CN109337365A - A kind of compound anti-atomic oxygen Kapton and the preparation method and application thereof - Google Patents
A kind of compound anti-atomic oxygen Kapton and the preparation method and application thereof Download PDFInfo
- Publication number
- CN109337365A CN109337365A CN201811063980.4A CN201811063980A CN109337365A CN 109337365 A CN109337365 A CN 109337365A CN 201811063980 A CN201811063980 A CN 201811063980A CN 109337365 A CN109337365 A CN 109337365A
- Authority
- CN
- China
- Prior art keywords
- poss
- tsp
- solution
- atomic oxygen
- film
- 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.)
- Granted
Links
Classifications
-
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of compound anti-atomic oxygen Kapton and the preparation method and application thereof, the TSP-POSS resin solution being combined according to a certain percentage and the laminated film prepared by the resin solution shown in the film intrinsic anti-atomic oxygen PI polymer as shown in Formulas I and Formula II；Mass percent TSP-POSS shared in TSP-POSS/PI laminated film total amount is m%, in which: the integer of 0 m≤30 <.The film has dual anti-atomic oxygen characteristic, and PI base film itself adds the laminated film formed after TSP-POSS and more significantly enhance its anti-atomic oxygen performance because having the characteristic of intrinsic anti-atomic oxygen containing P elements.Molecular level is compound due to foring between TSP-POSS and PI matrix, and laminated film maintains the excellent optical transparence of PI film matrix.Polyimide composite film of the present invention is covered on the exposed transparent space flight equipment outer surface in space, can effectively improve its anti-atomic oxygen performance.
Description
Technical field
The present invention relates to functional polyalkylene imide membrane fields, specifically, being related to a kind of cage modle polysilsesquioxane
(POSS) compound polyimide anti-atomic oxygen film.
Background technique
Most of spacecraft operates in the Low Earth Orbit (low earth orbit, LEO) away from 200~700km of ground.
Have the operation and working life of many such environmental effects spacecrafts in this orbit altitude, for example, thermal cycle, space junk,
Ultraviolet irradiation and space elemental oxygen, wherein elemental oxygen (atomic oxygen, AO) is proved to be most important and most dangerous influence
Factor.Elemental oxygen in the spacecraft and running track of Low Earth Orbit operation is hit, and relative velocity is about 8km/
S, hitting momentum is about 1014~1015/cm2S can generate the impact energy of about 4~5eV on spacecraft surface, this is enough to make
Most organic materials on spacecraft surface occur chemical scission of link and are oxidized, and lead to its performance degradation.
In recent years, the atomic oxygen effects research of polymer material receives more and more extensive attention, it is not only LEO sky
Between an important content in environmental effect research, while being also one of the key factor that Spacecraft guidance and control must be taken into consideration.It is poly-
Acid imide (polyimide, PI) is one of aerospace field common materials, in order to which elemental oxygen is effectively reduced to boat
The erosion that its device surface generates, common method has following two: first is that surface covering method, i.e., Polymer Surface coating not with
The protective coating of elemental oxygen reaction, such as SiO2With Al2O3Etc. improving erosion of the AO to space material；Second is that matrix strengthening method, i.e.,
The elements such as the good silicon of anti-atomic oxygen erosion performance, phosphorus, zirconium, tin are introduced into polymeric matrix, using above-mentioned element in space
Have the function of " self-healing " or " selfreparing " in atomic oxygen environment to improve the anti-atomic oxygen performance of space material.
Surface covering method is easy to crack during transportation or coating shedding；And when outer space is on active service, due to
The inorganic coating on surface is different from interior polymer matrix thermal expansion coefficient (CTE), causes thermal cycle periodically shining upon
Under conditions of, it cracks or spacecraft is made the protection of material surface by the shock of space junk in the process of running
Layer generates fine crack or hole etc. and cracks defect.Elemental oxygen has certain probability to enter these when striking material surface
Defect reacts to touch the high molecular material under protective layer and generates base erosion cavity.With base erosion cavity
The protective layer of extension, material surface can even fall off, and the high molecular material area being exposed in atomic oxygen environment increases, material quilt
Atomic oxygen erosion influences enhancing.Therefore it is more likely to carry out matrix strengthening research to space material.
