CN105111475A - Colorless and transparent polyimide nanocomposite membrane and preparation method thereof - Google Patents
Colorless and transparent polyimide nanocomposite membrane and preparation method thereof Download PDFInfo
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- CN105111475A CN105111475A CN201510587994.6A CN201510587994A CN105111475A CN 105111475 A CN105111475 A CN 105111475A CN 201510587994 A CN201510587994 A CN 201510587994A CN 105111475 A CN105111475 A CN 105111475A
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Abstract
The invention discloses a colorless and transparent polyimide nanocomposite membrane. The polyimide nanocomposite membrane comprises, by weight, 0.01-5.00% of inorganic nanoparticles, and the balance polyimide. The structural unit of the polyimide is specified in the specification. The colorless transparency of the polyimide is achieved on the basis of the introduction of an alicyclic ring structure and a trifluoromethyl and phenylate structure, different combined methods and inorganic nanoparticles of different kinds are utilized for being combined, the colorless and transparent polyimide nanocomposite membrane with the good heat resistance is obtained by controlling the addition amount of the inorganic nanoparticles, the glass-transition temperature of the membrane exceeds 250 DEG C, the light transmissivity at the 450 nm position is higher than 90%, and the ultraviolet cut-off wavelength is about 300 nm.
Description
Technical field
The present invention relates to polymer based nanocomposites field, particularly relate to a kind of water white polyimide nano-composite material membrane and preparation method thereof.
Background technology
Polyimide (polyimides, PI) be the macromolecular material that a class temperature classification is higher, have excellent over-all properties, but general PI is yellow-brown transparent material, this is mainly owing to causing with intermolecular easy formation charge transfer complex (CTC) in PI molecule.At present, the transparency improving PI film adopts following means usually: (1) introduces containing fluoro substituents or side base in PI molecular structure, utilizes the electronegativity that fluorine atom is larger, cuts off the conjugation of electronic cloud, suppresses the formation of CTC; (2) reducing the content of aromatic structure in PI molecular structure, as adopted dianhydride with alicyclic structure or diamine monomer, reducing the probability that CTC is formed; (3) introduce non-co-planar structure, the formation of CTC can be reduced; (4) in PI molecular structure, between introducing, position replaces the diamines of structure.This can hinder flow of charge along molecular chain fragrance because position replaces structure, conjugation between reducing point; (5) introduce sulfuryl structure, utilize the strong electron attraction of sulfuryl to reduce the formation of CTC.Compared with traditional polyimide, water white polyimide has good thermostability and optical transparence, and some dissolves in common solvent, as acetone, tetrahydrofuran (THF), DMF etc.Water white polyimide film has application prospect comparatively widely in photoelectric device and semi-conductor etc.
Along with the development of nanotechnology, nano composite material relies on its special performance more and more to cause the interest of people, and especially polyimide/inorganic nano hybridization material more obtains with the thermotolerance of its excellence and mechanical property and pays close attention to widely.As polyimide/clay hybrid material has higher thermostability, high strength, high rigidity and gas barrier characteristics; Polyimide/SiO2 hybrid material has good thermotolerance, dimensional stability; Polyimide/carbon nano-tube hybridization film has good mechanical property and thermal characteristics, and (0.1vol%) can obtain good electroconductibility when content of carbon nanotubes is relatively low, can be used as conduction or antistatic material; Polyimide/silver hybrid material has good reflective character and electroconductibility etc.But the transparency of Kapton is often sacrificed in the interpolation of nano-component, affect its application at optical field.
At exercise question " SynthesisandCharacterizationofColorlessPolyimideNanocomp ositeFilmsContainingPendantTrifluoromethylGroups(Macromo lecularResearch, 2008, in document 16(6): 503-509) ", author with 6FDA and TFDB for monomer reacts, add a certain amount of (0-1.0wt%) organized clay, prepare a series of colourless polyimide nano-composite material membrane, these PI nano-composite material membranes have good thermostability, less than 490 DEG C there is not obvious thermolysis, second-order transition temperature is at 280-287 DEG C, in visible-range, (400-700nm) has the excellent transparency, and the transmitance at 450nm place is more than 90%, and ultraviolet cut-on wavelength is at 352-356nm, a small amount of clay can increase substantially the tensile property of Kapton.And this polyimide hybrid material has lower thermal expansivity.
