CN105906808B - One kind contains tertiary butyl and polynary aryl oxide structure soluble polyimide and preparation method thereof - Google Patents
One kind contains tertiary butyl and polynary aryl oxide structure soluble polyimide and preparation method thereof Download PDFInfo
- Publication number
- CN105906808B CN105906808B CN201610270129.3A CN201610270129A CN105906808B CN 105906808 B CN105906808 B CN 105906808B CN 201610270129 A CN201610270129 A CN 201610270129A CN 105906808 B CN105906808 B CN 105906808B
- Authority
- CN
- China
- Prior art keywords
- tertiary butyl
- oxide structure
- aryl oxide
- soluble polyimide
- polynary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses one kind to contain tertiary butyl and polynary aryl oxide structure soluble polyimide and preparation method thereof, the polyimides is by containing tertiary butyl and polynary aryl oxide structure diamine monomer and aromatic dianhydride monomer, in phenol solvent, using isoquinolin or quinoline as catalyst, it is prepared by one-step method polycondensation reaction.Gained polyimides not only has good heat resistance, while is also equipped with excellent dissolubility（Chloroform, tetrahydrofuran low boiling point solvent are such as dissolved at room temperature）, can machine-shaping at normal temperatures.
Description
Technical field
The present invention relates to polyimides technical fields, and in particular to one kind contains tertiary butyl and polynary aryl oxide structure soluble poly
Acid imide and preparation method thereof.
Background technology
Polyimides (Polyimide, PI) is the polymer material containing imide ring structure on molecular backbone, due to tool
There is excellent comprehensive performance, have very extensive answer in the every field such as Aeronautics and Astronautics, electrical, machinery, chemical industry, microelectronics
With.Traditional aroma type polyimides is due to rigid backbone structure, being insoluble in most of organic solvent, and fusing point is very
Height is even more than its decomposition temperature, and therefore, it is difficult to be processed by conventional forming method.At present in industrial production, polyimides leads to
It is synthesized frequently with " two-step method ", i.e., the intermediate polyamic acid of first synthesizing soluble obtains after machine-shaping through high temperature imidization again
To corresponding polyimides product.But intermediate polyamic acid is usually not sufficiently stable, it is difficult to it is long-term to preserve, and post-process number
It is tired.Therefore, exploitation can be processed with conventional method, and can keep the polyimides of high-fire resistance and good mechanical properties as having
The research topic of challenge.
In order to improve the processing performance of polyimide, scientists have carried out numerous studies work, mainly from following several sides
Set about improving the solubility of polyimides in face:Introduce fatty segment, aliphatic ring structure, flexible connection group, fluorine atom and big
Side group etc..Wherein, fatty segment, aliphatic ring structure, the introducing for being flexibly connected group, can lead to its glass transition problem (Tg)
It reduces；The introducing of fluorine atom will cause polyimides cost to be substantially increased.And polyimides point can not only be weakened by introducing big side group
Interaction between subchain changes chain accumulation mode, increases substantially its dissolubility.Meanwhile big side group can also hinder polyamides sub-
The rotation of amine molecule chain improves its glass transition temperature and thermal stability.
2005, Der-Jang Liaw etc. report a kind of biphenyl type diamine monomer containing big side group (1- naphthalenes) and its
Corresponding polyimides (Macromolecules, 2005,38,4024-4029), the polyimides have following repetitive structure list
Member:
This contains naphthalene diamine monomer and 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acids, 3,3 ', 4,4 '-diphenylsulfone acid
Polyimides obtained by dianhydride is dissolved in the highly polar aprotic solvent such as NMP, DMAc and DMF；And with 3,3 ', 4,4 '-two
Polyimides obtained by benzophenone tetracarboxylic dianhydride is only partially soluble in NMP, and fairly insoluble in DMAc, DMF.
As one of big side group, tertiary butyl is also often introduced into aromatic diamine monomers.Chinese invention patent
CN01112809.7 discloses a kind of polyimides based on the aromatic diamine monomers containing tertiary butyl, with following repetitive structure list
Member:
The extremely excellent dissolubility of the quasi-polyimide, dissolves in the low boiling point organic solvents such as chloroform.
