CN108530627A - A kind of preparation method of microfabricated tunable polyimides - Google Patents
A kind of preparation method of microfabricated tunable polyimides Download PDFInfo
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- CN108530627A CN108530627A CN201810320976.5A CN201810320976A CN108530627A CN 108530627 A CN108530627 A CN 108530627A CN 201810320976 A CN201810320976 A CN 201810320976A CN 108530627 A CN108530627 A CN 108530627A
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- preparation
- polyimide material
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- tunable
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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides a kind of preparation methods of microfabricated tunable polyimide material, belong to macromolecule material preparation area.The present invention is in aprotic polar solvent, and dicarboxylic anhydride and diamine first carry out low-temperature polycondensation, obtain soluble polyamic acid；Then dehydration is cyclic to get microfabricated tunable polyimide material at high temperature.The present invention realizes the system regulation to polyimide material micro-structure by studying the matching of steric hindrance between different dicarboxylic anhydrides and diamine on the basis of controlling time and the high temperature cyclization temperature and time of low-temperature polycondensation.
Description
Technical field
The invention belongs to macromolecule material preparation areas, are related to a kind of preparation side of microfabricated tunable polyimide material
Method.
Background technology
With the appearance and application of nanotechnology and nano material, it has been found that the performance of material not only with material itself
Chemical constituent is related, also with its microstructure close relation.When substance changes in microcosmos, then in macroscopic view
In the world, the behavior of substance can also change therewith.The micro-structure of material largely can be by preparation process, growth course etc.
The influence of factor.Therefore, the influence factor of research material micro-structure, step control its micro-structure of going forward side by side, can not only control material
The microscopic pattern of material can also change its physics, chemical property.
The study on regulation of material microstructure focuses primarily upon carbon material, metal material, Janus materials etc. at present, fresh to relate to less
Sufficient the field of polymers.And focus preparation and the system regulation of polymer microstructure, can be novel high polymer material in phototube
Solid foundation is established in application in the fields such as part, biomedicine, environment and energy technology.Polyimides is that comprehensive performance is best
One of high-molecular organic material is widely used in the necks such as space flight and aviation, microelectronics, nanometer as a kind of special engineered material
Domain.In recent years, each state all by the research of polyimides, exploitation and using be included in 21 century most promising engineering plastics it
One.However, the method by regulating and controlling polyimide microstructures is there is no at present, to expand the correlation of polyimide material application field
Technology or document report.
Invention content
The object of the present invention is to provide a kind of preparation methods of microfabricated tunable polyimide material.
The preparation method of microfabricated tunable polyimide material of the present invention, be in aprotic polar solvent, dicarboxylic anhydride and
Diamine first carries out low-temperature polycondensation, obtains soluble polyamic acid；Then dehydration cyclization is poly- to get microfabricated tunable at high temperature
Acid imide material.
The dicarboxylic anhydride is 4,4 '-biphenyl ether dianhydrides, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 3,3 ', 4,4 '-hexichol first
At least one of ketone tetracarboxylic dianhydride, hexafluorodianhydride (6FDA), pyromellitic dianhydride；The diamine is benzidine, to benzene
Diamines, 2, at least one of 2 '-bis- (trifluoromethyl) benzidines, 3,3 '-diaminobenzidines, and dicarboxylic anhydride and binary
The molar ratio of amine is 1:1 ~ 1:5.
The aprotic polar solvent is in N,N-dimethylformamide, dimethylacetylamide, N-Methyl pyrrolidone
It is at least one.
The low-temperature polycondensation is polycondensation reaction at room temperature 5 ~ 15 hours.
The high temperature cyclization is reacted 1 ~ 12 hour at 140 ~ 200 DEG C.
The present invention is controlling low-temperature polycondensation by the matching of steric hindrance between the different dicarboxylic anhydrides of research and diamine
On the basis of time and high temperature cyclization temperature and time, the system regulation to polyimide material micro-structure is realized.It selects empty
Between steric hindrance match good dicarboxylic anhydride and diamine, the low-temperature polycondensation time is controlled by water bath with thermostatic control, is operated using incubation water heating
The temperature and time of high temperature cyclization is controlled, bundle shape is presented in finally obtained polyimide material and nanometer sheet pattern is uniform, thick
Spend relatively thin, averagely about 3.8 nm.Its SEM microscopic appearance figure is shown in Fig. 1.It is primarily useful for Aeronautics and Astronautics, microelectronics, nanometer, liquid
The fields such as crystalline substance, seperation film, laser.
