CN106280440B - A kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof - Google Patents
A kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof Download PDFInfo
- Publication number
- CN106280440B CN106280440B CN201610847478.7A CN201610847478A CN106280440B CN 106280440 B CN106280440 B CN 106280440B CN 201610847478 A CN201610847478 A CN 201610847478A CN 106280440 B CN106280440 B CN 106280440B
- Authority
- CN
- China
- Prior art keywords
- nano
- preparation
- polyamic acid
- particle
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof, and the nano-particle of set amount is uniformly mixed with PAMAM dendrimers, obtains mixed solution one;The polyamic acid solution that acid anhydrides blocks is uniformly mixed with the mixed solution one, reacts, obtains mixed solution two;By the mixed solution two into membranization processing, polyamic acid gel mould is obtained;The polyamic acid gel mould is further heated, makes polyamic acid cyclisation for polyimides so as to obtain Polyimide/Nano particle composite film.Using the preparation method of the present invention, nano-particle can be made dispersed in polyimide matrix.There are the connection of chemical bond in end and polyamic acid additionally, due to PAMAM dendrimers, and prepared Polyimide/Nano particle composite material has preferable heat-resisting quantity, low temperature resistant, excellent mechanical performance and good chemical stability.
Description
Technical field
The present invention relates to a kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof, belong to function
Polymeric material field.
Background technology
The development of science and technology proposes material property new requirement, nanocomposite as a kind of new material just
It is valued by people.Polyimides is a kind of high molecular material of excellent performance, it has excellent within the scope of very wide temperature
Different high temperature resistant, low temperature resistant, radiation hardness, excellent mechanical performance and good chemical stability, therefore in aerospace, micro- electricity
The field such as son and electrical apparatus insulation tool has been widely used.It is more excellent that polyimides with Nanocomposites can be obtained into performance
Composite material.
It is nano-particle uniformly dividing in polyimides to prepare the Polyimide/Nano particle composite material most critical issue
The problem of dissipating, it is in-situ dispersion polymerization method and colloidal sol-solidifying to prepare the most important method of Polyimide/Nano particle composite material at present
Glue method.In-situ dispersion polymerization method is using means such as ultrasonic disperse, mechanical blendings, nano-particle is uniformly divided in the polymer
Dissipate, then in-situ polymerization under certain condition, so as to obtain Polyimide/Nano particle composite material.Prepared by this method
Composite material, nano-particle is scattered very uneven in polyimides, usually the surface of nano-particle is modified.It is molten
Glue-gel method is hydrolyzed and is condensed in the cosolvent of polyimides or monomer using the presoma of inorganic nano-particle, is formed
Gel be not separated with polymer, so as to obtain Polyimide/Nano particle composite material.The difficulty of this method is
Cosolvent of the selection with excellent dissolution performance, and the field of its application is also subject to certain restrictions.
The content of the invention
The purpose of the present invention is exactly to solve the deficiency of the above, there is provided a kind of polymolecularity Polyimide/Nano particle is compound
Film and preparation method thereof, this method have the advantages that it is simple, conveniently, wide application.
The technical solution adopted by the present invention is as follows:
The present invention provides a kind of Polyimide/Nano particle composite film, and the composition of the film is received for polyimides doping
Rice corpuscles, its main feature is that:The doping way of nano-particle is:It is tree-shaped big that the nano-particle is present in polyamide-amide (PAMAM)
In the cavity of molecule, PAMAM carries out chemical bond crosslinking by the anhydride group in terminal amido and the polyimides.
The thickness of the film is set according to actual conditions, generally 70~100um.
The present invention also provides a kind of preparation method of Polyimide/Nano particle composite film, comprise the following steps:
(1) nano-particle of set amount is uniformly mixed from the PAMAM dendrimers of different algebraically, obtains mixed solution
One;
(2) polyamic acid solution that acid anhydrides blocks is uniformly mixed with the mixed solution one, reacts, obtain mixed solution
Two;
(3) mixed solution two is subjected to film process, obtains polyamic acid gel mould;
(4) gel mould of step (3) is warming up at 190~210 DEG C 1~3h of vacuum drying, then heat to 230~
0.5~1.5h of re-dry at 250 DEG C, obtains Polyimide/Nano particle composite film after amidatioon.