The method that matrix strengthening method introduces silicon, phosphorus, zirconium, the elements such as tin in the base, the in recent years poly- silsesquioxane of cage modle
Alkane (Polyhedral Oligomeric Silsesquioxanes, POSS) is standby in the anti-atomic oxygen aspect of performance for improving material
It is concerned.POSS has the three-dimensional cage type inorganic silicon oxygen skeleton structure of spatially high degree of symmetry, have concurrently inorganic nano-particle and
The property of organic compound.POSS-PI composite material can form a SiO on surface when being attacked by elemental oxygen2Protective layer,
Middle Si-O key can be just destroyed in 8eV, be far longer than the erosiveness of elemental oxygen, therefore can effectively reduce the erosion of elemental oxygen
Degree, and then extend the service life of spacecraft.For example, domestic patent, which has, introduces PMDA-ODA Kapton for POSS
In, realize the promotion of material anti-atomic oxygen performance.Still an alternative is that improving the structure of polyimides itself, such as phosphorous
The polyimides anti-atomic oxygen film of structure, also improves the anti-atomic oxygen performance of material to a certain extent.For example, the U.S. is special
Benefit also published a kind of intrinsic anti-atomic oxygen PI film containing phosphorous.But the modified PI film of either POSS or intrinsic antigen
Sub- oxygen PI film is not able to satisfy spacecraft to the application requirement of long-life anti-atomic oxygen film, needs to seek new method
With technology.
Summary of the invention
The present invention is precisely in order to a kind of compound anti-atomic oxygen Kapton for solving above-mentioned technical problem and designing
And the preparation method and application thereof.The compound anti-atomic oxygen Kapton has dual anti-atomic oxygen characteristic and excellent light
The transparency is learned, can be widely applied to the outer surface of transparent space flight equipment in space.
The technical solution adopted by the present invention to solve the technical problems is:
Shown in a kind of compound anti-atomic oxygen Kapton, intrinsic anti-atomic oxygen PI polymer shown in Formulas I and Formula II
The TSP-POSS resin solution being proportionally combined and the laminated film prepared by the resin solution；
Mass percent TSP-POSS shared in TSP-POSS/PI laminated film total amount is m%, in which: 0 < m≤
30 integer.
A kind of compound anti-atomic oxygen Kapton, intrinsic anti-atomic oxygen PI polymer are one kind PI containing phosphorous
Film, by 4,4'- [hexafluoroisopropyli,ene] double phthalic anhydrides [6FDA] and 2,5- bis- { [4- amino-benzene oxygen] phenyl }
Diphenyl phosphine oxide [BADPO] synthesis.
A kind of preparation method of compound anti-atomic oxygen Kapton, laminated film can be made as steps described below
It is standby and obtain:
Step 1: diphenyl phosphine oxide BADPO is dissolved in non-proton intensive polar solvent, homogeneous phase solution is formed after stirring, is added
Enter dicarboxylic acid anhydride monomer 6FDA, is reacted 0.5-1 hours at 15-25 DEG C in temperature, obtain polyamic acid PAA solution；
Step 2: being heated to 180-200 DEG C for toluene, isoquinolin are added in above-mentioned polyamic acid PAA solution, 20- is reacted
Soluble PI solution is obtained after 25 hours；
PI resin is obtained step 3: above-mentioned solubility PI solution is deposited in dehydrated alcohol, by resin separation, is washed
Wash, dry after obtain soluble PI resin, i.e. compound described in Formulas I, polyimide resin；
Step 4: the PI resin of 1-25% by weight percentage, which is dissolved in non-proton intensive polar solvent, is made PI solution；
TSP- is made step 5: the TSP-POSS of weight percent 1-60% is dissolved in non-proton intensive polar solvent
POSS solution；
Step 6: TSP-POSS solution obtained in PI solution made from the 4th step and the 5th step is pressed 1:1 mixed configuration
At compound resin solution；
Step 7: the compound resin solution matched is evenly applied on clean glass plate, it is placed in 100 grades of clean programs
In temperature-controlled drying case, it is gradually warmed up solidification, cooled to room temperature；Glass plate is soaked in deionized water, removing obtains PI
Laminated film.
A kind of preparation method of compound anti-atomic oxygen Kapton, PI resin percentage by weight in the 4th step
It is dissolved in non-proton intensive polar solvent than 10-20% and PI solution is made.
A kind of preparation method of compound anti-atomic oxygen Kapton, TSP-POSS by weight hundred in the 5th step
Divide to be dissolved in non-proton intensive polar solvent than 20-30% and TSP-POSS solution is made.
A kind of preparation method of compound anti-atomic oxygen Kapton, non-proton intensive polar solvent are selected from N- first
Base pyrrolidones NMP, DMAC N,N' dimethyl acetamide DMAc, N,N-dimethylformamide DMF are pressed by its any two or three
Arbitrary proportion mixes.