Invention content
Based on above-mentioned technical background, the present invention is using a kind of containing tertiary butyl and polynary aryl oxide structure diamine monomer and various quotient
Product aromatic dianhydride monomer is prepared for a series of new type polyimide resins containing big side group, such polyimide resin is not only protected
Good heat resistance (the T of traditional polyimides is heldg>260 DEG C), while excellent dissolubility is also equipped with, it can be relatively low
Machine-shaping at temperature (room temperature~70 DEG C), and it is simple for process, cost is relatively low.
Technical scheme is as follows：
Synthesized it is a kind of novel containing tertiary butyl and polynary aryl oxide structure diamine monomer (1), with following chemical constitution：
Following constitutional repeating unit is had based on the soluble PI that diamine monomer 1 and various aromatic dianhydrides are prepared：
Wherein：10<n<1000, Ar refer to the chemical constitution of aromatic dianhydride.
It is described containing tertiary butyl, polynary diether linkage structure soluble polyimide in some specific embodiments of the present invention
Aromatic dianhydride structure Ar is selected from one or more of following chemical structural units in constitutional repeating unit:
The present invention also provides a kind of preparation method of above-mentioned soluble polyimide simultaneously, and the preparation method is using phenols to be molten
Agent using a small amount of isoquinolin or quinoline as catalyst, passes through a step by containing tertiary butyl and polynary aryl oxide structure diamines and aromatic dianhydride
The method polycondensation generation soluble polyimide, wherein described containing tertiary butyl and polynary aryl oxide structure diamines and aromatic dianhydride
Molar ratio is 1:0.95~1.05.
Preferably, the preparation method of above-mentioned novel soluble polyimides includes the following steps：
A) under inert gas shielding, by phenol solvent, a small amount of isoquinolin or quinoline, containing tertiary butyl and polynary aryl oxide structure
Diamines and aromatic dianhydride are added in reactor, and polyamic acid solution is obtained by the reaction at a temperature of room temperature~100 DEG C；Catalyst content
Can be 1~5 drop in being reacted in laboratory for common catalytic amount, specific dosage can be by those skilled in the art according to usual warp
It tests and is determined 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 the reaction was continued 12~obtain soluble polyimide solution for 24 hours；Wherein, polyamic acid solution be warming up to 120 DEG C~
The process of 150 DEG C of 5~12h of reaction can be a temperature reaction process or temperature-programmed reaction process；
C) by step B) gained polyimide solution in polyimides be precipitated out, and detach drying.Wherein, precipitation side
Method can be：Gained polyimide solution is diluted and is poured slowly into alcohol precipitating agent, fibrous polyimides is precipitated, through taking out
It filters and is dried under vacuum to constant weight.Wherein, the precipitating reagent can be methanol, ethyl alcohol etc..
The above-mentioned synthetic method containing tertiary butyl and polynary aryl oxide structure diamine monomer is as follows：
Using 2- tertiary butyls aniline as raw material, in the presence of sodium bicarbonate, water as solvent, under room temperature with Iod R 5~6 hours,
Obtain 2- tertiary butyl -4- Iodoanilines；Then for the 2- tertiary butyl -4- Iodoanilines in the presence of triethylamine, dichloromethane makees solvent, with
Chloroacetic chloride generates N- (2- tertiary butyl -4- iodobenzenes) acetamide after reacting 8h at room temperature, with ethyl alcohol recrystallization, obtains pure N- (2-
Tertiary butyl -4- iodobenzenes) acetamide；Then N- (2- tertiary butyl -4- iodobenzenes) acetamide makees catalyst, 1,10- phenanthrolines with CuI
Make ligand, K3PO4In the presence of, it is protected with nitrogen, and 4, coupling reaction occurs for 4 '-dihydroxy diphenyl ether, is reacted under enclosed system
4,4 '-(3- tertiary butyl -4- acetylaminos phenoxy group)-diphenyl ether are generated after 36h.By 4,4 ' after column chromatography purifies-(3-
Tertiary butyl -4- acetylaminos phenoxy group)-diphenyl ether is added in the mixed solution of hydrochloric acid and ethyl alcohol, and generation is containing uncle after the 12h that flows back
Butyl and polynary aryl oxide structure diamine monomer 4,4 '-(3- tertiary butyl -4- amino-benzene oxygens)-diphenyl ether, equally using column chromatography
Method is purified.The details such as the design parameter do not mentioned in above description can be by those skilled in the art according to common sense or limited number of time
Experiment determines.In Figure of description, Fig. 1 is the nuclear magnetic resonance spectroscopy of diamine monomer 1 that synthesizes of inventor, each characteristic peak
Corresponding chemical constitution is indicated in figure, shows that the new diamine monomer 1 of the present invention has successfully been made in inventor.