In the document of exercise question " Preparationandpropertiesoffluorine-containingcolorlesspo lyimidenanocompositefilmswithorgano-modifiedmontmorillon itesforpotentialflexiblesubstrate(Nanoscienceandnanotech nology; 2008; 8:1700-1706) ", author with 6FDA and TFDB for monomer reacts, add 0.5-2.0wt% organic montmorillonoid, obtain a series of water white polyimide nano-composite material membrane.Result of study shows, increase with organo montmorillonite content, the transparency of polyimide nano-composite material membrane is slightly lost, but aggregate performance goes out to be better than the performance of pure PI film, as increased with organo montmorillonite content, thermal expansivity reduces, second-order transition temperature improves.
At exercise question " Colorlesspolyimidenanocompositefilms:Thermomechanicalpro perties, morphology, andopticaltransparency(
journalofAppliedPolymerScience, 2007,107(1): 109-117) " document in, author synthesizes a series of polyimide/organic clay nano composite material film by solution intercalation method.When clay content is less than 0.5wt%, clay particles is uniformly dispersed; When clay content is more than 0.75wt%, agglomeration can be there is.These polyimide nano hybridized film show good optical transparence and near colorless, but the transparency can be in a slight decrease along with the increase of clay content.
Therefore, the present invention synthesizes basis with water white polyimide, utilize different complex methods and different types of inorganic nano-particle phase compound, by controlling the addition of inorganic nano-particle, thermotolerance and the mechanical property of polyimide is improved under the prerequisite of the less sacrifice polyimide film transparency, reduce its thermal expansivity, obtain the polyimide nano-composite material membrane that near colorless is transparent, the substrate material of flexible transparent conducting film can be used as, OLED flexible substrate material, optical waveguide material, semiconductor material etc., this is to widening its range of application, improve its premium properties significant.
Summary of the invention
The object of the invention is to the above problem overcoming prior art existence, a kind of water white polyimide nano-composite material membrane and preparation method thereof is provided, using alicyclic dianhydride (abbreviation dianhydride) and fluorinated diamine (abbreviation diamines) as the monomer of synthesizing colourless clear polyimides, utilize different complex methods and different types of inorganic nano-particle phase compound, obtain water white polyimide nano-composite material membrane through Low-temperature Solution Polycondensation reaction and hot-imide process.By controlling the addition of inorganic nano-particle, under the prerequisite of the less sacrifice polyimide film transparency, improving thermotolerance and the mechanical property of polyimide film, and give its special performance, as low thermal coefficient of expansion, electroconductibility, barrier properties for gases etc.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
A kind of water white polyimide nano-composite material membrane, containing weight ratio in described polyimide nano-composite material membrane is the inorganic nano-particle of 0.01 ~ 5.00wt%, and the polyimide of surplus, and the structural unit of described polyimide is:
。
Preferably, described Ar is selected from
in one,
R is selected from
,
,
,
,
,
,
,
,
in one.
Preferably, described inorganic nano-particle is selected from the one in talcum, mica, kaolin, polynite, clay, nano titanium oxide, nano silicon, nano aluminum nitride, nano-aluminium oxide, nano zine oxide, nano barium phthalate or carbon nanotube, and its particle diameter is less than 100nm.
Preferably, described inorganic nano-particle is in advance through surface activation process, and surface activation process is selected from the one in silane coupling agent, titante coupling agent, aluminate coupling agent, organic ion exchange modification, reactive monomer grafting, strong acid etching, highly basic etching or plasma etching treatment.