In step (1), the PAMAM is to study more mature one kind in current dendrimer chemistry, is three kinds
One of dendrimer of commercialization.Construction unit is often repeated once as once multiplying in dendrimer, is obtained
The algebraically of product is increased by 1, it was reported that polyamide-amide (PAMAM) dendrimer was synthesized to for 10.0 generations at present.Different generations
Several PAMAM synthesis or acquisition have been the conventional technical means of those skilled in the art.Used in the present invention first and second,
With three generations PAMAM synthesized by the method for Tomalia.
Nano-particle in the present invention does not have particular determination, for example, the nano-particle is nano silver, Nanometer Copper, receive
One in rice silica, nano-titanium dioxide, nano barium phthalate, nano-calcium carbonate, nano strontium titanate, nano barium-strontium titanate etc.
Kind is several.
Preferably, the nano-particle is 1~15% in the mass percentage of PAMAM dendrimers.
Nano-particle is uniformly mixed the method using ultrasonic disperse with PAMAM dendrimers;Temperature and time does not have
It is particularly limited to, for the purpose of being uniformly dispersed, the ultrasonic disperse time can be 30~60min;Temperature can be room temperature (18~37 DEG C).
In step (2), the organic solvent containing set amount in the polyamic acid solution.The polyamide of the acid anhydrides end-blocking
The technological means for being prepared as those skilled in the art and routinely knowing of acid solution, its preparation method are not particularly limited, can be with
Prepared according to existing literature, universal method is using diamines and two anhydride reactants generation polyamic acid, in some of the present invention
In implementation, preferred following methods:Under nitrogen protection, it is 1.02~1.05 by molar ratio:1 dianhydride (is also referred to as binary
Acid anhydrides) and the diamines amine of binary (also referred to as) be added to the solution that solid content 10~15% (wt/wt) is made into organic solvent,
And 20~28h (preferably 24h) is reacted in ice-water bath, obtain the polyamic acid solution of acid anhydrides end-blocking;
Wherein, the dianhydride is pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracid two
Acid anhydride, 3,3 ', 4,4 '-oxydiphthalic, 2,2 '-bis- [4- (3,4- diacid phenoxy group) phenyl] propane tetracarboxylic dianhydrides, 2,2 '-
It is any in double (bis- carboxy phenyls of 3,4-) hexafluoropropane tetracarboxylic dianhydrides.
The diamines for 4,4 '-diaminodiphenyl ether, hexafluoro methyl biphenyl diamines, diaminodiphenylmethane, 4,4 '-it is bis-
Any of (4- amino-benzene oxygens) diphenyl sulphone (DPS), double [3,5- dimethyl -4- (4- amino) phenol] methane.
The solvent is high boiling point polar aprotic solvent, including n,N-Dimethylformamide, n,N-dimethylacetamide,
Any of n-methyl-2-pyrrolidone.
The anhydride group of the polyamic acid occurs anti-with the amido in the PAMAM dendrimers in the mixed solution one
Should.
The polyamic acid solution of the acid anhydrides end-blocking and the mass ratio of the mixed solution one are 1~10:100.
The condition of the reaction is ice-water bath;The ice-water bath time is 10~14h, and the preferably time is 12h.
In step (3), the method for film process is not particularly limited, and it is ability that mixed solution, which is prepared as film,
Field technique personnel's conventional technology.Following methods are used in certain embodiments of the present invention:The mixed solution two is poured
On note to mould, then mould is dried, solvent is removed, obtains polyamic acid gel mould.
In order to make the excellent performance of the laminated film finally obtained, described dry using being dried in vacuo, vacuum drying is divided into
In two stages, be dried in vacuo 1~3h at 70~90 DEG C first, is then dried in vacuo 1~3h at 140~160 DEG C.Preferably, 80
DEG C vacuum drying 2h, 150 DEG C vacuum drying 2h.