In some specific embodiments of the present invention, the aromatic dianhydride is selected from 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid two
Acid anhydride, 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acids, Bisphenol A Type Diether Dianhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride, 3,3 ',
4,4 '-benzophenone tetracarboxylic dianhydride, the equal benzene tertacarbonic acid's dianhydrides of 1,2,4,5-, 1,4,5,8 naphthalenetetracarboxylic acid acid anhydride, 3,3,4,4- hexichol
One or both of 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
It measures as 5wt%~20wt%.
Present invention simultaneously provides a kind of methods that above-mentioned novel soluble polyimides is used to prepare polyimides product, will
The polyimides at room temperature~70 DEG C, be dissolved in n,N-dimethylacetamide (DMAc), n,N-Dimethylformamide (DMF),
Be configured to solution in N-Methyl pyrrolidone (NMP), chloroform, tetrahydrofuran, metacresol isopolarity organic solvent, casting film or
Directly apply.
In above application method preferably, the solid content of the polyimide solution is 0.5wt%~10wt%.
Compared with prior art, beneficial effects of the present invention are as follows：
First, the present invention has prepared novel soluble polyimides by suitable preparation method (one-step method)；
Second, present invention gained novel soluble polyimides not only has good heat resistance (Tg>260 DEG C), simultaneously
Good dissolubility is also equipped with, it can the machine-shaping at relatively low temperature (room temperature~70 DEG C).
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Description of the drawings
The nuclear magnetic resonance spectroscopy of diamine monomer 1 that Fig. 1 present invention synthesizes；
The infrared spectrum for the polyimides that Fig. 2 embodiment of the present invention one synthesizes；
The infrared spectrum for the polyimides that Fig. 3 embodiment of the present invention two synthesizes；
The infrared spectrum for the polyimides that Fig. 4 embodiment of the present invention three synthesizes.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than restriction protection scope of the present invention.Those skilled in the art change according to what the present invention made in practical applications
Into and adjustment, still fall within protection scope of the present invention.
In the present invention, the aromatic dianhydride monomer for being used to prepare novel soluble polyimides is not particularly limited, Ren Hehe
Suitable commercialization aromatic dianhydride is used equally for preparing the novel soluble polyimides of the present invention, and the aromatic dianhydride monomer can
Think but be not limited to mentioned in following embodiment 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-diphenyl ether
In tetracarboxylic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acids (6FDA) and Bisphenol A Type Diether Dianhydride (BPADA)
One or two.
Raw material in following embodiment, catalyst and aromatic dianhydride monomer be it is commercially available, diamine monomer (1) by inventor for the first time
Synthesis, preparation method in Summary it is stated that.
In following embodiment, the performance test methods of sample are as follows obtained by each embodiment：
Its molecular weight and molecular weight distribution are in the 200 GPC instrument of PE Series equipped with differential refractive index detector (RI)
On be detected (test condition：DMF is used as eluent, 25 DEG C, flow velocity 1.0mL/min of column temperature is mark with polystyrene (PS)
Sample)；
Its glass transition temperature (Tg) (test condition is measured using TA Q2000 differential scanning calorimeters (DSC)：
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 thermal history is eliminated
It is obtained in secondary temperature elevation curve；
Its thermal stability is detected (test condition using TA Q5000IR thermogravimetric analyzers (TGA)：Respectively in nitrogen or
It is carried out under air atmosphere, heating rate is 20 DEG C/min, 50 DEG C~800 DEG C of temperature range, selects weightless temperature when being 5wt%
(T5wt%) as its decomposition temperature).