A kind of preparation method of the compound anti-atomic oxygen Kapton, in the 6th step, PI solution and TSP-
The mixed method of POSS solution includes mechanical mixing method and ultrasonic dispersion.
A kind of preparation method of the compound anti-atomic oxygen Kapton, in the 6th step, PI solution with
The mixed method of TSP-POSS solution is mechanical mixing method.
A kind of preparation method of compound anti-atomic oxygen Kapton is gradually warmed up solidification in the 7th step, multiple
Resin solution elevated cure according to the procedure below: the 0.5h under 50 DEG C of environment；The 3h under 80 DEG C of environment；Under 120 DEG C of environment
1h；The 1h under 150 DEG C of environment；The 1h under 180 DEG C of environment；The 1h under 250 DEG C of environment；The 1h under 300 DEG C of environment.
A kind of application of compound anti-atomic oxygen Kapton, polyimide composite film is covered on exposed
Transparent space flight equipment outer surface in space, can effectively improve its anti-atomic oxygen performance.
The beneficial effects of the present invention are: the film has dual anti-atomic oxygen characteristic, PI base film itself is because contain
P elements and characteristic with intrinsic anti-atomic oxygen, the laminated film that is formed more significantly enhances its antigen after adding TSP-POSS
Sub- oxygen performance.Since to form molecular level in organic solvent compound for TSP-POSS and PI matrix resin, compared with prior art phase
The more uniform dispersion than may be implemented avoids filler grain that degradation problem caused by reunion occurs.Further, since
Form that molecular level is compound between TSP-POSS and PI matrix, therefore laminated film maintains the excellent optics of PI film matrix
The transparency.Polyimide composite film of the present invention is covered on the exposed transparent space flight equipment outer surface in space, can be effective
Its anti-atomic oxygen performance is improved, and does not reduce its transparency substantially.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the laminated film of 2~embodiment of the embodiment of the present invention 5 and comparative example 1.
Fig. 2 is the infrared spectrogram of the laminated film of 2~comparative example of comparative example 7.
Fig. 3 is the UV-Vis figure of the laminated film of 1~embodiment of embodiment 5 and comparative example 1.
Fig. 4 is the UV-Vis figure of the laminated film of 2~comparative example of comparative example 7.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
A kind of compound anti-atomic oxygen Kapton of the present invention, intrinsic anti-atomic oxygen PI polymer and formula shown in Formulas I
The resin solution that TSP-POSS shown in II is proportionally combined and the laminated film prepared by the resin solution；
Mass percent TSP-POSS shared in TSP-POSS/PI laminated film total amount is m%, in which: 0 < m≤
30 integer.
A kind of compound anti-atomic oxygen Kapton, intrinsic anti-atomic oxygen PI polymer are one kind PI containing phosphorous
Film, by 4,4'- [hexafluoroisopropyli,ene] double phthalic anhydrides [6FDA] and 2,5- bis- { [4- amino-benzene oxygen] phenyl }
Diphenyl phosphine oxide [BADPO] synthesis.
A kind of preparation method of compound anti-atomic oxygen Kapton, laminated film can be made as steps described below
It is standby and obtain:
Step 1: diphenyl phosphine oxide BADPO is dissolved in non-proton intensive polar solvent, homogeneous phase solution is formed after stirring, is added
Enter dicarboxylic acid anhydride monomer 6FDA, is reacted 0.5-1 hours at 15-25 DEG C in temperature, obtain polyamic acid PAA solution；
Step 2: being heated to 180-200 DEG C for toluene, isoquinolin are added in above-mentioned polyamic acid PAA solution, 20- is reacted
Soluble PI solution is obtained after 25 hours；
PI resin is obtained step 3: above-mentioned solubility PI solution is deposited in dehydrated alcohol, by resin separation, is washed
Wash, dry after obtain soluble PI resin, i.e. compound described in Formulas I, polyimide resin；
Step 4: the PI resin of 1-25% by weight percentage, which is dissolved in non-proton intensive polar solvent, is made PI solution；
TSP- is made step 5: the TSP-POSS of weight percent 1-60% is dissolved in non-proton intensive polar solvent
POSS solution；
Step 6: TSP-POSS solution obtained in PI solution made from the 4th step and the 5th step is pressed 1:1 mixed configuration
At compound resin solution；
Step 7: the compound resin solution matched is evenly applied on clean glass plate, it is placed in 100 grades of clean programs
In temperature-controlled drying case, it is gradually warmed up solidification, cooled to room temperature；Glass plate is soaked in deionized water, removing obtains PI
Laminated film.
