric analyzer (TGA) carry out detecting (test condition: respectively at nitrogen or
Carrying out under air atmosphere, heating rate is 20 DEG C/min, temperature range 50 DEG C～800 DEG C, and selecting weightlessness is temperature during 5wt%
(T5wt%) as its decomposition temperature).
Embodiment one (synthesis of PI-1):
Preparation principle and the process of the PI-1 of the present embodiment are as follows:
The preparation method of the polyimides of the present embodiment is as follows:
Under nitrogen protection, 496.6mg (1.0mmol) diamine monomer 1 is added in 100mL three neck round bottom flask, then
Being sequentially added into 9mL metacresol and 294.2mg (1.0mmol) BPDA, instill two isoquinolin, at 85 DEG C, stirring reaction 12h, raw
Become polyamic acid solution, then be warming up to successively 120 DEG C, 150 DEG C respectively stirring reaction 5h, be finally warming up to 220 DEG C and continue to stir
Mix reaction 15h.After reactant liquor is cooled to room temperature, adds the dilution of 20mL chloroform, more slowly pour into the methanol that 300mL quickly stirs
In, separate out white fibrous solid.PI-1 resin is obtained through sucking filtration and at 150 DEG C of vacuum drying 24h.
At 70 DEG C, a certain amount of PI-1 resin is dissolved in NMP (solid content is 6wt%), then at clean sheet glass
(3×6cm2) upper casting film.Last vacuum drying 12h at 150 DEG C, can obtain faint yellow PI-1 thin film.Accompanying drawing 2 is this polymerization
The infrared spectrogram of thing thin film, wherein 1778cm-1And 1725cm-1The absworption peak at place is carbonyl on imide ring in polyimides
Characteristic absorption peak, the soluble polyimide PI-1 that the present embodiment is successfully prepared in above-mentioned reaction equation is described.
Measuring through said method, the number-average molecular weight of PI-1 is 3.2 × 104, molecular weight distribution (Mw/Mn) it is 2.74；Glass
Change transition temperature (Tg) it is 283 DEG C；Decomposition temperature (T in nitrogen5wt%) it is 529 DEG C.The dissolubility of this PI-1 resin see table
1。
Embodiment two (synthesis of PI-2):
Preparation principle and the process of the PI-2 of the present embodiment are as follows:
The preparation method of the polyimides of the present embodiment is as follows:
Under nitrogen protection, 496.6mg (1.0mmol) diamine monomer 1 is added in 100mL three neck round bottom flask, then
It is sequentially added into 10mL metacresol and 310.2mg (1.0mmol) ODPA, instills two isoquinolin, stirring reaction 12h at 85 DEG C,
Generate polyamic acid solution, then be warming up to successively 120 DEG C, 150 DEG C respectively stirring reaction 5h, be finally warming up to 220 DEG C and continue
Stirring reaction 15h.After reactant liquor is cooled to room temperature, adds the dilution of 20mL chloroform, more slowly pour into the first that 300mL quickly stirs
In alcohol, separate out white fibrous solid.PI-2 resin is obtained through sucking filtration and at 150 DEG C of vacuum drying 24h.
At room temperature, a certain amount of PI-2 resin is dissolved in NMP (solid content is 6wt%), then at clean sheet glass
(3×6cm2) upper casting film.Last vacuum drying 12h at 150 DEG C, can obtain faint yellow PI-2 thin film.Accompanying drawing 3 is this polymerization
The infrared spectrogram of thing thin film, wherein 1779cm-1And 1725cm-1The absworption peak at place is carbonyl on imide ring in polyimides
Characteristic absorption peak, the soluble polyimide PI-2 that the present embodiment is successfully prepared in above-mentioned reaction equation is described.
Measuring through said method, the number-average molecular weight of PI-2 is 3.7 × 104, molecular weight distribution (Mw/Mn) it is 2.25；Glass
Change transition temperature (Tg) it is 264 DEG C；Decomposition temperature (T in nitrogen5wt%) it is 527 DEG C.The dissolubility of this PI-2 resin is shown in Table 1.