In step (4), it is preferred that be dried in vacuo 2h at 200 DEG C, be then dried in vacuo 1h at 240 DEG C.
The present invention provides the Polyimide/Nano particle composite film that a kind of above method is prepared.
A technical solution in above-mentioned technical proposal has the advantages that:
Nano-particle is scattered in tree-shaped big point of PAMAM by the present invention using a large amount of cavitys present in dendritic macromole
In the cavity of son, then reacted for the polyamic acid of anhydride group with end, most afterwards through removing solvent, hot amidatioon obtains polyamides
Imines/Nanocomposites film.
Using the preparation method of the present invention, nano-particle can be made dispersed in polyimide matrix.Additionally, due to
PAMAM ends have the connection of chemical bond with polyamic acid, and prepared Polyimide/Nano particle composite material has preferable
Heat-resisting quantity, low temperature resistant, excellent mechanical performance and good chemical stability.In aerospace, microelectronics and electrical apparatus insulation
Have been widely used Deng field tool.
The method of the present invention provides a kind of new thinking to prepare Polyimide/Nano particle composite film.
Brief description of the drawings
Fig. 1 is scattered schematic diagram of the nano-particle in PAMAM.
Fig. 2 is that Polyimide/Nano particle composite membrane prepares schematic diagram, wherein, n is 100~200,Table
Show dianhydride, H2N-Ar′-NH2Represent diamines.
Embodiment
First and second and three generations PAMAM is conventionally synthesized by the method for Tomalia in the present embodiment.
Embodiment 1
The nano barium phthalate of 0.20g is added in the PAMAM solution of the 5.62g first generation, ultrasonic disperse 30min, such as Fig. 1
It is shown.Under nitrogen protection, by the 4 of the pyromellitic acid anhydride of 2.2248g and 2.0023g, 4 '-diaminodiphenyl ether is added to
The solution of solid content 15% (wt/wt) is made into the 1-methyl-2-pyrrolidinone of 28.18g, and 24h is reacted in ice-water bath, is obtained
The polyamic acid solution of acid anhydride end-blocking.The first generation PAMAM solution that 2.91g has been disperseed to nano barium phthalate particle is added to above-mentioned gather
In acid amides acid solution, after several minutes of ultrasonic disperse, the reaction was continued 12h obtains viscous fluid of polyamide acid.Take appropriate polyamic acid sticky
Liquid is poured into the glass board mould of cleaning.Mould is put into vacuum drying chamber, 80 DEG C of vacuum drying 2h, 150 DEG C of vacuum are done
Dry 2h, obtains polyamic acid gel mould.It is continuously heating to after being dried in vacuo 1h at 200 DEG C, is warming up at 240 DEG C and is dried in vacuo again
1h, obtains Polyimide/Nano particle composite film, and basic procedure is as shown in Figure 2.The thickness of the film is set according to actual conditions
It is fixed, generally 70~100um.By verification experimental verification, nano barium phthalate is uniformly dispersed in polyimides, and obtained film has
Preferable heat-resisting quantity, low temperature resistant, excellent mechanical performance and good chemical stability.
Embodiment 2
The nano silver particles of 0.3g are added in the PAMAM solution of the 5.45g second generations, ultrasonic disperse 40min.In nitrogen
Under protection, by the 4 of the pyromellitic acid anhydride of 2.2466g and 2.0023g, 4 '-diaminodiphenyl ether is added to the N of 42.49g,
The solution of solid content 10% (wt/wt) is made into N- dimethylacetylamides, and 23h is reacted in ice-water bath, obtains acid anhydride end-blocking
Polyamic acid solution.The second generation PAMAM solution that 2.46g has been disperseed to nano silver particles is added to above-mentioned polyamic acid solution
In, after several minutes of ultrasonic disperse, the reaction was continued 11h obtains viscous fluid of polyamide acid.Appropriate viscous fluid of polyamide acid is taken to be poured into clean
In net glass board mould.Mould is put into vacuum drying chamber, 80 DEG C of vacuum drying 2h, 150 DEG C of vacuum drying 2h, remove molten
Agent, obtains polyamic acid gel mould.It is continuously heating to after being dried in vacuo 2h at 200 DEG C, is warming up at 240 DEG C and is dried in vacuo 1h again,
Obtain Polyimide/Nano particle composite film.The thickness of the film is set according to actual conditions, generally 70~100um.Through
Overtesting verifies that nano silver particles are uniformly dispersed in polyimides, and obtained film has preferable heat-resisting quantity, resistance to low
Warm, excellent mechanical performance and good chemical stability.
