CN106280440A - 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
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- CN106280440A CN106280440A CN201610847478.7A CN201610847478A CN106280440A CN 106280440 A CN106280440 A CN 106280440A CN 201610847478 A CN201610847478 A CN 201610847478A CN 106280440 A CN106280440 A CN 106280440A
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention discloses a kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof, the nanoparticle of set amount is mixed homogeneously with PAMAM dendrimer, obtains mixed solution one；The polyamic acid solution that anhydride blocks is mixed homogeneously with described mixed solution one, reaction, obtain mixed solution two；Become membranization to process described mixed solution two, obtain polyamic acid gel film；By the described further heat treated of polyamic acid gel film, polyamic acid cyclisation is made for polyimides thus to obtain Polyimide/Nano particle composite film.Utilize the preparation method of the present invention, nanoparticle can be made dispersed in polyimide matrix.End and polyamic acid additionally, due to PAMAM dendrimer has the connection of chemical bond, 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 new requirement to material property, and nano composite material is as a kind of new material just
It is subject to people's attention.Polyimides is the macromolecular material of a kind of excellent performance, and it has excellent within the scope of the widest temperature
Different high temperature resistant, low temperature resistant, radiation hardness, excellent mechanical performance and good chemical stability, therefore at Aero-Space, micro-electricity
The field tools such as son and electrical apparatus insulation have been widely used.Polyimides and Nanocomposites can be obtained performance more excellent
Composite.
Preparing the Polyimide/Nano particle composite material most critical issue is nanoparticle uniformly dividing in polyimides
The problem of dissipating, preparing the topmost method of Polyimide/Nano particle composite material at present is in-situ dispersion polymerization method and colloidal sol-solidifying
Glue method.In-situ dispersion polymerization method is to use the means such as ultrasonic disperse, mechanical blending, makes nanoparticle the most uniformly divide
Dissipate, in-situ polymerization the most under certain condition, thus obtain Polyimide/Nano particle composite material.Prepared by this method
Composite, nanoparticle dispersion in polyimides is the most uneven, generally will be to the modifying surface of nanoparticle.Molten
Glue-gel method is that the presoma utilizing inorganic nano-particle hydrolyzes in the cosolvent of polyimides or monomer and is condensed, and is formed
Gel do not occur to be separated with polymer, thus obtain Polyimide/Nano particle composite material.The difficulty of this method is
Select the cosolvent with excellent dissolution performance, and the field of its application is also subject to certain restrictions.
Summary of the invention
The purpose of the present invention is exactly to solve above deficiency, it is provided that a kind of polymolecularity Polyimide/Nano particle is combined
Thin film and preparation method thereof, this method has the advantages such as simple, convenient, wide application.
The technical solution used in the present invention is as follows:
The present invention provides a kind of Polyimide/Nano particle composite film, and the polyimides doping that consists of of this thin film is received
Rice corpuscles, is characterized in: the doping way of nanoparticle is: it is tree-shaped greatly that described nanoparticle is present in polyamide-amide (PAMAM)
In the cavity of molecule, PAMAM carries out chemical bond crosslinking by terminal amido with the anhydride group in described polyimides.
The thickness of this thin film sets according to practical situation, generally 70～100um.
The present invention also provides for the preparation method of a kind of Polyimide/Nano particle composite film, comprises the following steps:
(1) by the PAMAM dendrimer mix homogeneously of the nanoparticle of set amount from different algebraically, mixed solution is obtained
One；
(2) polyamic acid solution that anhydride blocks is mixed homogeneously with described mixed solution one, reaction, obtain mixed solution
Two；
(3) described mixed solution two is carried out film forming process, obtain polyamic acid gel film；
(4) gel film of step (3) is warmed up at 190～210 DEG C vacuum drying 1～3h, then heat to 230～
It is dried 0.5～1.5h at 250 DEG C again, after amidatioon, obtains Polyimide/Nano particle composite film.
In step (1), described PAMAM is to study a more ripe class in current dendrimer chemistry, is three kinds
One of dendrimer of commercialization.In dendrimer, construction unit is often repeated once to become and once multiplies, and obtains
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
The PAMAM synthesis of number or acquisition have been the routine techniques means of those skilled in the art.In the present invention use first and second,
It is to be synthesized by the method for Tomalia with three generations PAMAM.