A preparation method for polyimide nano-composite material membrane, comprises the following steps:
1) inorganic nano-particle is carried out surface activation process;
2) adopt churned mechanically while, method obtained homodisperse aaerosol solution of nanoparticle in aprotic polar solvent of auxiliary ultrasonic dispersion;
3) in the suspension of nanoparticle, first diamines is added, after it dissolves completely, add dianhydride again carry out polyreaction, the mol ratio of diamines and dianhydride is 1:1, temperature of reaction is 0 ~ 25 DEG C, reaction times is 15 ~ 25 hours, and the solid content obtained by weight is the polyamic acid solution of the even thickness of 10 ~ 25%;
4) polyamic acid solution that step 3 obtains is coated on clean smooth sheet glass, adopts the hot-imide method of gradient increased temperature obtained water white polyimide nano-composite material membrane under nitrogen protection environment.
Preferably, described diamines is selected from down:
,
,
,
,
,
,
,
or
in one.
Preferably, described dianhydride is selected from:
,
,
,
,
or
in one.
Preferably, described aprotic polar solvent is selected from DMF, the one in N,N-dimethylacetamide or METHYLPYRROLIDONE.
Preferably, the surface activation process of described inorganic nano-particle is selected from the one in silane coupling agent, titante coupling agent, aluminate coupling agent, organic ion exchange modification, reactive monomer grafting, strong acid etching, highly basic etching or plasma etching treatment.
Preferably, described inorganic nano-particle is selected from the one in talcum, mica, kaolin, polynite, clay, nano titanium oxide, nano silicon, nano aluminum nitride, nano-aluminium oxide, nano zine oxide, nano barium phthalate or carbon nanotube.
Imidization method of the present invention is the hot-imide method of gradient increased temperature, and carries out in nitrogen protection environment.
The hot-imide method of the gradient increased temperature that the present invention adopts is: 80 DEG C of 2hrs, 120 DEG C of 1hr, 150 DEG C of 1hr, 200 DEG C of 1hr, 250 DEG C of 1hr, 300 DEG C of 0.5hr.
Imidization temperature of the present invention is between 200 ~ 350 DEG C, and the imidization time is 0.1 ~ 1 hour.
The invention has the beneficial effects as follows:
The present invention is based on and introduce alicyclic structure, trifluoromethyl and phenylate structure to realize the colorless transparency of polyimide, utilize different complex methods and different types of inorganic nano-particle phase compound, by controlling the addition of inorganic nano-particle, obtain thermotolerance good, and water white polyimide nano-composite material membrane, the second-order transition temperature of this film is more than 250 DEG C, and the light transmission rate at 450nm place is more than 90%, and ultraviolet cut-on wavelength is at about 300nm.
Embodiment
Embodiment 1
Utilize quaternary ammonium salt (CTAB) to make intercalator and ion-exchanged process has been carried out to polynite, obtain organic montmorillonoid.0.0427g organic montmorillonoid is joined in N,N-dimethylacetamide (DMAc) solvent of 6.38ml, under powerful mechanical agitation, disperse in 80 DEG C the DMAc solution obtaining organic montmorillonoid for 5 hours.Pass in three neck reaction flasks of mouth being equipped with agitator, thermometer and nitrogen, by 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the HFC-236fa 6.5445g(0.01mol of 2-) be dissolved in 45mlDMAc solvent, stir and make solution become clear.Then disposablely in this solution 1 is added; 2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA) 1.9611g(0.01mol); under nitrogen protection environment, continue reaction 15 ~ 25 hours after stirring makes it to dissolve completely, obtain clear viscous liquids-polyamic acid (PAA) solution.In PAA solution, add the DMAc solution of above-mentioned organophilic clay, continue stirring reaction obtains containing organic montmorillonoid PAA solution after 10 hours, PAA solid content is by weight 15wt%, limiting viscosity 1.22dL/g.This mixing solutions is coated on clean sheet glass, is positioned in the loft drier with nitrogen protection, heats up by following program: 80 DEG C of 2hrs, 120 DEG C of 1hr, 150 DEG C of 1hr, 200 DEG C of 1hr, 250 DEG C of 1hr, 280 DEG C of 0.5hr.Be down to until temperature and take out sheet glass after room temperature and be placed in warm water demoulding, in 100 DEG C of loft drier, obtain the polyimide nano-composite material membrane that polynite content is 0.5wt% after dry 2 hours.