It selects steric hindrance to match preferable dicarboxylic anhydride and diamine, the low-temperature polycondensation time is controlled by water bath with thermostatic control, is adopted
With the temperature and time of incubation water heating operation and control high temperature cyclization, the nano flower to interweave is presented in finally obtained polyimide material
Sheet, and nanometer sheet pattern is uniform, thinner thickness, averagely about 4.0 nm.Its SEM microscopic appearance figure is shown in Fig. 2.It is primarily useful for
The fields such as Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, seperation film, laser.
It selects steric hindrance to match poor dicarboxylic anhydride and diamine, the low-temperature polycondensation time is controlled by water bath with thermostatic control, is adopted
With the temperature and time of incubation water heating operation and control high temperature cyclization, mutually folded nanometer sheet is presented in finally obtained polyimide material
Shape structure, and nanometer sheet pattern is uniform, thickness is thicker, averagely about 7.9 nm.Its SEM microscopic appearance figure is shown in Fig. 3.It is main available
In fields such as Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, seperation film, laser.
Description of the drawings
Fig. 1 is the SEM figures that bundle shape nanometer sheet microfabricated tunable polyimide material is presented in structure.
Fig. 2 is the SEM figures that the nano flower sheet microstructure polyimide material to interweave is presented in structure.
Fig. 3 is the SEM figures for the polyimide material that structure is mutually folded nano-sheet microstructure.
Specific implementation mode
The preparation of polyimide material of the present invention and its adjustability of micro-structure are made into one below by specific embodiment
Walk explanation.
Embodiment 1
Weigh 0.184 g（1mmol）Benzidine is dissolved in 30 mL dimethylacetylamides, is then slowly added to 0.310
g（1mmol）4,4 '-biphenyl ether dianhydrides, react 8 h at room temperature.Later in 50 mL water heating kettles of transposition, controlling reaction temperature is 180
12 h are reacted at DEG C；It centrifuges after reaction, products therefrom is washed repeatedly with ethyl alcohol, dimethylacetylamide successively.Finally 60
DEG C vacuum drying oven drying, obtain final sample.The sem test of sample is shown in Fig. 1, which is presented bundle shape,
The thickness of nanometer sheet is averagely about 3.8 nm.
Embodiment 2
Weigh 0.324 g（3 mmol）P-phenylenediamine is dissolved in 30 mL n,N-Dimethylformamide, is then slowly added to 0.322
g （1 mmol）In 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides to above-mentioned solution, 12 h are reacted at room temperature.Transposition 50 later
In mL water heating kettles, control temperature reacts 6 h at 150 DEG C.It centrifuges after reaction, products therefrom uses ethyl alcohol, N, N- bis- successively
Methylformamide washing is multiple.Finally the vacuum drying oven at 60 DEG C is dried, and obtains final sample.The sem test of sample is shown in
Overlapping nano-sheet is presented in Fig. 3 material microstructures, and nanometer sheet thickness is thicker, averagely about 7.9 nm.
Embodiment 3
Weigh 0.428 g（2 mmol）3,3 '-diaminobenzidines are dissolved in 30 mL n,N-Dimethylformamide, then slow
It is slow that 0.218 g is added（1 mmol）In pyromellitic dianhydride to above-mentioned solution, 15 h are reacted at room temperature.50 mL water of transposition later
In hot kettle, control temperature reacts 8 h at 180 DEG C.It centrifuges after reaction, products therefrom uses ethyl alcohol, N, N- dimethyl methyls successively
Amide washing is multiple, and finally the vacuum drying oven at 60 DEG C is dried, and obtains final sample.The sem test of sample is shown in that Fig. 3 should
Overlapping nano-sheet is presented in material microstructure, and nanometer sheet thickness is thicker, averagely about 7.9 nm.
Embodiment 4
Weigh 0.320 g（1 mmol）2,2 '-bis- (trifluoromethyl) benzidines are dissolved in 30 mL N-Methyl pyrrolidones
In, it is then slowly added to 0.444 g（1 mmol）In hexafluorodianhydride (6FDA) to above-mentioned solution, 10 h are reacted at room temperature.Transposition 50 later
In mL water heating kettles, control temperature reacts 6 h at 170 DEG C.It centrifuges after reaction, products therefrom uses ethyl alcohol, N- methyl pyrroles successively
Pyrrolidone washing is multiple.Finally the vacuum drying oven at 60 DEG C is dried, and obtains final sample.The sem test of sample is shown in Fig. 1,
Bundle shape is presented in the material microstructure, and the thickness of nanometer sheet is averagely about 3.8 nm.