Nanoparticle in the present invention does not has particular determination, and such as, described nanoparticle is nanometer silver, Nanometer Copper, receives
In rice silicon dioxide, nano titanium oxide, nano barium phthalate, nano-calcium carbonate, nano strontium titanate, nano barium-strontium titanate etc. one
Plant or several.
Preferably, described nanoparticle is 1～15% at the weight/mass percentage composition of PAMAM dendrimer.
Nanoparticle mix homogeneously with PAMAM dendrimer use ultrasonic disperse method；Temperature and time is not
Being 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), described polyamic acid solution contains the organic solvent of set amount.The polyamide of described anhydride end-blocking
Acid solution be prepared as the technological means that those skilled in the art's routine is known, its preparation method is not particularly limited, permissible
Being prepared according to existing document, universal method is to utilize diamidogen and two anhydride reactants to generate polyamic acid, in some of the present invention
In enforcement, preferably following methods: under nitrogen protection, by dianhydride that mol ratio is 1.02～1.05:1 (also referred to as binary
Anhydride) and diamidogen (the also referred to as amine of binary) join and organic solvent be made into solid content 10～the solution of 15% (wt/wt),
And in ice-water bath, react 20～28h (preferably 24h), obtain the polyamic acid solution of anhydride end-blocking；
Wherein, described 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 '-
In double (3,4-bis-carboxy phenyl) HFC-236fa tetracarboxylic dianhydride any one.
Described diamidogen be 4,4 '-diaminodiphenyl ether, hexafluoro methyl biphenyl diamidogen, MDA, 4,4 '-bis-
Any one in (4-amino-benzene oxygen) diphenyl sulphone (DPS), double [3,5-dimethyl-4-(4-amino) phenol] methane.
Described solvent is high boiling point polar aprotic solvent, including DMF, N,N-dimethylacetamide,
Any one in METHYLPYRROLIDONE.
The anhydride group of described polyamic acid and the amido in the PAMAM dendrimer in described mixed solution one occur anti-
Should.
The polyamic acid solution of described anhydride end-blocking is 1～10:100 with the mass ratio of described mixed solution one.
The condition of described reaction is ice-water bath；The ice-water bath time is 10～14h, and the preferably time is 12h.
In step (3), the method that film forming processes is not particularly limited, and mixed solution preparation is become thin film is ability
Field technique personnel's conventional technique means.Certain embodiments of the present invention uses following methods: watered by described mixed solution two
Note to mould, then mould is dried, desolvation, obtains polyamic acid gel film.
In order to make the excellent performance of the laminated film finally given, described dry employing is vacuum dried, and vacuum drying is divided into
In two stages, first it is vacuum dried 1～3h at 70～90 DEG C, is then vacuum dried 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 vacuum dried 2h at 200 DEG C, be then vacuum dried 1h at 240 DEG C.
The present invention provides the Polyimide/Nano particle composite film that a kind of said method prepares.
A technical scheme in technique scheme has the advantages that
The present invention utilizes a large amount of cavitys present in dendritic macromole, and nanoparticle is scattered in tree-shaped big point of PAMAM
In the cavity of son, then react with the polyamic acid that end is anhydride group, after through removing solvent, hot amidatioon obtains polyamides
Imines/Nanocomposites thin film.
Utilize the preparation method of the present invention, nanoparticle can be made dispersed in polyimide matrix.Additionally, due to
PAMAM end and polyamic acid have the connection of chemical bond, and prepared Polyimide/Nano particle composite material has preferably
Heat-resisting quantity, low temperature resistant, excellent mechanical performance and good chemical stability.At Aero-Space, microelectronics and electrical apparatus insulation
Have been widely used Deng field tool.
The method of the present invention is to prepare Polyimide/Nano particle composite film to provide a kind of new thinking.
Accompanying drawing explanation
Fig. 1 is nanoparticle dispersion schematic diagram in PAMAM.
Fig. 2 be Polyimide/Nano particle composite membrane prepare schematic diagram, wherein, n is 100～200,Table
Show dianhydride, H2N-Ar′-NH2Represent diamidogen.
Detailed description of the invention
In the present embodiment, first and second and three generations PAMAM is all that the method by Tomalia is conventionally synthesized.