This polyimide nano-composite material membrane is water white transparency shape, its salient features: second-order transition temperature is 289 DEG C, and ultraviolet cut-on wavelength is the light transmission rate at 293nm, 450nm place is 93%.
Embodiment 2
0.0645g is scattered in the DMAc solvent of 27.23ml through the nano zine oxide (particle diameter 30nm) of γ aminopropyltriethoxy silane process under ultrasonication, obtain uniform mixing solutions after 2 hours, move to and be equipped with agitator, thermometer and nitrogen and pass in three neck reaction flasks of mouth.By Isosorbide-5-Nitrae-bis-(4-amino-2-4-trifluoromethylphenopendant) benzene 4.2833g(0.01mol) be dissolved in above-mentioned solution, stir and make solution become clear.Then disposablely in this solution 1 is added; 2; 4; 5-pentamethylene tetracarboxylic dianhydride (CPDA) 2.1014g(0.01mol); under nitrogen protection environment, reaction 15 ~ 25 hours is continued after stirring makes it to dissolve completely; the solid content obtained by weight is the clear viscous liquids-polyamic acid solution of 20wt%, and limiting viscosity is 1.15dL/g.This polyamic acid solution is coated on clean sheet glass, is positioned in the loft drier with nitrogen protection, heats up according to following program: 80 DEG C of 2hrs, 120 DEG C of 1hr, 150 DEG C of 1hr, 200 DEG C of 1hr, 250 DEG C of 1hr, 250 DEG C of 0.5hr.Be down to until temperature and take out sheet glass after room temperature and be placed in warm water demoulding, in 100 DEG C of loft drier, obtain the polyimide nano-composite material membrane that ZnO content is 1.0wt% after dry 2 hours.
This polyimide nano-composite material membrane is water white transparency shape, its salient features: second-order transition temperature is 250 DEG C, and ultraviolet cut-on wavelength is the light transmission rate at 316nm, 450nm place is 90%.
Embodiment 3
Pass in three neck reaction flasks of mouth being equipped with agitator, thermometer and nitrogen, by 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the HFC-236fa 6.5445g(0.01mol of 2-) be dissolved in the DMAc solvent of 53.08ml, stir and make solution become clear.Then disposablely in this solution 1 is added; 2; 4; 5-cyclopentanetetracarboxylic dianhydride (CHDA) 2.2417g(0.01mol); under nitrogen protection environment, reaction 15 ~ 25 hours is continued after stirring makes it to dissolve completely; the solid content obtained by weight is the clear viscous liquids-polyamic acid solution of 15wt%, and limiting viscosity is 1.00dL/g.0.1529g tetraethoxy (TEOS) and little water is added in this polyamic acid solution; stirring after 20 hours is coated on clean sheet glass by this mixing solutions; be positioned in the loft drier with nitrogen protection; heat up according to following program: 80 DEG C of 2hrs; 120 DEG C of 1hr, 150 DEG C of 1hr, 200 DEG C of 1hr; 250 DEG C of 1hr, 300 DEG C of 0.5hr.Be down to until temperature and take out sheet glass after room temperature and be placed in warm water demoulding, in 100 DEG C of loft drier, obtain the polyimide nano-composite material membrane that SiO2 content is 0.5wt% after dry 2 hours.
This polyimide nano-composite material membrane is water white transparency shape, its salient features: second-order transition temperature is 279 DEG C, and ultraviolet cut-on wavelength is the light transmission rate at 305nm, 450nm place is 91%.
