CN104987506B - Soluble polyimide containing the tert-butyl group and benzofuran structure and preparation method thereof - Google Patents
Soluble polyimide containing the tert-butyl group and benzofuran structure and preparation method thereof Download PDFInfo
- Publication number
- CN104987506B CN104987506B CN201510368092.3A CN201510368092A CN104987506B CN 104987506 B CN104987506 B CN 104987506B CN 201510368092 A CN201510368092 A CN 201510368092A CN 104987506 B CN104987506 B CN 104987506B
- Authority
- CN
- China
- Prior art keywords
- dianhydride
- tert
- benzofuran
- butyl group
- soluble polyimide
- 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.)
- Expired - Fee Related
Links
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a kind of soluble polyimide containing the tert-butyl group and benzofuran structure and preparation method thereof.The structural formula of the soluble polyimide containing the tert-butyl group and benzofuran structure is：；Using the polyimides that solubility is prepared by " three-step approach " reaction from various different tetracarboxylic dianhydrides with non-co-planar structure aromatic diamines.The polyimide material of the present invention has outstanding solubility property, can not only be dissolved completely in high boiling organic solvent N, N ' dimethylformamide（DMF）, N, N ' dimethyl acetamide（DMAc）, N methyl pyrrolidones（NMP）, dimethyl sulfoxide (DMSO)（DMSO）And in metacresol, and can also preferably be dissolved in lower boiling solvents tetrahydrofurane（THF）, chloroform（CHCl3）, dichloromethane（CH2Cl2）, in ethyl acetate and acetone.
Description
Technical field
It is more particularly to a kind of solvable containing the tert-butyl group and benzofuran structure the invention belongs to technical field of polymer materials
Property polyimides and preparation method thereof.
Background technology
Polyimides is a kind of important feature heat-resistant polymer, can be used as matrices of composite material, electronic seal
Package material, gas separation be applied to film modern high-tech field in, and have been widely used for space flight and aviation, auto industry,
Electronic and electrical industry etc..Polyimides（PI）It is a kind of high-performance polymer of the structure containing imide ring in molecular structure.Although
This kind of exotic material has excellent thermal property and a mechanical property, but possessed by them stiff backbone structures, with
And intermolecular existing strong interaction and strand is tightly packed, causes the polyimides of most of commercialization all to have very
High melting temperature, organic solvent is not dissolved in again（It is dissolved only in the concentrated sulfuric acid mostly）, difficulty is brought to its processing and forming.In addition, pass
The polyimides of system due in the aromatic conjugated property and strand of molecular backbone height electric charge be complexed transferance, its film is most
With very deep color and poor optical transparence.In order to overcome above-mentioned difficulties, it is good, easy to process etc. to prepare solubility property
The polyimide material of excellent combination property, related scientific research department has put into substantial amounts of human and material resources, financial resources are engaged in this respect
R＆D work.
Soluble polyimide is the focus of Recent study, wherein having large space steric hindrance and non-co-planar using synthesis
The polyimide material of structure, by the upright and outspoken chain structure for destroying main chain and intermolecular interaction force, so as to obtain height
Solvable polyimide material.The advantages that synthesis of the method monomer is simple, price is cheap, material excellent combination property, is current
Generally using one of method of synthesizing soluble polyimide.Huang Wei et al. reports the soluble polyimide hair containing naphthalene structure
Luminescent material and preparation method thereof（CN1171931C）；Yu Xin seas et al. are reported based on 3,3 '-diaminourea -4,4 '-dihydroxy connection
The polyimide fiber spinning solution of benzene and its preparation（CN102650080B）；Wangkai guest et al. reports sub- based on fluorine-containing polyamides
The nonlinear optical organic polymer and its synthetic method of amine（CN101942091B）.Such material have good hot property,
The combination properties such as excellent solubility property, high optical transparence, low-k and low hydroscopicity, in Aero-Space, micro- electricity
The field such as son and photoelectron is widely used.