Embodiment one (synthesis of PI-1)：
The preparation principle and process of the PI-1 of the present embodiment is 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
9mL metacresols and 294.2mg (1.0mmol) BPDA are sequentially added, two drop isoquinolin is instilled, 12h is stirred to react at 85 DEG C, it is raw
Into polyamic acid solution, then it is warming up to 120 DEG C, 150 DEG C successively and is stirred to react 5h respectively, be finally warming up to 220 DEG C and continue to stir
Mix reaction 15h.After reaction solution is cooled to room temperature, the dilution of 20mL chloroforms is added in, then slowly pour into the methanol that 300mL is quickly stirred
In, white fibrous solid is precipitated.Through filtering and obtaining PI-1 resins for 24 hours in 150 DEG C of vacuum drying.
At 70 DEG C, a certain amount of PI-1 resins are dissolved in NMP (solid content 6wt%), then in clean sheet glass
(3×6cm2) on casting film.12h finally is dried in vacuo at 150 DEG C, faint yellow PI-1 films can be obtained.Attached drawing 2 is the polymerization
The infrared spectrogram of object film, wherein 1778cm-1And 1725cm-1The absorption peak at place is carbonyl on imide ring in polyimides
Characteristic absorption peak, illustrate the soluble polyimide PI-1 that the present embodiment is successfully prepared in above-mentioned reaction equation.
It is measured through the above 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 the PI-1 resins see the table below
1。
Embodiment two (synthesis of PI-2)：
The preparation principle and process of the PI-2 of the present embodiment is 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
10mL metacresols and 310.2mg (1.0mmol) ODPA are sequentially added, two drop isoquinolin is instilled, 12h is stirred to react at 85 DEG C,
Polyamic acid solution is generated, then is warming up to 120 DEG C, 150 DEG C successively and is stirred to react 5h respectively, 220 DEG C is finally warming up to and continues
It is stirred to react 15h.After reaction solution is cooled to room temperature, the dilution of 20mL chloroforms is added in, then slowly pour into the first that 300mL is quickly stirred
In alcohol, white fibrous solid is precipitated.Through filtering and obtaining PI-2 resins for 24 hours in 150 DEG C of vacuum drying.
At room temperature, a certain amount of PI-2 resins are dissolved in NMP (solid content 6wt%), then in clean sheet glass
(3×6cm2) on casting film.12h finally is dried in vacuo at 150 DEG C, faint yellow PI-2 films can be obtained.Attached drawing 3 is the polymerization
The infrared spectrogram of object film, wherein 1779cm-1And 1725cm-1The absorption peak at place is carbonyl on imide ring in polyimides
Characteristic absorption peak, illustrate the soluble polyimide PI-2 that the present embodiment is successfully prepared in above-mentioned reaction equation.
It is measured through the above 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 the PI-2 resins is shown in Table 1.
Embodiment three (synthesis of PI-3)：
The preparation principle and process of the PI-3 of the present embodiment is 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
10mL metacresols and 444.2mg (1.0mmol) 6FDA are sequentially added, two drop isoquinolin is instilled, 12h is stirred to react at 85 DEG C,
Polyamic acid solution is generated, then is warming up to 120 DEG C, 150 DEG C successively and is stirred to react 5h respectively, 220 DEG C is finally warming up to and continues
It is stirred to react 15h.After reaction solution is cooled to room temperature, the dilution of 20mL chloroforms is added in, then slowly pour into the first that 300mL is quickly stirred
In alcohol, white fibrous solid is precipitated.Through filtering and obtaining PI-3 resins for 24 hours in 150 DEG C of vacuum drying.
At room temperature, a certain amount of PI-3 resins are dissolved in NMP (solid content 6wt%), then in clean sheet glass
(3×6cm2) on casting film.12h finally is dried in vacuo at 150 DEG C, colourless PI-3 films can be obtained.Attached drawing 4 is the polymer
The infrared spectrum of film, wherein 1787cm-1And 1730cm-1The absorption peak at place is the spy of carbonyl on imide ring in polyimides
Absorption peak is levied, illustrates the soluble polyimide PI-3 that the present embodiment is successfully prepared in above-mentioned reaction equation.