Embodiment 4
Rutile-phase nano-titanium dioxide (particle diameter 40nm) is processed with titante coupling agent, take 0.0529g after drying in the DMAc solvent of 42.32ml, under the effect of mechanical stirring and ultrasonic disperse, process moves to after 3 hours and is equipped with agitator, thermometer and nitrogen and passes in three neck reaction flasks of mouth.By 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) biphenyl 5.0442g(0.01mol) be dissolved in above-mentioned solution, stir and make solution become clear.Then disposablely in this solution 1 is added; 2; 3; 4-tetramethylene tetracarboxylic dianhydride (CBDA) 1.9611g(0.01mol); under nitrogen protection environment, reaction 15 ~ 25 hours is continued after stirring makes it to dissolve completely; the clear viscous liquids obtained is the presoma-polyamic acid of polyimide, and solid content is by weight 15wt%, and limiting viscosity is 1.16dL/g.This polyamic acid solution is coated on clean sheet glass, is positioned in the loft drier with nitrogen protection, heats up according to following program: 80 DEG C of 2hrs, 120 DEG C of 1hr, 150 DEG C of 1hr, 200 DEG C of 1hr, 250 DEG C of 1hr, 280 DEG C of 0.5hr.Be down to until temperature and take out sheet glass after room temperature and be placed in warm water demoulding, and in 100 DEG C of loft drier dry 2 hours, obtain the polyimide nano-composite material membrane that nano TiO 2 content is 0.75wt%.
This polyimide nano-composite material membrane is water white transparency shape, its salient features: second-order transition temperature is 287 DEG C, and ultraviolet cut-on wavelength is the light transmission rate at 305nm, 450nm place is 92%.
Embodiment 5
Under ultrasonication, 0.0037g is joined in 44.13mlDMAc solvent through the carbon nanotube (diameter 10nm) of Sulphanilic Acid grafting process, disperse within 2 hours, to obtain comparatively uniform mixed solution, immigration is equipped with agitator, thermometer and nitrogen and passes in three neck reaction flasks of mouth.By 4,4 '-bis-(4-amino-2-4-trifluoromethylphenopendant) phenyl ether 5.2042g(0.01mol) be dissolved in above-mentioned mixed solution, stir and make solution become clear.Then disposablely in this solution 1 is added; 2; 4; 5-pentamethylene tetracarboxylic dianhydride (CPDA) 2.1014g(0.01mol); under nitrogen protection environment, reaction 15 ~ 25 hours is continued after stirring makes it to dissolve completely; the solid content obtained by weight is the clear viscous liquids-polyamic acid solution of 15wt%, and limiting viscosity is 1.03dL/g.This mixing solutions is coated on clean sheet glass, is positioned in the loft drier with nitrogen protection, heats up according to following program: 80 DEG C of 2hrs, 120 DEG C of 1hr, 150 DEG C of 1hr, 200 DEG C of 1hr, 250 DEG C of 1hr, 280 DEG C of 0.5hr.Be down to until temperature and take out sheet glass after room temperature and be placed in warm water demoulding, be then placed in 100 DEG C of loft drier dryings and within 2 hours, obtain the polyimide nano-composite material membrane that content of carbon nanotubes is 0.05wt%.
This polyimide nano-composite material membrane is water white transparency shape, its salient features: second-order transition temperature is 252 DEG C, and ultraviolet cut-on wavelength is the light transmission rate at 310nm, 450nm place is 93%.
Embodiment 6
The nano silicon nitride aluminum particulate (particle diameter 50nm) crossed through aluminate coupling agent treatment by 0.0193g joins in 32.86mlDMAc solvent under mechanical stirring and ultrasonic disperse effect, acts on and obtains uniform mixing solutions after 2 hours.Immigration is equipped with agitator, thermometer and nitrogen and passes in three neck reaction flasks of mouth.By two for 2,2-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] propane 5.4650g(0.01mol) be dissolved in above-mentioned solution, stir and make solution become clear.Then disposablely in this solution 1 is added; 2; 4; 5-cyclopentanetetracarboxylic dianhydride (CHDA) 2.2417g(0.01mol); under nitrogen protection environment, reaction 15 ~ 25 hours is continued after stirring makes it to dissolve completely; the solid content obtained by weight is the clear viscous liquids-polyamic acid solution of 20wt%, and limiting viscosity is 1.10dL/g.This polyamic acid solution is coated on clean sheet glass, is positioned in the loft drier with nitrogen protection, heats up according to following program: 80 DEG C of 2hrs, 120 DEG C of 1hr, 150 DEG C of 1hr, 200 DEG C of 1hr, 250 DEG C of 1hr, 300 DEG C of 0.5hr.Be down to until temperature and take out sheet glass after room temperature and be placed in warm water demoulding, in 100 DEG C of loft drier dry 2 hours, obtain the polyimide nano-composite material membrane that nano-aluminum nitride content is 0.25wt%.