Embodiment 1
Being joined by the nano barium phthalate of 0.20g in the PAMAM solution of the 5.62g first generation, ultrasonic disperse 30min, such as Fig. 1
Shown in.Under nitrogen protection, the pyromellitic acid anhydride of 2.2248g and the 4，4′-diaminodipohenyl ether of 2.0023g are joined
The N-Methyl pyrrolidone of 28.18g is made into the solution of solid content 15% (wt/wt), and in ice-water bath, reacts 24h, obtain
The polyamic acid solution of acid anhydride end-blocking.The first generation PAMAM solution that 2.91g has disperseed nano barium phthalate particle joins above-mentioned poly-
In amic acid solution, after ultrasonic disperse several minutes, continue reaction 12h, obtain viscous fluid of polyamide acid.Take appropriate polyamic acid thickness
Liquid is poured in the glass board mould of cleaning.Being put in vacuum drying oven by mould, 80 DEG C of vacuum drying 2h, 150 DEG C of vacuum are done
Dry 2h, obtains polyamic acid gel film.After being continuously heating at 200 DEG C be vacuum dried 1h, it is warming up at 240 DEG C be vacuum dried again
1h, obtains Polyimide/Nano particle composite film, and basic procedure is as shown in Figure 2.The thickness of this thin film sets according to practical situation
Fixed, generally 70～100um.Through verification experimental verification, nano barium phthalate is uniformly dispersed in polyimides, and the thin film obtained has
Preferably heat-resisting quantity, low temperature resistant, excellent mechanical performance and good chemical stability.
Embodiment 2
The nano silver particles of 0.3g is joined in the PAMAM solution of the 5.45g second filial generation, ultrasonic disperse 40min.At nitrogen
Under protection, the pyromellitic acid anhydride of 2.2466g and the 4，4′-diaminodipohenyl ether of 2.0023g are joined the N of 42.49g,
N-dimethyl acetylamide is made into the solution of solid content 10% (wt/wt), and in ice-water bath, reacts 23h, obtain acid anhydride end-blocking
Polyamic acid solution.The second filial generation PAMAM solution that 2.46g has disperseed nano silver particles joins above-mentioned polyamic acid solution
In, after ultrasonic disperse several minutes, continue reaction 11h, obtain viscous fluid of polyamide acid.Take appropriate viscous fluid of polyamide acid and be poured into clean
In clean glass board mould.Mould is put in vacuum drying oven, 80 DEG C of vacuum drying 2h, 150 DEG C of vacuum drying 2h, removes molten
Agent, obtains polyamic acid gel film.After being continuously heating at 200 DEG C be vacuum dried 2h, it is warming up at 240 DEG C be vacuum dried again 1h,
Obtain Polyimide/Nano particle composite film.The thickness of this thin film sets according to practical situation, generally 70～100um.Warp
Overtesting is verified, nano silver particles is uniformly dispersed in polyimides, and the thin film obtained 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 joined in 3.31g third generation PAMAM solution, ultrasonic disperse 30min.
Under nitrogen protection, the pyromellitic acid anhydride of 2.2903g and the 4，4′-diaminodipohenyl ether of 2.0023g are joined
The DMF of 28.62g is made into the solution of solid content 15% (wt/wt), and in ice-water bath, reacts 22h,
Polyamic acid solution to acid anhydride end-blocking.The third generation polyamide-amide solution that 1.95g has disperseed nano silicon joins
State in polyamic acid solution, after ultrasonic disperse several minutes, continue reaction 13h, obtain viscous fluid of polyamide acid.Take appropriate polyamic acid
Viscous solution is poured in the glass board mould of cleaning.Being put in vacuum drying oven by mould, 80 DEG C of vacuum drying 2h, 150 DEG C true
Empty dry 2h, desolvation, obtain polyamic acid gel film.After being continuously heating at 200 DEG C be vacuum dried 2h, it is warming up to 240 DEG C
Under be vacuum dried 1h again, obtain Polyimide/Nano particle composite film.The thickness of this thin film sets according to practical situation, and one
As be 70～100um.Through verification experimental verification, nano-silicon dioxide particle is uniformly dispersed in polyimides, the thin film tool obtained
There are preferable heat-resisting quantity, low temperature resistant, excellent mechanical performance and good chemical stability.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. a Polyimide/Nano particle composite film, this thin film consist of polyimides doped with nanometer particle, its feature
It is: the doping way of described nanoparticle is: described nanoparticle is present in the cavity of Polyamidoamine Dendrimers, institute
State Polyamidoamine Dendrimers and carry out chemical bond crosslinking by self terminal amido with the anhydride group in described polyimides,
Thus obtain the laminated film of polyimides doped with nanometer particle.