Non-co-planar structure and substituted radical are incorporated into polyimide structures by MOLECULE DESIGN and prepare soluble poly
Acid imide.The large-substituent tert-butyl group and benzofuranyl are introduced in polyimides, improves the solubility property of polyimides, no
Only it is soluble in high boiling organic solvent N, N '-dimethylformamide（DMF）, N, N '-dimethyl acetamide（DMAc）, N- first
Base pyrrolidones（NMP）, dimethyl sulfoxide (DMSO)（DMSO）And in metacresol, and can also preferably be dissolved in lower boiling solvent four
Hydrogen furans（THF）, chloroform（CHCl3）, dichloromethane（CH2Cl2）, in ethyl acetate and acetone so that the polyimides of indissoluble is low
Warm film-forming is possibly realized.This kind of polyimide material also has excellent hot property, optical property and dielectric properties etc..
In terms of hot property, compared with the polyimides of commercialization, although the reduction of hot property to a certain extent, its glass transition temperature
（T g）Still remain in more than 300 DEG C, heat decomposition temperature（T d）More than 500 DEG C, such material is in Aero-Space, microelectronics
And the application field such as photoelectron is sufficient for its requirement.
The content of the invention
It is an object of the invention to provide a kind of soluble polyimide containing the tert-butyl group and benzofuran structure and its preparation
Method.
The structural formula of the soluble polyimide containing the tert-butyl group and benzofuran structure of the present invention is：
。
Wherein Ar is one kind in following 11 kinds of aromatic structure formulas：
。
The preparation process of the soluble polyimide containing the tert-butyl group and benzofuran structure of the present invention is：
(1) under nitrogen protection, equimolar aromatic diamine monomers and aromatic dianhydride monomer are completely dissolved in non-proton pole
Property solvent hexamethyl phosphoramide in, the total dosage of monomer of reaction system makes its solid content be 10%, is reacted at room temperature after stirring
24 hours obtained presoma PAA.
(2) by the use of acetic anhydride as dehydrating agent, pyridine is as dehydration catalyst to PAA made from step (1) at 80 ~ 120 DEG C
Lower progress dehydration 6 ~ 10 hours, is made performed polymer polyisoimide.
(3) polyisoimide made from step (2) is polymerize in 150 ~ 200 DEG C of blanket of nitrogen under catalyst action anti-
Answer 4 ~ 6 hours and obtain sticky polymer solution, be cooled to room temperature, add methanol thereto or ethanol does precipitating reagent, filter, do
It is dry, that is, the fibrous soluble polyimide containing the tert-butyl group and benzofuran structure is made.
The aromatic diamine monomers contain the tert-butyl group and benzofuran based structures, chemistry entitled 3,3 '-di-t-butyl -4,
4 '-diamino-phenyl -3 '-benzofuran methane, its structural formula are：
。
The aromatic dianhydride monomer be 3,3 ', 4,4 '-pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride,
3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic
Dianhydride, 3,3 ', 4,4 '-diphenyl thio-ether tetrformate dianhydride, 1,4- double (3,4- di carboxyl phenyloxies) -2,2 ', 3- trimethylbenzenes two
Double (3,4- dicarboxyphenyis) hexafluoropropane dianhydrides of acid anhydride, 2,2-, 1,1- are double（3,4- di carboxyl phenyloxies）Benzophenone dianhydride, 2,2- are double
(3,4- dicarboxyphenyis) propane dianhydride or double [4- (3,4- di carboxyl phenyloxies) phenyl] hexafluoropropane dianhydrides of 2,2-.
The catalyst is HCl and/or KOH, and the mass percent that its dosage accounts for total amount of feeding is 2 ~ 5%.
Advantages of the present invention：
(1) preparation method of the invention is simple to operate, is easy to large-scale promotion.
(2) polyimide material of the invention has good dissolubility energy, dissolves in conventional high boiling organic solventN,N'- dimethylformamide（DMF）、N,N'- dimethyl acetamide（DMAc）, 1-METHYLPYRROLIDONE（NMP）, dimethyl sulfoxide (DMSO)
（DMSO）And metacresol（m-Cresol）Deng, moreover it is possible to it is dissolved in low boiling point solvent THF, CHCl3、CH2Cl2, ethyl acetate and acetone
In.Wherein dissolution characteristics of the polymer in low boiling point solvent, low-temperature setting film-forming process can be achieved, so that material is micro-
Electronic applications are widely used.
(3) polyimide material of the invention has superior heat-resistant stability, glass transition temperature（T g）300
More than DEG C, initial temperature is thermally decomposed（T d）Scope is more than 500 DEG C, and carbon yield is all more than 60%.