Embodiment 3
The nano-silicon dioxide particle of 0.40g is added in 3.31g third generation PAMAM solution, ultrasonic disperse 30min.
Under nitrogen protection, by the 4 of the pyromellitic acid anhydride of 2.2903g and 2.0023g, 4 '-diaminodiphenyl ether is added to
The solution of solid content 15% (wt/wt) is made into the n,N-Dimethylformamide of 28.62g, and 22h is reacted in ice-water bath, is obtained
To the polyamic acid solution of acid anhydride end-blocking.The third generation polyamide-amide solution that 1.95g has been disperseed to nano silicon dioxide is added to
State in polyamic acid solution, after several minutes of ultrasonic disperse, the reaction was continued 13h obtains viscous fluid of polyamide acid.Take appropriate polyamic acid
Viscous fluid is poured into the glass board mould of cleaning.Mould is put into vacuum drying chamber, 80 DEG C of vacuum drying 2h, 150 DEG C true
The dry 2h of sky, removes solvent, obtains polyamic acid gel mould.It is continuously heating to after being dried in vacuo 2h at 200 DEG C, is warming up to 240 DEG C
Under be dried in vacuo 1h again, obtain Polyimide/Nano particle composite film.The thickness of the film is set according to actual conditions, and one
As be 70~100um.By verification experimental verification, nano-silicon dioxide particle is uniformly dispersed in polyimides, obtained film tool
There are preferable heat-resisting quantity, low temperature resistant, excellent mechanical performance and good chemical stability.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (13)
1. a kind of Polyimide/Nano particle composite film, the composition of the film is polyimides dopen Nano particle, its feature
It is:The doping way of the nano-particle is:The nano-particle is present in the cavity of Polyamidoamine Dendrimers, institute
State Polyamidoamine Dendrimers and chemical bond crosslinking carried out by the anhydride group in itself terminal amido and the polyimides,
So as to obtain the laminated film of polyimides dopen Nano particle.
2. a kind of preparation method of Polyimide/Nano particle composite film, it is characterized in that, comprise the following steps:
(1) nano-particle of set amount is uniformly mixed with Polyamidoamine Dendrimers, obtains mixed solution one;
(2) polyamic acid solution that acid anhydrides blocks is uniformly mixed with the mixed solution one, reacts, obtain mixed solution two;
(3) mixed solution two is subjected to film process, obtains polyamic acid gel mould;
(4) gel mould of step (3) is continued to be warming up to 1~3h of vacuum drying at 190~210 DEG C, is warming up to 230~250 DEG C
0.5~1.5h of lower re-dry, obtains Polyimide/Nano particle composite film after amidatioon.
3. preparation method as claimed in claim 2, it is characterized in that:In step (1), the nano-particle is nano silver, nanometer
In copper, nano silicon dioxide, nano-titanium dioxide, nano barium phthalate, nano-calcium carbonate, nano strontium titanate, nano barium-strontium titanate
One or more.
4. preparation method as claimed in claim 2, it is characterized in that:In step (1), the nano-particle is in polyamide-amide tree
The mass percentage of shape macromolecular is 1~15%.
5. preparation method as claimed in claim 2, it is characterized in that:In step (2), the polyamic acid solution of acid anhydrides end-blocking is profit
It is prepared with diamines and two anhydride reactants generation polyamic acid.