It is measured through the above 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 the PI-3 resins is shown in Table 1.
Visible the following table 1 of dissolubility test result of each polyimide resin synthesized in embodiment described above 1-3；Its
In, deliquescent specific test method is：It weighs 10mg samples and is placed in 1mL and correspond in solvent, add in stirrer in room temperature or 60
DEG C stirring 0.5-12h, observe its dissolution degree.
The dissolubility test table of 1 polyimides of table
| PI-1 | PI-2 | PI-3 | |
| m-cresol | + | + | + |
| DMAc | + | + | + |
| DMF | + | + | + |
| NMP | + | + | + |
| THF | + | + | + |
| CHCl3 | + | + | + |
| Toluene | (+) | (+) | + |
Note：+ represent to be completely dissolved at room temperature, (+) represents to be partly dissolved at room temperature.
As can be seen from Table 1, the polyimides of 1~3 gained of above example in the present invention greatly can be compared with low temperature
(room temperature) is dissolved in most solvents under degree, the favorable solubility of embodiment one, embodiment two and embodiment three, is convenient for adding
Work.
Under the introduction 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 enumerated or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention and each original
The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
Claims (9)
1. a kind of soluble polyimide containing tertiary butyl and polynary aryl oxide structure, which is characterized in that the soluble polyimide
Include following constitutional repeating unit：
Wherein：10<n<1000；
The soluble polyimide is anti-by one-step method polycondensation by containing tertiary butyl and polynary aryl oxide structure diamines and aromatic dianhydride
It should generate, described containing tertiary butyl and polynary aryl oxide structure diamines is 4,4 '-(3- tertiary butyl -4- ammonia shown in following structural formula
Phenoxyl)-diphenyl ether (1)：
It is prepared via a method which：
Using 2- tertiary butyls aniline as raw material, in the presence of sodium bicarbonate, water as solvent with Iod R 5~6 hours under room temperature, obtains
2- tertiary butyl -4- Iodoanilines；Then the 2- tertiary butyl -4- Iodoanilines are in the presence of triethylamine, and dichloromethane makees solvent, with acetyl
Chlorine generates N- (2- tertiary butyl -4- iodobenzenes) acetamide after reacting 8h at room temperature, with ethyl alcohol recrystallization, obtains pure N- (the tertiary fourths of 2-
Base -4- iodobenzenes) acetamide；Then N- (2- tertiary butyl -4- iodobenzenes) acetamides make catalyst with CuI, 1,10- phenanthrolines work is matched
Body, K3PO4In the presence of, it is protected with nitrogen, and 4, coupling reaction occurs for 4 '-dihydroxy diphenyl ether, reacts 36h under enclosed system
After generate 4,4 '-(3- tertiary butyl -4- acetylaminos phenoxy group)-diphenyl ether；By 4,4 ' after column chromatography purifies-(uncle 3-
Butyl -4- acetylaminos phenoxy group)-diphenyl ether is added in the mixed solution of hydrochloric acid and ethyl alcohol, and generation is containing tertiary fourth after the 12h that flows back
Base and polynary aryl oxide structure diamine monomer 4,4 '-(3- tertiary butyl -4- amino-benzene oxygens)-diphenyl ether, and using column chromatography into
Row purification.