Embodiment three (synthesis of PI-3):
Preparation principle and the process of the PI-3 of the present embodiment are as follows:
The preparation method of the polyimides of the present embodiment is as follows:
Under nitrogen protection, 496.6mg (1.0mmol) diamine monomer 1 is added in 100mL three neck round bottom flask, then
It is sequentially added into 10mL metacresol and 444.2mg (1.0mmol) 6FDA, instills two isoquinolin, stirring reaction 12h at 85 DEG C,
Generate polyamic acid solution, then be warming up to successively 120 DEG C, 150 DEG C respectively stirring reaction 5h, be finally warming up to 220 DEG C and continue
Stirring reaction 15h.After reactant liquor is cooled to room temperature, adds the dilution of 20mL chloroform, more slowly pour into the first that 300mL quickly stirs
In alcohol, separate out white fibrous solid.PI-3 resin is obtained through sucking filtration and at 150 DEG C of vacuum drying 24h.
At room temperature, a certain amount of PI-3 resin is dissolved in NMP (solid content is 6wt%), then at clean sheet glass
(3×6cm2) upper casting film.Last vacuum drying 12h at 150 DEG C, can obtain colourless PI-3 thin film.Accompanying drawing 4 is this polymer
The infrared spectrum of thin film, wherein 1787cm-1And 1730cm-1The absworption peak at place is the spy of carbonyl on imide ring in polyimides
Levy absworption peak, the soluble polyimide PI-3 that the present embodiment is successfully prepared in above-mentioned reaction equation is described.
Measuring through said method, the number-average molecular weight of PI-3 is 2.1 × 104, molecular weight distribution (Mw/Mn) it is 2.42；Glass
Change transition temperature (Tg) it is 266 DEG C；Decomposition temperature (T in nitrogen5wt%) it is 525 DEG C.The dissolubility of this PI-3 resin is shown in Table 1.
Table 1 below seen from the dissolubility test result of each polyimide resin of synthesis in embodiment described above 1-3；Its
In, deliquescent concrete method of testing is: weighs 10mg sample and is placed in 1mL correspondence solvent, adds stirrer in room temperature or 60
DEG C stirring 0.5-12h, observe its dissolution degree.
The dissolubility test table of table 1 polyimides
| PI-1 | PI-2 | PI-3 | |
| m-cresol | + | + | + |
| DMAc | + | + | + |
| DMF | + | + | + |
| NMP | + | + | + |
| THF | + | + | + |
| CHCl3 | + | + | + |
| Toluene | (+) | (+) | + |
Note: be completely dissolved under+expression room temperature, (+) represent that room temperature lower part is dissolved.
As can be seen from Table 1, the polyimides of above example 1～3 gained in the present invention greatly can be at relatively low temperature
Under degree, (room temperature) is dissolved in the middle of most solvent, embodiment one, embodiment two and the favorable solubility of embodiment three, it is simple to add
Work.
Under the teaching of the present invention and above-described embodiment, those skilled in the art are easy to it is envisioned that cited by the present invention
Or each raw material or its equivalent alterations, each processing method or its equivalent alterations enumerated can realize the present invention and each former
Material and the parameter bound value of processing method, interval value can realize the present invention, embodiment numerous to list herein.
Claims (10)
1. a class contains the tert-butyl group and the soluble polyimide of polynary aryl oxide structure, it is characterised in that this soluble polyimide
Comprise following constitutional repeating unit:
Wherein: 10 < n < 1000.
2. novel soluble polyimides as claimed in claim 1, it is characterised in that Ar choosing in described constitutional repeating unit
One or more in following chemical structural units:
3. according to any one of a claim 1 or 2 containing the tert-butyl group and the system of polynary aryl oxide structure soluble polyimide
Preparation Method, it is characterised in that with phenols as solvent, with a small amount of isoquinolin or quinoline as catalyst, by containing the tert-butyl group and polynary virtue
Ether structure diamidogen and aromatic dianhydride are by the soluble polyimide described in one-step method polycondensation reaction generation, wherein said containing tertiary fourth
The mol ratio of base and polynary aryl oxide structure diamidogen and aromatic dianhydride is 1:0.95～1.05.