6. preparation method as claimed in claim 5, it is characterized in that:Under nitrogen protection, it is 1.02~1.05 by molar ratio:1
Dianhydride and diamines be added to the solution that solid content 10~15% (wt/wt) is made into organic solvent, and reacted in ice-water bath
20~28h, obtains the polyamic acid solution of acid anhydrides end-blocking.
7. preparation method as claimed in claim 5, it is characterized in that:The dianhydride is pyromellitic acid anhydride, bibenzene tetracarboxylic
Dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-oxydiphthalic, 2,2 '-bis- [4- (3,4- diacid
Phenoxy group) phenyl] it is propane tetracarboxylic dianhydride, any in 2,2 '-bis- (bis- carboxy phenyls of 3,4-) hexafluoropropane tetracarboxylic dianhydrides;Described two
Amine is 4,4 '-diaminodiphenyl ether, hexafluoro methyl biphenyl diamines, diaminodiphenylmethane, 4,4 '-bis- (4- amino-benzene oxygens) two
Any of benzene sulfone, double [3,5- dimethyl -4- (4- amino) phenol] methane.
8. preparation method as claimed in claim 2, it is characterized in that:In step (2), the polyamic acid solution of the acid anhydrides end-blocking
Mass ratio with the mixed solution one is 1~10:100.
9. preparation method as claimed in claim 2, it is characterized in that:In step (2), the condition of the reaction is ice-water bath;Ice
Water bath time is 10~14h.
10. preparation method as claimed in claim 9, it is characterized in that:The ice-water bath time is 12h.
11. preparation method as claimed in claim 2, it is characterized in that:In step (3), the mixed solution two is poured into mould
On tool, then mould is dried, solvent is removed, obtains polyamic acid gel mould.
12. preparation method as claimed in claim 2, it is characterized in that:In step (4), 2h, Ran Hou are dried in vacuo at 200 DEG C
240 DEG C of vacuum drying 1h.
13. the Polyimide/Nano particle THIN COMPOSITE being prepared using the method any one of claim 2~12
Film.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610847478.7A CN106280440B (en) | 2016-09-23 | 2016-09-23 | A kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610847478.7A CN106280440B (en) | 2016-09-23 | 2016-09-23 | A kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106280440A CN106280440A (en) | 2017-01-04 |
CN106280440B true CN106280440B (en) | 2018-04-13 |
Family
ID=57714832
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610847478.7A Expired - Fee Related CN106280440B (en) | 2016-09-23 | 2016-09-23 | A kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106280440B (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107033502B (en) * | 2017-05-17 | 2019-04-23 | 南京航空航天大学 | A kind of neodymium-doped titanium acid barium/organic matrix composite membrane of simple high energy storage density and preparation method thereof |
CN107603215A (en) * | 2017-09-22 | 2018-01-19 | 安庆市虹泰新材料有限责任公司 | A kind of preparation method of polyamide copper composite membrane |
CN108036532B (en) * | 2017-11-18 | 2021-08-06 | 山东龙光天旭太阳能有限公司 | Preparation method of low-temperature-resistant spectrum selective absorption coating of solar heat collecting pipe |
CN107841137A (en) * | 2017-11-29 | 2018-03-27 | 广东聚航新材料研究院有限公司 | A kind of high-dielectric composite material containing Nanometer Copper/polyimides and preparation method thereof |
CN112375381A (en) * | 2020-12-09 | 2021-02-19 | 安徽威能电源科技有限公司 | Preparation method of high-temperature-resistant polyimide material |
CN113555553A (en) * | 2021-06-03 | 2021-10-26 | 浙江中科玖源新材料有限公司 | Polyimide binder for lithium ion battery, preparation method of polyimide binder and silicon-carbon negative plate |
CN113621162B (en) * | 2021-06-28 | 2023-04-07 | 浙江中科玖源新材料有限公司 | Transparent conductive film |
CN113956658B (en) * | 2021-10-21 | 2024-01-30 | 北京宇程科技有限公司 | Polyimide/titanium dioxide composite microsphere and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101381514A (en) * | 2008-09-11 | 2009-03-11 | 东华大学 | Method for improving dispersion of nano silica granules in polyimide resin |