(4) polyimide material of the invention has excellent optical property, and cutoff wavelength scope is 300 ~ 350 nm,
Transmitance is 80% nm of wavelength 400 ~ 550.
(5) polyimide material of the invention has low-k, and dielectric constant is all between 1.50 ~ 3.00.
Brief description of the drawings
Fig. 1 is the general structure of the soluble polyimide containing the tert-butyl group and benzofuran structure of the present invention.
Fig. 2 is the structure of the soluble polyimide containing the tert-butyl group and benzofuran structure prepared by the embodiment of the present invention 1
Formula.
Fig. 3 is the structure of the soluble polyimide containing the tert-butyl group and benzofuran structure prepared by the embodiment of the present invention 2
Formula.
Fig. 4 is the structure of the soluble polyimide containing the tert-butyl group and benzofuran structure prepared by the embodiment of the present invention 3
Formula.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within claims appended by the application and limited
Scope.
Embodiment 1：
In 50 milliliters of three neck round bottom flask that one is equipped with mechanical agitator, reflux condensing tube, nitrogen airway tube respectively
Add 3,3 '-di-t-butyl -4,4 '-diamino-phenyl -3 ' 1.0000 grams of-benzofuran methane（2.3442 mM）, 3,3 ',
0.5113 gram of 4,4 '-pyromellitic acid anhydride（2.3442 mM）, 13.60 grams of hexamethyl phosphoramide, stir, room temperature
Lower reaction obtains presoma PAA in 24 hours.Then added in the PAA obtained at 2 milliliters, 100 DEG C of 25 ml acetic anhydrides and pyridine
Reaction obtains performed polymer polyisoimide in 8 hours.It is last toward 1 milliliter of dense HCl of addition in polyisoimide, nitrogen is protected in 150 ~
Back flow reaction 5 hours at 200 DEG C, finally give sticky polymer solution.After being cooled to room temperature, 500 milliliters of ethanol are added, are sunk
Form sediment, filter and dry, finally obtain fibrous polyimide material.Its structural formula is as follows：
。
Embodiment 2：
In 50 milliliters of three neck round bottom flask that one is equipped with mechanical agitator, reflux condensing tube, nitrogen airway tube respectively
Add 3,3 '-di-t-butyl -4,4 '-diamino-phenyl -3 ' 1.0000 grams of-benzofuran methane（2.3442 mM）, 3,3 ',
0.6897 gram of 4,4 '-bibenzene tetracarboxylic dianhydride（2.3442 mM）, 15.20 grams of hexamethyl phosphoramide, room temperature after stirring
Lower reaction obtains presoma PAA in 24 hours.Then added in the PAA obtained at 1 milliliter, 100 DEG C of 25 ml acetic anhydrides and pyridine
Reaction obtains performed polymer polyisoimide in 8 hours.It is last toward adding 1 milliliter of dense HCl in polyisoimide, nitrogen protect under in
150 ~ 200 DEG C of back flow reactions 5 hours.Finally give sticky polymer solution.After being cooled to room temperature, 500 milliliters of ethanol are added,
Precipitation, filter and dry, finally obtain fibrous polyimide material.Its structural formula is as follows：
。
Embodiment 3：
In 50 milliliters of three neck round bottom flask that one is equipped with mechanical agitator, reflux condensing tube, nitrogen airway tube respectively
Add 3,3 '-di-t-butyl -4,4 '-diamino-phenyl -3 ' 1.0000 grams of-benzofuran methane（2.3442 mM）, 3,3 ',
0.7272 gram of 4,4 '-diphenyl ether tetraformic dianhydride（2.3442 mM）, 15.54 grams of hexamethyl phosphoramide, stir rear chamber
The lower reaction of temperature obtains presoma PAA in 24 hours.Then 1.5 milliliters of 25 ml acetic anhydrides and pyridine are added in the PAA obtained, 100
Reacted 8 hours at DEG C and obtain performed polymer polyisoimide.It is last toward adding 1 milliliter of dense HCl in polyisoimide, under nitrogen is protected
In 150 ~ 200 DEG C of back flow reactions 5 hours.Finally give sticky polymer solution.After being cooled to room temperature, 500 milliliters of second are added
Alcohol, precipitation, filter and dry, finally obtain fibrous polyimide material.Its structural formula is as follows：
。
Claims (1)
1. a kind of preparation method of the soluble polyimide containing the tert-butyl group and benzofuran structure, it is characterised in that this contains tertiary fourth