This polyimide nano-composite material membrane is water white transparency shape, its salient features: second-order transition temperature is 275 DEG C, and ultraviolet cut-on wavelength is the light transmission rate at 315nm, 450nm place is 90%.
Embodiment 7
0.0899g is scattered in 13.41mlDMF solvent through the nano-aluminium oxide (particle diameter 30nm) of dispersion agent process under powerful mechanical stirring and ultrasonication, after 2 hours, obtains uniform mixing solutions.Pass in three neck reaction flasks of mouth being equipped with agitator, thermometer and nitrogen, by 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the HFC-236fa 6.5445g(0.01mol of 2-) be dissolved in the DMF solvent of 40ml, stir and make solution become clear.Then disposablely in this solution dicyclo [2.2.1] heptane-2 is added; 3:5; 6-tetracarboxylic dianhydride 2.3618g(0.01mol); under nitrogen protection environment, reaction 15 ~ 25 hours is continued after stirring makes it to dissolve completely; the solid content obtained by weight is the clear viscous liquids-polyamic acid solution of 15wt%, and limiting viscosity is 1.08dL/g.The mixing solutions of homogeneous transparent is obtained after this polyamic acid solution is mixed 5 hours with the DMF solution of nano-scale alumina under powerful mechanical agitation; be coated on clean sheet glass; be positioned in the loft drier with nitrogen protection; heat up according to following program: 80 DEG C of 2hrs; 120 DEG C of 1hr, 150 DEG C of 1hr, 200 DEG C of 1hr; 250 DEG C of 1hr, 300 DEG C of 0.5hr.Be down to until temperature and take out sheet glass after room temperature and be placed in warm water demoulding, in 100 DEG C of loft drier, obtain the polyimide nano-composite material membrane that Al2O3 content is 1.0wt% after dry 2 hours.
This polyimide nano-composite material membrane is water white transparency shape, its salient features: second-order transition temperature is 270 DEG C, and ultraviolet cut-on wavelength is the light transmission rate at 294nm, 450nm place is 93%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a water white polyimide nano-composite material membrane, it is characterized in that: containing weight ratio in described polyimide nano-composite material membrane is the inorganic nano-particle of 0.01 ~ 5.00wt%, and the polyimide of surplus, the structural unit of described polyimide is:
。
2. polyimide nano-composite material membrane according to claim 1, is characterized in that: described Ar is selected from
in one,
R is selected from
,
,
,
,
,
,
,
,
in one.
3. polyimide nano-composite material membrane according to claim 1, it is characterized in that: described inorganic nano-particle is selected from the one in talcum, mica, kaolin, polynite, clay, nano titanium oxide, nano silicon, nano aluminum nitride, nano-aluminium oxide, nano zine oxide, nano barium phthalate or carbon nanotube, its particle diameter is less than 100nm.
4. polyimide nano-composite material membrane according to claim 1, it is characterized in that: described inorganic nano-particle is in advance through surface activation process, and surface activation process is selected from the one in silane coupling agent, titante coupling agent, aluminate coupling agent, organic ion exchange modification, reactive monomer grafting, strong acid etching, highly basic etching or plasma etching treatment.
5. a preparation method for the polyimide nano-composite material membrane according to any one of claim 1-4, is characterized in that, comprises the following steps:
1) inorganic nano-particle is carried out surface activation process;
2) adopt churned mechanically while, method obtained homodisperse aaerosol solution of nanoparticle in aprotic polar solvent of auxiliary ultrasonic dispersion;
3) in the suspension of nanoparticle, first diamines is added, after it dissolves completely, add dianhydride again carry out polyreaction, the mol ratio of diamines and dianhydride is 1:1, temperature of reaction is 0 ~ 25 DEG C, reaction times is 15 ~ 25 hours, and the solid content obtained by weight is the polyamic acid solution of the even thickness of 10 ~ 25%;
4) polyamic acid solution that step 3 obtains is coated on clean smooth sheet glass, adopts the hot-imide method of gradient increased temperature obtained water white polyimide nano-composite material membrane under nitrogen protection environment.
6. preparation method according to claim 5, is characterized in that: described diamines is selected from down:
,
,
,
,
,
,
,
or
in one.
7. preparation method according to claim 5, is characterized in that: described dianhydride is selected from:
,
,
,
,
or
in one.
8. preparation method according to claim 5, is characterized in that: described aprotic polar solvent is selected from DMF, the one in N,N-dimethylacetamide or METHYLPYRROLIDONE.
9. preparation method according to claim 5, is characterized in that: the surface activation process of described inorganic nano-particle is selected from the one in silane coupling agent, titante coupling agent, aluminate coupling agent, organic ion exchange modification, reactive monomer grafting, strong acid etching, highly basic etching or plasma etching treatment.
10. preparation method according to claim 5, is characterized in that: described inorganic nano-particle is selected from the one in talcum, mica, kaolin, polynite, clay, nano titanium oxide, nano silicon, nano aluminum nitride, nano-aluminium oxide, nano zine oxide, nano barium phthalate or carbon nanotube.
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| CN105802222A (en) * | 2016-04-22 | 2016-07-27 | 广东精达里亚特种漆包线有限公司 | Nanometer polyamide imide film containing inorganic oxide and preparation method of nanometer polyamide imide film |
| CN106188534A (en) * | 2016-08-23 | 2016-12-07 | 万华化学集团股份有限公司 | A kind of polyamide and preparation method thereof, polyamide material prepared therefrom |
| CN106589737A (en) * | 2016-11-28 | 2017-04-26 | 天津盼易科技有限公司 | Novel macromolecular composite material and preparation method thereof |
| CN107793758A (en) * | 2017-11-15 | 2018-03-13 | 江苏亚宝绝缘材料股份有限公司 | A kind of polymer of CNT compound polyimide resin and its preparation and application |
| CN108473764A (en) * | 2016-01-08 | 2018-08-31 | 日产化学工业株式会社 | Flexible device substrate formation composition |
| CN108822295A (en) * | 2018-06-05 | 2018-11-16 | 中国科学院长春应用化学研究所 | A kind of flexible display substrates material and preparation method thereof |
| CN108884317A (en) * | 2016-04-05 | 2018-11-23 | 三菱瓦斯化学株式会社 | Polyimide resin composition and its manufacturing method and Kapton |
| CN111500065A (en) * | 2020-05-29 | 2020-08-07 | 浙江中科玖源新材料有限公司 | High-barrier polyimide film and preparation method thereof |
| CN111533911A (en) * | 2020-05-14 | 2020-08-14 | 深圳大学 | Polyimide nano hybrid material and preparation method thereof |
| CN113174072A (en) * | 2021-03-30 | 2021-07-27 | 浙江中科玖源新材料有限公司 | Water-proof transparent polyimide film and preparation method and application thereof |
| WO2022142305A1 (en) * | 2020-12-31 | 2022-07-07 | 宁波长阳科技股份有限公司 | Colorless transparent polyimide thin film and preparation method therefor, and led film screen |
| CN117567742A (en) * | 2024-01-17 | 2024-02-20 | 株洲时代新材料科技股份有限公司 | Preparation method of yellowing-resistant transparent polyimide substrate material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005123837A1 (en) * | 2004-06-21 | 2005-12-29 | Mitsubishi Gas Chemical Company, Inc. | Colorless transparent polyimide composite film and method for producing same |
| CN101392059A (en) * | 2008-11-05 | 2009-03-25 | 东华大学 | Colorless transparent aromatic polyimide film and preparation method thereof |
| CN101831175A (en) * | 2010-04-01 | 2010-09-15 | 辽宁科技大学 | Colorless and transparent polyimide nano-composite material membrane and preparation method thereof |
-
2015
- 2015-09-16 CN CN201510587994.6A patent/CN105111475A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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