CN104797327A (en) * | 2012-11-20 | 2015-07-22 | 环球油品公司 | Cross-linked polyimide membranes for separations |
CN105153699A (en) * | 2015-07-31 | 2015-12-16 | 江苏省电力公司泰州供电公司 | Preparation method of hyper branched copolymerized polyimide/zinc oxide (ZnO) hybrid insulated film |
-
2016
- 2016-09-23 CN CN201610847478.7A patent/CN106280440B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101381514A (en) * | 2008-09-11 | 2009-03-11 | 东华大学 | Method for improving dispersion of nano silica granules in polyimide resin |
CN104797327A (en) * | 2012-11-20 | 2015-07-22 | 环球油品公司 | Cross-linked polyimide membranes for separations |
CN105153699A (en) * | 2015-07-31 | 2015-12-16 | 江苏省电力公司泰州供电公司 | Preparation method of hyper branched copolymerized polyimide/zinc oxide (ZnO) hybrid insulated film |
Also Published As
Publication number | Publication date |
---|---|
CN106280440A (en) | 2017-01-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106280440B (en) | A kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof | |
CN108610631B (en) | A kind of high thermal conductivity Kapton and preparation method thereof | |
CN105566633B (en) | A kind of super-branched polyimide containing carbazole structure and its production and use | |
CN100494280C (en) | Method for preparing polyimide/ silicon dioxide hollow micro-sphere composite film | |
CN103524767B (en) | The Novel electronic grade Kapton of a kind of low linear expansion coefficient and manufacture method thereof | |
CN108530673A (en) | A kind of linear polyimides aeroge and preparation method thereof | |
CN108727818A (en) | A kind of hydrophobic type silica/polyimides aerogel composite and preparation method | |
CN103772981A (en) | Low-dielectric-constant polymer/fluorinated graphene composite material and preparation method thereof | |
CN106167547B (en) | A kind of crystallinity copolyimide resin of the easy melt-processed of low melt viscosity and application | |
CN109929129A (en) | A kind of carboxylic carbon nano-tube/polyimide composite film and preparation method thereof | |
CN101168598A (en) | Method for preparing ultra-thick polyimide film with high heat conductivity and low thermal expansion coefficient | |
CN108864473A (en) | Ultralight heat-insulated resilient polyimide nano-fiber aeroge and preparation method thereof | |
CN1911985A (en) | Ultralow dielectric constant polyimide film and its preparation method | |
CN103923330A (en) | Method for preparing high-thermal conductivity polyimide/magnesium oxide composite film | |
CN109438735A (en) | A kind of high thermal conductivity polyimides based coextruded film and preparation method thereof | |
CN104672900A (en) | High dielectric constant polyimide/multiwalled carbon nanotube/nano barium titanate composite film and preparation method thereof | |
CN105968393A (en) | Preparation method of polyimide and fluorinated graphene oxide composite material | |
TW201722969A (en) | Amino-containing silica particle, composition for forming polyimide aerogel, polyimide aerogel and method of fabricating the same, polyimide aerogel-containing composite material | |
CN105111476A (en) | Preparation method for polyimide film | |
CN105670029A (en) | Method for preparing polyimide aerogel through direct vacuum drying | |
CN106046373B (en) | A kind of solvable polyimide film and preparation method with anti-flammability | |
CN107384189A (en) | A kind of preparation method of fluorinated graphene/polyimide enameled wire | |
CN106497054A (en) | Nano-TiO2/ polyimide composite film and preparation method thereof | |
CN108794748A (en) | A kind of Kapton of low-k and preparation method thereof | |
CN105085915B (en) | A kind of high dielectric polyimides/carbon nano tube compound material 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 | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180413 Termination date: 20190923 |