The structural formula of base and the soluble polyimide of benzofuran structure is：
；
Wherein Ar is one kind in following 11 kinds of aromatic structure formulas：
；
Concretely comprise the following steps：
(1) under nitrogen protection, that equimolar aromatic diamine monomers and aromatic dianhydride monomer are completely dissolved in into aprotonic polar is molten
In agent hexamethyl phosphoramide, the total dosage of monomer of reaction system makes its solid content be 10%, and it is small to react 24 after stirring at room temperature
When presoma PAA is made；
(2) PAA made from step (1) is entered at 80 ~ 120 DEG C as dehydration catalyst by the use of acetic anhydride as dehydrating agent, pyridine
Row dehydration 6 ~ 10 hours, performed polymer polyisoimide is made；
(3) by polyisoimide made from step (2) under catalyst action in 150 ~ 200 DEG C of blanket of nitrogen polymerisation 4 ~
Obtain sticky polymer solution within 6 hours, be cooled to room temperature, add methanol thereto or ethanol does precipitating reagent, filter, dry,
The fibrous soluble polyimide containing the tert-butyl group and benzofuran structure is made；
The aromatic diamine monomers contain the tert-butyl group and benzofuran based structures, chemistry entitled 3,3 '-di-t-butyl -4, and 4 '-two
Aminophenyl -3 '-benzofuran methane, its structural formula are：
；
The aromatic dianhydride monomer be 3,3 ', 4,4 '-pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 3,3 ',
4,4 '-diphenyl ether tetraformic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA),
3,3 ', 4,4 '-diphenyl thio-ether tetrformate dianhydride, 1,4- double (3,4- di carboxyl phenyloxies) -2,2 ', 3- trimethylbenzenes dianhydride, 2,
Double (3,4- dicarboxyphenyis) hexafluoropropane dianhydrides of 2-, 1,1- are double（3,4- di carboxyl phenyloxies）Double (the 3,4- of benzophenone dianhydride, 2,2-
Dicarboxyphenyi) double [4- (3,4- di carboxyl phenyloxies) phenyl] hexafluoropropane dianhydrides of propane dianhydride or 2,2-；
The catalyst is HCl and/or KOH, and the mass percent that its dosage accounts for total amount of feeding is 2 ~ 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510368092.3A CN104987506B (en) | 2015-06-29 | 2015-06-29 | Soluble polyimide containing the tert-butyl group and benzofuran structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510368092.3A CN104987506B (en) | 2015-06-29 | 2015-06-29 | Soluble polyimide containing the tert-butyl group and benzofuran structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104987506A CN104987506A (en) | 2015-10-21 |
| CN104987506B true CN104987506B (en) | 2017-12-12 |
Family
ID=54299415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510368092.3A Expired - Fee Related CN104987506B (en) | 2015-06-29 | 2015-06-29 | Soluble polyimide containing the tert-butyl group and benzofuran structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104987506B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784462A (en) * | 2016-12-09 | 2017-05-31 | 德阳九鼎智远知识产权运营有限公司 | A kind of lithium battery for new-energy automobile |
| CN114920934B (en) * | 2022-06-29 | 2024-03-22 | 深圳职业技术学院 | Preparation method and application of photosensitive polyimide resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007086550A1 (en) * | 2006-01-27 | 2007-08-02 | Nippon Steel Chemical Co., Ltd. | Laminate for wiring board |
| CN103497336A (en) * | 2013-10-14 | 2014-01-08 | 桂林理工大学 | Soluble polyimide with tertiary butyl and non-coplanar structure and preparation method thereof |
| CN103524738A (en) * | 2013-10-14 | 2014-01-22 | 桂林理工大学 | Method for preparing soluble polyimide by use of aromatic diamine monomer containing naphthaline and tertiary-butyl structure |
| CN104356387A (en) * | 2014-11-11 | 2015-02-18 | 桂林理工大学 | Soluble polyimide material having non-coplanar structure and preparation method thereof |
| CN104370751A (en) * | 2014-11-11 | 2015-02-25 | 桂林理工大学 | Diamine monomers containing asymmetric non-coplanar structure and preparation method thereof |
-
2015
- 2015-06-29 CN CN201510368092.3A patent/CN104987506B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007086550A1 (en) * | 2006-01-27 | 2007-08-02 | Nippon Steel Chemical Co., Ltd. | Laminate for wiring board |