The most according to claim 3 containing the tert-butyl group with the preparation method of polynary aryl oxide structure soluble polyimide, it is special
Levy and be, comprise the steps:
A) by phenol solvent, a small amount of isoquinolin or quinoline, add anti-containing the tert-butyl group and polynary aryl oxide structure diamidogen and aromatic dianhydride
Answering in device, under room temperature～100 DEG C and nitrogen protection, stirring reaction obtains transparent polyamide acid solution；
B) by step A) gained polyamic acid solution be warming up to 120 DEG C～150 DEG C reaction 5～12h；It is warming up to 180 DEG C the most again
～220 DEG C of continuation reactions 12～24h, obtain soluble polyimide solution；
C) by step B) after gained polyimide solution is cooled to room temperature, pours in a certain amount of precipitant, make polyimides sink
Form sediment out, be then peeled off being dried.
5. according to described in claim 3 and 4 containing the tert-butyl group and the preparation method of polynary aryl oxide structure soluble polyimide, its
Be characterised by, described containing the tert-butyl group and polynary aryl oxide structure diamine monomer be shown in following structural formula 4,4 '-(the 3-tert-butyl group-
4-amino-benzene oxygen)-diphenyl ether (1):
6., according to containing the tert-butyl group and the preparation method of polynary aryl oxide structure soluble polyimide described in claim 3 or 4, it is special
Levying and be, described aromatic dianhydride is selected from 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidenyl) two phthalandione
Acid anhydride, Bisphenol A Type Diether Dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 1,2,4,
One or two in 5-equal benzene tertacarbonic acid dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid acid anhydride, 3,3,4,4-sulfobenzide. tetrabasic carboxylic acid dicarboxylic anhydride
Kind.
The most according to claim 4 containing the tert-butyl group and the preparation method of polynary aryl oxide structure soluble polyimide, its feature
Be, step A) in the solid content of polyamic acid solution be 5wt%～20wt%.
The most according to claim 4 containing the tert-butyl group and the preparation method of polynary aryl oxide structure soluble polyimide, its feature
It is, step B) in, it can be that a step heats up or temperature-programmed reaction that polyamic acid solution is warming up to the process of 180 DEG C～220 DEG C
Process.
9. add containing the tert-butyl group and polynary aryl oxide structure soluble polyimide resin according to any one of a class claim 3 or 4
Work becomes the method for polyimides goods, it is characterised in that by described polyimides at room temperature～70 DEG C, be dissolved in polarity organic molten
Agent is configured to solution, and casting film or directly apply.
Soluble polyimide the most according to claim 9 is for the method preparing polyimides goods, and its feature exists
In, the solid content of described polyimide solution is 0.5wt%～10wt%.
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| CN108384002A (en) * | 2017-02-03 | 2018-08-10 | 台虹科技股份有限公司 | Polyimide polymer and polyimide film |
| CN109734910A (en) * | 2019-01-24 | 2019-05-10 | 银禧工程塑料（东莞）有限公司 | A kind of polyimides and its preparation method and application |
| CN109734910B (en) * | 2019-01-24 | 2021-05-04 | 银禧工程塑料（东莞）有限公司 | Polyimide, and preparation method and application thereof |
| CN110128684A (en) * | 2019-04-10 | 2019-08-16 | 华南理工大学 | Transparent solvable biphenyl polyimide film of high heat resistance and the preparation method and application thereof |
| CN110128684B (en) * | 2019-04-10 | 2020-08-18 | 华南理工大学 | High-heat-resistance transparent soluble biphenyl polyimide film and preparation method and application thereof |
| CN113799457A (en) * | 2021-09-30 | 2021-12-17 | 深圳泰得思科技有限公司 | Frosted release film |
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|---|---|
| CN105906808B (en) | 2018-07-03 |
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