2. a preparation method for Polyimide/Nano particle composite film, is characterized in that, comprises the following steps:
(1) nanoparticle of set amount is mixed homogeneously with Polyamidoamine Dendrimers, obtain mixed solution one；
(2) polyamic acid solution that anhydride blocks is mixed homogeneously with described mixed solution one, reaction, obtain mixed solution two；
(3) described mixed solution two is carried out film forming process, obtain polyamic acid gel film；
(4) continue the gel film of step (3) to be warmed up at 190～210 DEG C vacuum drying 1～3h, be warming up to 230～250 DEG C
Under be dried 0.5～1.5h again, obtain Polyimide/Nano particle composite film after amidatioon.
3. preparation method as claimed in claim 2, is characterized in that: in step (1), and described nanoparticle is nanometer silver, nanometer
In copper, nano silicon, nano titanium oxide, nano barium phthalate, nano-calcium carbonate, nano strontium titanate, nano barium-strontium titanate
One or more.
4. preparation method as claimed in claim 2, is characterized in that: in step (1), described nanoparticle is in polyamide-amide tree
The weight/mass percentage composition of shape macromole is 1～15%.
5. preparation method as claimed in claim 2, is characterized in that: in step (2), and the polyamic acid solution of anhydride end-blocking is profit
Generate polyamic acid with diamidogen and two anhydride reactants to prepare；Preferably, under nitrogen protection, by mol ratio be 1.02～
The dianhydride of 1.05:1 and diamidogen join and are made into solid content 10～the solution of 15% (wt/wt) in organic solvent, and at ice-water bath
Middle reaction 20～28h, obtains the polyamic acid solution of anhydride end-blocking；It is further preferred that described dianhydride is Pyromellitic Acid two
Acid anhydride, bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-oxydiphthalic, 2,2 '-bis-
In [4-(3,4-diacid phenoxy group) phenyl] propane tetracarboxylic dianhydride, 2,2 '-bis-(3,4-bis-carboxy phenyl) HFC-236fa tetracarboxylic dianhydrides
Any one；Described diamidogen is 4,4 '-diaminodiphenyl ether, hexafluoro methyl biphenyl diamidogen, MDA, 4,4 '-bis-(4-
Amino-benzene oxygen) diphenyl sulphone (DPS), any one in double [3,5-dimethyl-4-(4-amino) phenol] methane.
6. preparation method as claimed in claim 2, is characterized in that: in step (2), the polyamic acid solution of described anhydride end-blocking
It is 1～10:100 with the mass ratio of described mixed solution one.
7. preparation method as claimed in claim 2, is characterized in that: in step (2), and the condition of described reaction is ice-water bath；Ice
Water bath time is 10～14h, and the preferably time is 12h.
8. preparation method as claimed in claim 2, is characterized in that: in step (3), described mixed solution two is poured into mould
On, then mould is dried, desolvation, obtains polyamic acid gel film.
9. preparation method as claimed in claim 2, is characterized in that: in step (4), is vacuum dried 2h at 200 DEG C, then exists
240 DEG C of vacuum drying 1h.
10. use the Polyimide/Nano particle composite film that the method according to any one of claim 2～9 prepares.
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| CN107033502A (en) * | 2017-05-17 | 2017-08-11 | 南京航空航天大学 | Sour barium/organic matrix composite membrane of the neodymium-doped titanium of a kind 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 |
| 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 |
| CN108036532A (en) * | 2017-11-18 | 2018-05-15 | 山东龙光天旭太阳能有限公司 | A kind of preparation method of the low temperature resistant spectral selective absorbing coating of solar energy heat collection pipe |
| 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 |
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| CN108036532A (en) * | 2017-11-18 | 2018-05-15 | 山东龙光天旭太阳能有限公司 | A kind of preparation method of the low temperature resistant spectral selective absorbing coating of solar energy heat collection 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 |
| CN113621162A (en) * | 2021-06-28 | 2021-11-09 | 浙江中科玖源新材料有限公司 | Transparent conductive film |
| CN113956658A (en) * | 2021-10-21 | 2022-01-21 | 北京宇程科技有限公司 | Polyimide/titanium dioxide composite microsphere and preparation method thereof |
| 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 |
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