Embodiment 5
Weigh 0.640 g（1.4 mmol）2,2 '-bis- (trifluoromethyl) benzidines are dissolved in 30 mL N, N- dimethyl formyls
In amine, it is then slowly added to 0.322 g（1 mmol）In 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides to above-mentioned solution, room
Temperature is lower to react 7 h.Later in 50 mL water heating kettles of transposition, control temperature reacts 12 h at 140 DEG C.It centrifuges after reaction, gained
Product washs repeatedly successively and with ethyl alcohol, N,N-dimethylformamide.Finally the vacuum drying oven at 60 DEG C is dried, and obtains final samples
Product.The sem test of sample is shown in Fig. 2, which is presented the nano flower laminated structure to interweave, the thickness of nanometer flower piece
Degree is averagely about 4.0 nm.
Embodiment 6
Weigh 0.736 g（4.35 mmol）Benzidine is dissolved in 30 mL dimethylacetylamides, is then slowly added to
0.218 g（1 mmol）In pyromellitic dianhydride to above-mentioned solution, 10 h are reacted at room temperature.Later in 50 mL water heating kettles of transposition,
Control temperature reacts 10 h at 180 DEG C.It centrifuges after reaction, products therefrom is washed with ethyl alcohol, dimethylacetylamide more successively
It is secondary.Finally the vacuum drying oven at 60 DEG C is dried, and obtains final sample.The sem test of sample is shown in Fig. 1, the material microstructure
Bundle shape is presented, the thickness of nanometer sheet is averagely about 3.8 nm.
Claims (7)
1. a kind of preparation method of microfabricated tunable polyimide material is dicarboxylic anhydride and binary in aprotic polar solvent
Amine first carries out low-temperature polycondensation, obtains soluble polyamic acid；Then dehydration cyclization is sub- to get microfabricated tunable polyamides at high temperature
Amine material.
2. the preparation method of microfabricated tunable polyimide material as described in claim 1, it is characterised in that：The dicarboxylic anhydride is
4,4 '-biphenyl ether dianhydrides, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, hexafluoro two
At least one of acid anhydride, pyromellitic dianhydride.
3. the preparation method of microfabricated tunable polyimide material as described in claim 1, it is characterised in that：The diamine is
At least one in benzidine, p-phenylenediamine, 2,2 '-bis- (trifluoromethyl) benzidines, 3,3 '-diaminobenzidines
Kind.
4. the preparation method of microfabricated tunable polyimide material as described in claim 1, it is characterised in that：The dicarboxylic anhydride and
The molar ratio of diamine is 1:1~1:5.
5. the preparation method of microfabricated tunable polyimide material as described in claim 1, it is characterised in that：The non-proton pole
Property solvent be N,N-dimethylformamide, dimethylacetylamide, at least one of N-Methyl pyrrolidone.
6. the preparation method of microfabricated tunable polyimide material as described in claim 1, it is characterised in that：The low-temperature polycondensation
It is polycondensation reaction at room temperature 5 ~ 15 hours.
7. the preparation method of microfabricated tunable polyimide material as described in claim 1, it is characterised in that：The high temperature cyclization
It is to be reacted 1 ~ 12 hour at 140 ~ 200 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244433A (en) * | 2020-01-15 | 2020-06-05 | 华南师范大学 | Polyamine composite material, slurry, electrode plate, lithium-sulfur battery and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690415A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院化学研究所 | Polyimide microspheres and preparation method and application thereof |
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- 2018-04-11 CN CN201810320976.5A patent/CN108530627A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690415A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院化学研究所 | Polyimide microspheres and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ZHIXIAO XU ET AL.: "Nitrogen-Doped Porous Carbon Superstructures Derived from Hierarchical Assembly of Polyimide Nanosheets", 《ADVANCED MATERIALS》 * |
| 徐志骁: "基于聚酰亚胺自组装的多级结构氮掺杂碳材料及其性能研究", 《万方数据知识服务平台》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244433A (en) * | 2020-01-15 | 2020-06-05 | 华南师范大学 | Polyamine composite material, slurry, electrode plate, lithium-sulfur battery and preparation method |
| CN111244433B (en) * | 2020-01-15 | 2021-05-11 | 华南师范大学 | Polyamine composite material, slurry, electrode plate, lithium-sulfur battery and preparation method |
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Application publication date: 20180914 |