| CN103497336A (en) * | 2013-10-14 | 2014-01-08 | 桂林理工大学 | Soluble polyimide with tertiary butyl and non-coplanar structure and preparation method thereof |
| CN103524738A (en) * | 2013-10-14 | 2014-01-22 | 桂林理工大学 | Method for preparing soluble polyimide by use of aromatic diamine monomer containing naphthaline and tertiary-butyl structure |
| CN104356387A (en) * | 2014-11-11 | 2015-02-18 | 桂林理工大学 | Soluble polyimide material having non-coplanar structure and preparation method thereof |
| CN104370751A (en) * | 2014-11-11 | 2015-02-25 | 桂林理工大学 | Diamine monomers containing asymmetric non-coplanar structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104987506A (en) | 2015-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105566633B (en) | A kind of super-branched polyimide containing carbazole structure and its production and use | |
| CN102757560B (en) | Soluble functional polyimide with carbazole structure and preparation method and application thereof | |
| CN105085281B (en) | Diamine monomer, preparation method containing diphenylamines fluorenes and its application in polyimides is prepared | |
| KR100205963B1 (en) | Novel soluble polyimide resin for liquid crystal orientation film | |
| CN102604091B (en) | Polyimide containing benzimidazole unit and preparation method thereof | |
| CN102807675A (en) | Flexible transparent polyimide film material and preparation method thereof | |
| CN102352039B (en) | Soluble functional polyimide based on fluorene structure as well as preparation method and application thereof | |
| CN101880389B (en) | Phthalonitrile-terminated polyimide resin containing phthalazinone structure, cured product and preparation method thereof | |
| CN105254882B (en) | A kind of polyimides of the structure containing bipyridyl and preparation method thereof | |
| CN104804188B (en) | A kind of preparation method of Kapton | |
| CN103497336A (en) | Soluble polyimide with tertiary butyl and non-coplanar structure and preparation method thereof | |
| CN107602857A (en) | The preparation method and application of polyimides | |
| CN108102097A (en) | A kind of polyimides of base containing benzyne, preparation method and applications | |
| CN102816327A (en) | Polyimides containing ditrifluoromethyl group and unsymmetrical structure and preparation method thereof | |
| CN103524738A (en) | Method for preparing soluble polyimide by use of aromatic diamine monomer containing naphthaline and tertiary-butyl structure | |
| US4173700A (en) | Bis (difluoromaleimide) capped propolymers and polymers | |
| CN104987506B (en) | Soluble polyimide containing the tert-butyl group and benzofuran structure and preparation method thereof | |
| KR100205962B1 (en) | Novel soluble polyimide resin | |
| KR100270406B1 (en) | Novel soluble polyimides comprising polyalicyclic structure | |
| CN106832278A (en) | One class high transparency copoly type fluorine-containing polyimide film material and preparation method thereof | |
| CN105504281A (en) | High-barrier function polyimide containing naphthaline structure and preparation method and application thereof | |
| CN108997578B (en) | High-heat-resistance hyperbranched polyimide and preparation method and application thereof | |
| CN104356383B (en) | Polyimide containing four substituent pendant groups and distorted non-coplanar structure synchronously and preparation method thereof | |
| CN111154101A (en) | High-temperature-resistant ethynyl terminated polyimide material and preparation method thereof | |
| CN109928907A (en) | One kind having excellent machining property and reactive diluent resistant to high temperature 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 |
Effective date of registration: 20200710 Address after: 541004 502, 5th floor, building 1, No. 19, gualuan Road, Qixing District, Guilin City, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Yunzhi Jiuwo Experimental Instrument Co., Ltd Address before: 541004 the Guangxi Zhuang Autonomous Region Guilin Construction Road No. 12 Patentee before: GUILIN University OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171212 Termination date: 20210629 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |