CN106633129A - Method for preparing polyimide/TiO2 composite material nanometer film - Google Patents

Method for preparing polyimide/TiO2 composite material nanometer film Download PDF

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CN106633129A
CN106633129A CN201611019426.7A CN201611019426A CN106633129A CN 106633129 A CN106633129 A CN 106633129A CN 201611019426 A CN201611019426 A CN 201611019426A CN 106633129 A CN106633129 A CN 106633129A
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tio
polyimides
composite material
parts
nanometer film
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彭志勤
赵芬芬
万军民
王秉
胡智文
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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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
    • 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
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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

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  • 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)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a method for preparing a polyimide/TiO2 composite material nanometer film. The method comprises the following steps of preparation of a sol-gel; aging of the sol-gel; film formation with a steeping pulling method; separation and washing of a polyimide/TiO2 composite thin film; and heat treatment. A modifying agent, a complexing agent and a catalyst are added in the process of forming the sol-gel, so that the prepared polyimide/TiO2 composite material nanometer film is compact and uniform and free of cracking or peeling, and is firmly attached to the surface of the base material, so that the practicability of the polyimide/TiO2 composite material nanometer film is strengthened.

Description

One kind prepares polyimides/TiO2The method of composite material nanometer film
Technical field
The present invention relates to a kind of preparation method of composite, more particularly to one kind prepare polyimides/ TiO2The method of composite material nanometer film.
Background technology
Organic/inorganic hybridization material is a kind of new material developed in recent years, and organic/inorganic hybridization material is different In traditional composite, with inorganic phase site size in nanometer range, what is had even divides its organic phase Sub- levels.Organic/inorganic hybridization material overcomes the defect on homogenous material and conventional composite materials performance, it with The advantage of machine material and the advantage of inorganic material.Organic/inorganic hybridization material form and performance can change in very large range, Inoganic particle modified organic polymer can be obtained by a small amount of inorganic component that adulterates, so as to improve or improve macromolecular material Performance, it is also possible to a small amount of organic principle improves inorganic material, so as to obtain mechanics, calorifics, optics, electromagnetism and biology etc. The excellent properties of aspect.
Polyimides is expected in modern boat with performances such as its excellent dielectric properties, radiation resistance and high-strength, Gao Mo The fields such as sky, military affairs, navigation, environmental project, auto industry, microelectronics are widely used, and are the height of most development prospect One of performance polymeric material, on the one hand, though polyimide fiber is with excellent combination property, due to performed polymer polyamide Sour structure and imidizate process characteristic so that technology difficulty is high, and the property such as intensity, modulus in process Be able to can be decreased obviously；On the other hand, with the development of science and technology, material property is put forward higher requirement, this is just limited Some high-tech applications of polyimides.In numerous conductor photocatalysis materials, TiO2With its stable chemical nature, oxygen Change-reproducibility is strong, anti-light burn into is nontoxic and low cost and become widely used photocatalyst.Titanium dioxide is used as multiple Close nanometer film reinforcing material.It is compound with polyimides, it is intended to improve the electric conductivity of polyimides, expand its use range, together When, titanium dioxide is filled in polyimide film as inorganic phase, is expected to improve the mechanical property and thermal property of polyimides.
Polyimides/the TiO obtained using sol-gel process in prior art2Composite material nanometer film, one-pass film-forming Thickness has very big restriction, needs repeatedly lifting to meet the composite material nanometer film thickness of needs, and obtains in repeatedly lifting Composite material nanometer film easily occur crackle and peel off etc. defect.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide one kind prepares polyimides/TiO2It is compound The method of material nano film, to solve prior art in polyimides/TiO2Easily there is crackle, peels off in composite material nanometer film And in the unstable defect of attachment of matrix surface.
For achieving the above object, the invention provides following technical scheme：One kind prepares polyimides/TiO2Composite The method of nanometer film, comprises the following steps：
Step one：The preparation of collosol and gel：Under the conditions of magnetic agitation, titanium tetrachloride is dropwise added drop-wise to absolute ethyl alcohol In, modifying agent, complexing agent, catalyst, antifoaming agent and bactericide are separately added into, continue for stirring 2h, clear solution is obtained, claim Take octadecylamine monomer to be added in reaction system, persistently stir and be dividedly in some parts until completely dissolved 3,3 ', 4,4 ' --- benzophenone four Acid dianhydride, under the conditions of stir speed (S.S.) is 1200r/min, persistently stirs 2h, and addition is dried anti-cracking agent, continues to stir 3h；
Step 2：The ageing of collosol and gel：Under agitation, watery hydrochloric acid is added dropwise, adjusts reaction system PH to 3, continued Stirring 2h, by reaction system ageing 24h colloidal sol is obtained；
Step 3：Dip-coating method film forming：Glass substrate is soaked in chromic acid lotion, then respectively with clear water, anhydrous Ethanol and deionized water are rinsed successively, are then dried, and the glass substrate for cleaning up is dipped vertically in colloidal sol, will with czochralski method It is at the uniform velocity lifted upwards, and pull rate is maintained at 1.6mm/sec, and spontaneously dries in atmosphere, solidifies 36-48h, in glass base Polyimides/TiO is formed on plate2Laminated film；
Step 4：Polyimides/TiO2The separating, washing of laminated film：Step 3 is obtained into glass substrate to naturally cool to Normal temperature, is acidified with the hydrochloric acid solution of 1mol/L, makes hydrochloric acid solution PH remain 1.5, afterwards repeatedly with distilled water flushing extremely It is neutral；
Step 5：Heat treatment：Polyimides/the TiO of neutrality will be washed into2Laminated film processes 2- in vapor 3min, then stands at room temperature and atmospheric pressure 0.5-1h, repeats 3-6 time, is placed on afterwards in Muffle furnace, with the liter of 2-6 DEG C/min Warm speed is progressively warmed up to 200-250 DEG C, keeps 1.5-2h, has both obtained finished product.
As a further improvement on the present invention, the weight portion content of each component in the preparation of step one collosol and gel It is：
Octadecylamine monomer：5-15 parts；
3,3 ', 4,4 ' --- benzophenone tetracarboxylic dianhydride：10-20 parts；
Titanium tetrachloride：10-20 parts；
Absolute ethyl alcohol：20-50 parts；
Modifying agent：0.4-0.6 parts；
Complexing agent：0.3-0.5 parts；
Catalyst：0.2-1.5 parts；
Antifoaming agent：0.2-0.5 parts；
Bactericide：0.1-0.3 parts；
It is dried anti-cracking agent：0.1-0.3 parts.
As a further improvement on the present invention, the modifying agent be hexamethyldisilane amine, the silicon imido alkane of prestox ring four, One or more in 3- aminopropyl triethoxysilanes or diethylin MTES.
As a further improvement on the present invention, the complexing agent is polyethylene glycol 2000.
As a further improvement on the present invention, the catalyst is that silane closes triethylamine.
As a further improvement on the present invention, the antifoaming agent is benzyl carbinol oleate.
As a further improvement on the present invention, it is described to be dried anti-cracking agent for 1- methyl -2,4- cyclohexanediamine or N- ethyls two One kind in cyclohexylamine.
As a further improvement on the present invention, the bactericide is one or more in garlic oil or origanum oil.
The present invention prepares polyimides/TiO2The method of composite material nanometer film, by the process for forming collosol and gel Middle addition modifying agent, complexing agent and catalyst, make the polyimides/TiO of preparation2Composite material nanometer film compacts, uniformly, will not There is crackle, peel off, in the adhesion-tight of matrix surface, enhance polyimides/TiO2The practicality of composite material nanometer film.
Specific embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：One kind prepares polyimides/TiO2The method of composite material nanometer film, comprises the following steps：
Step one：The preparation of collosol and gel：Under the conditions of magnetic agitation, 10g titanium tetrachlorides are dropwise added drop-wise to into 20g anhydrous In ethanol, it is separately added into 0.4g hexamethyldisilane amines, 0.3g polyethylene glycol 2000s, 0.2g silane and closes triethylamine, 0.2g benzene second Alcohol oleate and 0.1g garlic oils, continue for stirring 2h, obtain clear solution, weigh 5g octadecylamine monomers and are added to reactant In system, persistently stir and divide 5 batches of addition 10g 3,3 ', 4,4 ' --- benzophenone tetracarboxylic dianhydrides until completely dissolved, be in stir speed (S.S.) Under the conditions of 1200r/min, 2h is persistently stirred, add 0.1g1- methyl -2,4- cyclohexanediamine to continue to stir 3h；
Step 2：The ageing of collosol and gel：Under agitation, watery hydrochloric acid is added dropwise, adjusts reaction system PH to 3, continued Stirring 2h, by reaction system ageing 24h colloidal sol is obtained；
Step 3：Dip-coating method film forming：Glass substrate is soaked in chromic acid lotion, then respectively with clear water, anhydrous Ethanol and deionized water are rinsed successively, are then dried, and the glass substrate for cleaning up is dipped vertically in colloidal sol, will with czochralski method It is at the uniform velocity lifted upwards, and pull rate is maintained at 1.6mm/sec, and spontaneously dries in clean air, solidifies 36h, in glass Polyimides/TiO is formed on glass substrate2Laminated film；
Step 4：Polyimides/TiO2The separating, washing of laminated film：Step 3 is obtained into glass substrate to naturally cool to Normal temperature, is acidified with the hydrochloric acid solution of 1mol/L, makes hydrochloric acid solution PH remain 1.5, afterwards repeatedly with distilled water flushing extremely It is neutral；
Step 5：Heat treatment：Polyimides/the TiO of neutrality will be washed into2Laminated film processes 2min in vapor, Then 0.5h is stood at room temperature and atmospheric pressure, is repeated 3 times, be placed on afterwards in Muffle furnace, progressively risen with the heating rate of 2 DEG C/min Temperature keeps 1.5h to 200 DEG C, has both obtained finished product.
Polyimides/the TiO for obtaining2Laminated film flawless, adhesive force grade is 0 grade.
Embodiment 2：One kind prepares polyimides/TiO2The method of composite material nanometer film, comprises the following steps：
Step one：The preparation of collosol and gel：Under the conditions of magnetic agitation, 15g titanium tetrachlorides are dropwise added drop-wise to into 30g anhydrous In ethanol, be separately added into the silicon imido alkane of 0.5g prestoxs ring four, 0.35g polyethylene glycol 2000s, 0.3g silane close triethylamine, 0.25g benzyl carbinols oleate and 0.15g origanum oils, continue for stirring 2h, obtain clear solution, weigh 6g octadecylamine monomers and add Enter in reaction system, persistently stir and divide until completely dissolved 6 batches of addition 12g 3,3 ', 4,4 ' --- benzophenone tetracarboxylic dianhydrides, Stir speed (S.S.) is under the conditions of 1200r/min, persistently to stir 2h, adds 0.12gN- ethyl dicyclohexyl amines, continues to stir 3h；
Step 2：The ageing of collosol and gel：Under agitation, watery hydrochloric acid is added dropwise, adjusts reaction system PH to 3, continued Stirring 2h, by reaction system ageing 24h colloidal sol is obtained；
Step 3：Dip-coating method film forming：Glass substrate is soaked in chromic acid lotion, then respectively with clear water, anhydrous Ethanol and deionized water are rinsed successively, are then dried, and the glass substrate for cleaning up is dipped vertically in colloidal sol, will with czochralski method It is at the uniform velocity lifted upwards, and pull rate is maintained at 1.6mm/sec, and spontaneously dries in clean air, solidifies 38h, in glass Polyimides/TiO is formed on glass substrate2Laminated film；
Step 4：Polyimides/TiO2The separating, washing of laminated film：Step 3 is obtained into glass substrate to naturally cool to Normal temperature, is acidified with the hydrochloric acid solution of 1mol/L, makes hydrochloric acid solution PH remain 1.5, afterwards repeatedly with distilled water flushing extremely It is neutral；
Step 5：Heat treatment：Polyimides/the TiO of neutrality will be washed into2Laminated film processes 2min in vapor, Then 0.5h is stood at room temperature and atmospheric pressure, is repeated 4 times, be placed on afterwards in Muffle furnace, progressively risen with the heating rate of 3 DEG C/min Temperature keeps 1.5h to 210 DEG C, has both obtained finished product.
Polyimides/the TiO for obtaining2Laminated film flawless, adhesive force grade is 0 grade.
Embodiment 3：One kind prepares polyimides/TiO2The method of composite material nanometer film, comprises the following steps：
Step one：The preparation of collosol and gel：Under the conditions of magnetic agitation, 15g titanium tetrachlorides are dropwise added drop-wise to into 30g anhydrous In ethanol, it is separately added into 0.6g3- aminopropyl triethoxysilanes, 0.5g polyethylene glycol 2000s, 1g silane and closes triethylamine, 0.5g Benzyl carbinol oleate and 0.3g garlic oils, continue for stirring 2h, obtain clear solution, weigh 15g octadecylamine monomers and are added to In reaction system, persistently stir and divide 5 batches of addition 20g 3,3 ', 4,4 ' --- benzophenone tetracarboxylic dianhydrides until completely dissolved, in stirring Speed is under the conditions of 1200r/min, persistently to stir 2h, adds 0.3g1- methyl -2,4- cyclohexanediamine to continue to stir 3h；
Step 2：The ageing of collosol and gel：Under agitation, watery hydrochloric acid is added dropwise, adjusts reaction system PH to 3, continued Stirring 2h, by reaction system ageing 24h colloidal sol is obtained；
Step 3：Dip-coating method film forming：Glass substrate is soaked in chromic acid lotion, then respectively with clear water, anhydrous Ethanol and deionized water are rinsed successively, are then dried, and the glass substrate for cleaning up is dipped vertically in colloidal sol, will with czochralski method It is at the uniform velocity lifted upwards, and pull rate is maintained at 1.6mm/sec, and spontaneously dries in clean air, solidifies 48h, in glass Polyimides/TiO is formed on glass substrate2Laminated film；
Step 4：Polyimides/TiO2The separating, washing of laminated film：Step 3 is obtained into glass substrate to naturally cool to Normal temperature, is acidified with the hydrochloric acid solution of 1mol/L, makes hydrochloric acid solution PH remain 1.5, afterwards repeatedly with distilled water flushing extremely It is neutral；
Step 5：Heat treatment：Polyimides/the TiO of neutrality will be washed into2Laminated film processes 3min in vapor, Then 1h is stood at room temperature and atmospheric pressure, is repeated 6 times, be placed on afterwards in Muffle furnace, progressively heated up with the heating rate of 6 DEG C/min To 250 DEG C, 2h is kept, both obtained finished product.
Polyimides/the TiO for obtaining2Laminated film flawless, adhesive force grade is 0 grade.
Embodiment 4：One kind prepares polyimides/TiO2The method of composite material nanometer film, comprises the following steps：
Step one：The preparation of collosol and gel：Under the conditions of magnetic agitation, 15g titanium tetrachlorides are dropwise added drop-wise to into 40g anhydrous In ethanol, it is separately added into 0.5g diethylin MTESs, 0.3g polyethylene glycol 2000s, 1.5g silane and closes three second Amine, 0.5g benzyl carbinols oleate and 0.1g garlic oils, continue for stirring 2h, obtain clear solution, weigh 15g octadecylamine monomers In being added to reaction system, persistently stir and be dividedly in some parts 15g 3,3 ', 4,4 ' until completely dissolved --- benzophenone tetracarboxylic dianhydride, Under the conditions of stir speed (S.S.) is 1200r/min, 2h is persistently stirred, add 0.3gN- ethyl dicyclohexyl amines, continue to stir 3h；
Step 2：The ageing of collosol and gel：Under agitation, watery hydrochloric acid is added dropwise, adjusts reaction system PH to 3, continued Stirring 2h, by reaction system ageing 24h colloidal sol is obtained；
Step 3：Dip-coating method film forming：Glass substrate is soaked in chromic acid lotion, then respectively with clear water, anhydrous Ethanol and deionized water are rinsed successively, are then dried, and the glass substrate for cleaning up is dipped vertically in colloidal sol, will with czochralski method It is at the uniform velocity lifted upwards, and pull rate is maintained at 1.6mm/sec, and spontaneously dries in clean air, solidifies 40h, in glass Polyimides/TiO is formed on glass substrate2Laminated film；
Step 4：Polyimides/TiO2The separating, washing of laminated film：Step 3 is obtained into glass substrate to naturally cool to Normal temperature, is acidified with the hydrochloric acid solution of 1mol/L, makes hydrochloric acid solution PH remain 1.5, afterwards repeatedly with distilled water flushing extremely It is neutral；
Step 5：Heat treatment：Polyimides/the TiO of neutrality will be washed into2Laminated film processes 2min in vapor, Then 1h is stood at room temperature and atmospheric pressure, is repeated 5 times, be placed on afterwards in Muffle furnace, progressively heated up with the heating rate of 6 DEG C/min To 230 DEG C, 2h is kept, both obtained finished product.
Polyimides/the TiO for obtaining2Laminated film flawless, adhesive force grade is 0 grade.
Embodiment 5：One kind prepares polyimides/TiO2The method of composite material nanometer film, comprises the following steps：
Step one：The preparation of collosol and gel：Under the conditions of magnetic agitation, 20g titanium tetrachlorides are dropwise added drop-wise to into 45g anhydrous In ethanol, it is separately added into 0.6g diethylin MTESs, 0.3g polyethylene glycol 2000s, 0.8g silane and closes three second Amine, 0.3g benzyl carbinols oleate and 0.2g origanum oils, continue for stirring 2h, obtain clear solution, weigh 13g octadecylamine monomers In being added to reaction system, persistently stir and divide 5 batches of addition 20g 3,3 ', 4,4 ' --- benzophenone tetracarboxylic dianhydrides until completely dissolved, Under the conditions of stir speed (S.S.) is 1200r/min, 2h is persistently stirred, add 0.1gN- ethyl dicyclohexyl amines, continue to stir 3h；
Step 2：The ageing of collosol and gel：Under agitation, watery hydrochloric acid is added dropwise, adjusts reaction system PH to 3, continued Stirring 2h, by reaction system ageing 24h colloidal sol is obtained；
Step 3：Dip-coating method film forming：Glass substrate is soaked in chromic acid lotion, then respectively with clear water, anhydrous Ethanol and deionized water are rinsed successively, are then dried, and the glass substrate for cleaning up is dipped vertically in colloidal sol, will with czochralski method It is at the uniform velocity lifted upwards, and pull rate is maintained at 1.6mm/sec, and spontaneously dries in clean air, solidifies 36-48h, Polyimides/TiO is formed on glass substrate2Laminated film；
Step 4：Polyimides/TiO2The separating, washing of laminated film：Step 3 is obtained into glass substrate to naturally cool to Normal temperature, is acidified with the hydrochloric acid solution of 1mol/L, makes hydrochloric acid solution PH remain 1.5, afterwards repeatedly with distilled water flushing extremely It is neutral；
Step 5：Heat treatment：Polyimides/the TiO of neutrality will be washed into2Laminated film processes 2- in vapor 3min, then stands at room temperature and atmospheric pressure 0.5-1h, repeats 3-6 time, is placed on afterwards in Muffle furnace, with the liter of 2-6 DEG C/min Warm speed is progressively warmed up to 200-250 DEG C, keeps 1.5-2h, has both obtained finished product.
Polyimides/the TiO for obtaining2Laminated film flawless, adhesive force grade is 0 grade.
Embodiment 6：One kind prepares polyimides/TiO2The method of composite material nanometer film, comprises the following steps：
Step one：The preparation of collosol and gel：Under the conditions of magnetic agitation, 12g titanium tetrachlorides are dropwise added drop-wise to into 44g anhydrous In ethanol, be separately added into 0.4g3- aminopropyl triethoxysilanes, 0.3g polyethylene glycol 2000s, 0.9g silane close triethylamine, 0.4g benzyl carbinols oleate and 0.3g origanum oils, continue for stirring 2h, obtain clear solution, weigh 13g octadecylamine monomers and add Enter in reaction system, persistently stir and divide until completely dissolved 4 batches of addition 16g 3,3 ', 4,4 ' --- benzophenone tetracarboxylic dianhydrides, Stir speed (S.S.) is under the conditions of 1200r/min, persistently to stir 2h, adds 0.3g1- methyl -2,4- cyclohexanediamine to continue to stir 3h；
Step 2：The ageing of collosol and gel：Under agitation, watery hydrochloric acid is added dropwise, adjusts reaction system PH to 3, continued Stirring 2h, by reaction system ageing 24h colloidal sol is obtained；
Step 3：Dip-coating method film forming：Glass substrate is soaked in chromic acid lotion, then respectively with clear water, anhydrous Ethanol and deionized water are rinsed successively, are then dried, and the glass substrate for cleaning up is dipped vertically in colloidal sol, will with czochralski method It is at the uniform velocity lifted upwards, and pull rate is maintained at 1.6mm/sec, and spontaneously dries in clean air, solidifies 40h, in glass Polyimides/TiO is formed on glass substrate2Laminated film；
Step 4：Polyimides/TiO2The separating, washing of laminated film：Step 3 is obtained into glass substrate to naturally cool to Normal temperature, is acidified with the hydrochloric acid solution of 1mol/L, makes hydrochloric acid solution PH remain 1.5, afterwards repeatedly with distilled water flushing extremely It is neutral；
Step 5：Heat treatment：Polyimides/the TiO of neutrality will be washed into2Laminated film processes 2- in vapor 3min, then stands at room temperature and atmospheric pressure 0.5h, is repeated 3 times, and is placed on afterwards in Muffle furnace, with the heating rate of 5 DEG C/min 240 DEG C are progressively warmed up to, 2h is kept, finished product has both been obtained.
Polyimides/the TiO for obtaining2Laminated film flawless, adhesive force grade is 0 grade.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned enforcement Example, all technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It should be pointed out that for the art Those of ordinary skill for, some improvements and modifications without departing from the principles of the present invention, these improvements and modifications Should be regarded as protection scope of the present invention.

Claims (8)

1. one kind prepares polyimides/TiO2The method of composite material nanometer film, it is characterised in that：Comprise the following steps：
Step one：The preparation of collosol and gel：Under the conditions of magnetic agitation, titanium tetrachloride is dropwise added drop-wise in absolute ethyl alcohol, point Not Jia Ru modifying agent, complexing agent, catalyst, antifoaming agent and bactericide, continue for stir 2h, obtain clear solution, weigh ten Eight amine monomers are added in reaction system, are persistently stirred and be dividedly in some parts until completely dissolved 3,3 ', 4,4 ' --- benzophenone tetracid two Acid anhydride, under the conditions of stir speed (S.S.) is 1200r/min, persistently stirs 2h, and addition is dried anti-cracking agent, continues to stir 3h；
Step 2：The ageing of collosol and gel：Under agitation, watery hydrochloric acid is added dropwise, adjusts reaction system PH to 3, persistently stirred 2h, by reaction system ageing 24h colloidal sol is obtained；
Step 3：Dip-coating method film forming：Glass substrate is soaked in chromic acid lotion, clear water, absolute ethyl alcohol are then used respectively And deionized water is rinsed successively, then dry, the glass substrate for cleaning up is dipped vertically in colloidal sol, it is with czochralski method that its is even Speed is lifted upwards, and pull rate is maintained at 1.6mm/sec, and spontaneously dries in atmosphere, solidifies 36-48h, on the glass substrate Form polyimides/TiO2Laminated film；
Step 4：Polyimides/TiO2The separating, washing of laminated film：Step 3 is obtained into glass substrate and naturally cools to normal temperature, It is acidified with the hydrochloric acid solution of 1mol/L, makes hydrochloric acid solution PH remain 1.5, afterwards repeatedly with distilled water flushing to neutrality；
Step 5：Heat treatment：Polyimides/the TiO of neutrality will be washed into2Laminated film processes 2-3min in vapor, then 0.5-1h is stood at room temperature and atmospheric pressure, is repeated 3-6 time, be placed on afterwards in Muffle furnace, with the heating rate of 2-6 DEG C/min progressively 200-250 DEG C is warmed up to, 1.5-2h is kept, finished product has both been obtained.
2. it is according to claim 1 to prepare polyimides/TiO2The method of composite material nanometer film, it is characterised in that：It is described The weight portion content of each component in the preparation of step one collosol and gel is：
Octadecylamine monomer：5-15 parts；
3,3 ', 4,4 ' --- benzophenone tetracarboxylic dianhydride：10-20 parts；
Titanium tetrachloride：10-20 parts；
Absolute ethyl alcohol：20-50 parts；
Modifying agent：0.4-0.6 parts；
Complexing agent：0.3-0.5 parts；
Catalyst：0.2-1.5 parts；
Antifoaming agent：0.2-0.5 parts；
Bactericide：0.1-0.3 parts；
It is dried anti-cracking agent：0.1-0.3 parts.
3. it is according to claim 2 to prepare polyimides/TiO2The method of composite material nanometer film, it is characterised in that：It is described Modifying agent is hexamethyldisilane amine, the silicon imido alkane of prestox ring four, 3- aminopropyl triethoxysilanes or diethylin methyl One or more in triethoxysilane.
4. it is according to claim 3 to prepare polyimides/TiO2The method of composite material nanometer film, it is characterised in that：It is described Complexing agent is polyethylene glycol 2000.
5. polyimides/TiO is prepared according to any one of claim 1-42The method of composite material nanometer film, its feature It is：The catalyst is that silane closes triethylamine.
6. it is according to claim 5 to prepare polyimides/TiO2The method of composite material nanometer film, it is characterised in that：It is described Antifoaming agent is benzyl carbinol oleate.
7. it is according to claim 6 to prepare polyimides/TiO2The method of composite material nanometer film, it is characterised in that：It is described Anti-cracking agent is dried for the one kind in 1- methyl -2,4- cyclohexanediamine or N- ethyl dicyclohexyl amines.
8. it is according to claim 7 to prepare polyimides/TiO2The method of composite material nanometer film, it is characterised in that：It is described Bactericide is one or more in garlic oil or origanum oil.
CN201611019426.7A 2016-11-18 2016-11-18 Method for preparing polyimide/TiO2 composite material nanometer film Pending CN106633129A (en)

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CN113956786A (en) * 2021-11-15 2022-01-21 高梵(浙江)信息技术有限公司 Aqueous anti-tearing auxiliary agent for synthetic leather
CN114534990A (en) * 2022-01-11 2022-05-27 西安理工大学 ITO thin film suitable for flexible device and preparation method thereof

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