2. the soluble polyimide containing tertiary butyl and polynary aryl oxide structure as described in claim 1, which is characterized in that described
Constitutional repeating unit in Ar be selected from one or more of following chemical structural units:
3. a kind of system containing tertiary butyl and polynary aryl oxide structure soluble polyimide described in any one of claims 1 or 2
Preparation Method, which is characterized in that using phenols as solvent, using a small amount of isoquinolin or quinoline as catalyst, by containing tertiary butyl and polynary virtue
Ether structure diamines and aromatic dianhydride are by the one-step method polycondensation reaction generation soluble polyimide, wherein described contain tertiary fourth
Base and the molar ratio of polynary aryl oxide structure diamines and aromatic dianhydride are 1:0.95~1.05；
Described is 4,4 '-(3- tertiary butyl -4- amino shown in following structural formula containing tertiary butyl and polynary aryl oxide structure diamine monomer
Phenoxy group)-diphenyl ether (1)：
It is prepared via a method which：
Using 2- tertiary butyls aniline as raw material, in the presence of sodium bicarbonate, water as solvent with Iod R 5~6 hours under room temperature, obtains
2- tertiary butyl -4- Iodoanilines；Then the 2- tertiary butyl -4- Iodoanilines are in the presence of triethylamine, and dichloromethane makees solvent, with acetyl
Chlorine generates N- (2- tertiary butyl -4- iodobenzenes) acetamide after reacting 8h at room temperature, with ethyl alcohol recrystallization, obtains pure N- (the tertiary fourths of 2-
Base -4- iodobenzenes) acetamide；Then N- (2- tertiary butyl -4- iodobenzenes) acetamides make catalyst with CuI, 1,10- phenanthrolines work is matched
Body, K3PO4In the presence of, it is protected with nitrogen, and 4, coupling reaction occurs for 4 '-dihydroxy diphenyl ether, reacts 36h under enclosed system
After generate 4,4 '-(3- tertiary butyl -4- acetylaminos phenoxy group)-diphenyl ether；By 4,4 ' after column chromatography purifies-(uncle 3-
Butyl -4- acetylaminos phenoxy group)-diphenyl ether is added in the mixed solution of hydrochloric acid and ethyl alcohol, and generation is containing tertiary fourth after the 12h that flows back
Base and polynary aryl oxide structure diamine monomer 4,4 '-(3- tertiary butyl -4- amino-benzene oxygens)-diphenyl ether, and using column chromatography into
Row purification.
4. the preparation method according to claim 3 containing tertiary butyl and polynary aryl oxide structure soluble polyimide, special
Sign is, includes the following steps：
A it) is added in by phenol solvent, a small amount of isoquinolin or quinoline, containing tertiary butyl and polynary aryl oxide structure diamines and aromatic dianhydride anti-
It answers in device, under room temperature~100 DEG C and nitrogen protection, is stirred to react to obtain 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；Then it is warming up to 180 DEG C again
~220 DEG C the reaction was continued 12~for 24 hours, obtain soluble polyimide solution；
C) by step B) gained polyimide solution be cooled to room temperature after, pour into a certain amount of precipitating reagent, polyimides made to sink
Shallow lake comes out, and then detaches drying.
5. the preparation method containing tertiary butyl and polynary aryl oxide structure soluble polyimide according to claim 3 or 4, special
Sign is, the aromatic dianhydride is selected from 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidenyl) two phthalandiones
Acid anhydride, Bisphenol A Type Diether Dianhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 1,2,4,
One kind or two in the equal benzene tertacarbonic acid's dianhydrides of 5-, 1,4,5,8 naphthalenetetracarboxylic acid acid anhydride, 3,3,4,4- diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydrides
Kind.
6. the preparation method containing tertiary butyl and polynary aryl oxide structure soluble polyimide according to claim 4, feature
Be, step A) in polyamic acid solution solid content be 5wt%~20wt%.
7. the preparation method containing tertiary butyl and polynary aryl oxide structure soluble polyimide according to claim 4, feature
It is, step B) in, the process that polyamic acid solution is warming up to 180 DEG C~220 DEG C can be step heating or temperature-programmed reaction
Process.
8. add described in any one of a kind of claim 3 or 4 containing tertiary butyl and polynary aryl oxide structure soluble polyimide resin
Work is into the method for polyimides product, which is characterized in that by the polyimides at room temperature~70 DEG C, it is organic molten to be dissolved in polarity
Solution, and casting film or directly application are configured in agent.
9. according to claim 8 be used to prepare polyimides containing tertiary butyl and polynary aryl oxide structure soluble polyimide
The method of product, which is characterized in that the solid content of the polyimide solution is 0.5wt%~10wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610270129.3A CN105906808B (en) | 2016-04-27 | 2016-04-27 | One kind contains tertiary butyl and polynary aryl oxide structure soluble polyimide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610270129.3A CN105906808B (en) | 2016-04-27 | 2016-04-27 | One kind contains tertiary butyl and polynary aryl oxide structure soluble polyimide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105906808A CN105906808A (en) | 2016-08-31 |
| CN105906808B true CN105906808B (en) | 2018-07-03 |
Family
ID=56751933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610270129.3A Active CN105906808B (en) | 2016-04-27 | 2016-04-27 | One kind contains tertiary butyl and polynary aryl oxide structure soluble polyimide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105906808B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI658066B (en) * | 2017-02-03 | 2019-05-01 | 台虹科技股份有限公司 | Polyimide polymer and polyimide film |
| 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 |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148399C (en) * | 2001-04-30 | 2004-05-05 | 上海交通大学 | Soluble polyimide material containing tert-butyl and its preparing process |
| CN101037393B (en) * | 2007-04-26 | 2011-06-15 | 南京工业大学 | Synthetic process for preparing arylamine by reduction of aromatic nitro compound |
| CN101239919B (en) * | 2008-01-11 | 2011-01-12 | 南京工业大学 | Synthetic method of aromatic diamine monomer |
| CN104725636A (en) * | 2015-02-02 | 2015-06-24 | 上海交通大学 | Soluble polyimide containing ether bond and tertiary butyl and preparation method thereof |
-
2016
- 2016-04-27 CN CN201610270129.3A patent/CN105906808B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105906808A (en) | 2016-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105906808B (en) | One kind contains tertiary butyl and polynary aryl oxide structure soluble polyimide and preparation method thereof | |
| CN108219133A (en) | A kind of polyimide resin containing furan nucleus and preparation method thereof | |
| CN104151823B (en) | Kapton and preparation method thereof | |
| JP2007246772A (en) | Multibranched polyimide-based hybrid material | |
| EP0417770A1 (en) | Polyimide membranes and their use for gas separation | |
| US6307002B1 (en) | Polyimide composition and process for producing the same | |
| EP1832618A1 (en) | Fluorinated diamine and polymer made from the same | |
| CN105315665A (en) | Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article | |
| CN106046376B (en) | The B of the B ' containing tert-butyl2Type Triamine monomer and its super-branched polyimide and preparation method | |
| TWI401279B (en) | Polyamic acid, polyimide and a method for producing the same | |
| JP2006206825A (en) | Aromatic polyimide resin precursor and aromatic polyimide resin | |
| CN108383733A (en) | Diamine monomer containing tertiary butyl and cycloaliphatic ring and its preparation and application | |
| KR20170125973A (en) | A novel tetracarboxylic acid dianhydride, and a polyimide and polyimide copolymer obtained from an acid dianhydride | |
| CN102803337B (en) | New polyamide, polyimide or polyamide-imide comprising dibenzodiazocine units | |
| Zhuo et al. | Synthesis of soluble and thermally stable polyimides with phthalimide as pendent group from pyridine-containing triamine | |
| CN103910882A (en) | High-Tg soluble polyimide and preparation method thereof | |
| Yi et al. | Synthesis and characterization of hyperbranched polyimides from a novel B’B2-type triamine with tert-butyl side group | |
| JPH11152332A (en) | Novel soluble polyimide resin | |
| CN107163248B (en) | A kind of phosphorous and trifluoromethyl soluble polyimide and preparation method thereof | |
| CN111423583A (en) | Polyimide resin with furan structure and preparation method thereof | |
| CN105968355A (en) | Polyimide synthesis method | |
| CN104861162A (en) | Soluble polyimide with tert-butyl and triphenylamine structure and preparation method of soluble polyimide | |
| CN104725636A (en) | Soluble polyimide containing ether bond and tertiary butyl and preparation method thereof | |
| JPH05230211A (en) | Polyimide resin | |
| CN104130408A (en) | Hight-Tg soluble polyimide containing fluorene and tertiary butyl and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230627 Address after: Floor 2, Building 3, No. 111, Real Estate Road, Pudong New Area, Shanghai, 200000 Patentee after: Shanghai mat macromolecule material Co.,Ltd. Address before: 200240 No. 800, Dongchuan Road, Shanghai, Minhang District Patentee before: SHANGHAI JIAO TONG University |