A kind of preparation method of compound anti-atomic oxygen Kapton, PI resin percentage by weight in the 4th step
It is dissolved in non-proton intensive polar solvent than 10-20% and PI solution is made.
A kind of preparation method of compound anti-atomic oxygen Kapton, TSP-POSS by weight hundred in the 5th step
Divide to be dissolved in non-proton intensive polar solvent than 20-30% and TSP-POSS solution is made.
A kind of preparation method of compound anti-atomic oxygen Kapton, non-proton intensive polar solvent are selected from N- first
Base pyrrolidones NMP, DMAC N,N' dimethyl acetamide DMAc, N,N-dimethylformamide DMF are pressed by its any two or three
Arbitrary proportion mixes.
A kind of preparation method of the compound anti-atomic oxygen Kapton, in the 6th step, PI solution and TSP-
The mixed method of POSS solution includes mechanical mixing method and ultrasonic dispersion.
A kind of preparation method of the compound anti-atomic oxygen Kapton, in the 6th step, PI solution with
The mixed method of TSP-POSS solution is mechanical mixing method.
A kind of preparation method of compound anti-atomic oxygen Kapton is gradually warmed up solidification in the 7th step, multiple
Resin solution elevated cure according to the procedure below: the 0.5h under 50 DEG C of environment；The 3h under 80 DEG C of environment；Under 120 DEG C of environment
1h；The 1h under 150 DEG C of environment；The 1h under 180 DEG C of environment；The 1h under 250 DEG C of environment；The 1h under 300 DEG C of environment.
A kind of application of compound anti-atomic oxygen Kapton, polyimide composite film is covered on exposed
Transparent space flight equipment outer surface in space, can effectively improve its anti-atomic oxygen performance.
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The material can be gotten from open business unless otherwise instructed.
The method of evaluating performance of PI film obtained by following embodiments is as follows:
FTIR spectrum:
It is measured using 27 type Fourier transformation infrared spectrometer of Tensor, method for making sample uses membrane process, range 4000
~400cm-1.
Thin-film transparent evaluation method:
Uv-vis spectra (UV-Vis).By the PI film of preparation in ultraviolet specrophotometer (Hitachi, Japan, U-
3210) it tests, 190~800nm of test wavelength range.
Anti-atomic oxygen method of evaluating performance:
The PI film of preparation is tested using THE FILAMENT DISCHARGE plasma-type AO effect analog equipment, atomic oxygen flux is
4.02×1020atom/cm2。
1 TSP-POSS content of embodiment is the TSP-POSS/PI laminated film (m=5) of 5wt%
It takes PI resin 10g to be dissolved in 37.1g DMAc, is configured to PI solution A；TSP-POSS 0.5263g is taken to be dissolved in
TSP-POSS solution B is configured in 5g DMAc；It filters, stands de- after solution A is sufficiently mixed under mechanical stirring with solution B
The TSP-POSS/PI compound resin solution that solid content is 20wt% is made in bubble, and it is compound that TSP-POSS content accounts for TSP-POSS/PI
The 5wt% of film total amount.The solution matched is evenly applied on clean glass plate by automatic film applicator, is placed in 100 grades
In clean temperature programmed control drying box, elevated cure according to the procedure below: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/
1h；180℃/1h；250℃/1h.Cooled to room temperature.Glass plate is soaked in deionized water, removing obtains PI THIN COMPOSITE
Film.
The TSP-POSS/PI laminated film that obtained TSP-POSS content is 5wt% uses 2 × 2cm2The sample of size into
Row AO corrodes simulated experiment, is 4.02 × 10 in atomic oxygen flux20atom/cm2When, mass loss 0.00032g, atom
Oxygen attack rate is 0.14015 × 10-24cm3/atom。
UV transmission spectrum is as shown in Fig. 3.
Specific data are as shown in table 1.
2 TSP-POSS content of embodiment is the TSP-POSS/PI laminated film (m=10) of 10wt%
It takes PI resin 10g to be dissolved in 39.4g DMAc, is configured to PI solution A；TSP-POSS 1.1111g is taken to be dissolved in
TSP-POSS solution B is configured in 5g DMAc；It filters, stands de- after solution A is sufficiently mixed under mechanical stirring with solution B
The TSP-POSS/PI compound resin solution that solid content is 20wt% is made in bubble, and it is compound that TSP-POSS content accounts for TSP-POSS/PI
The 10wt% of film total amount.The solution matched is evenly applied on clean glass plate by automatic film applicator, is placed in 100 grades
In clean temperature programmed control drying box, elevated cure according to the procedure below: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/
1h；180℃/1h；250℃/1h.Cooled to room temperature.Glass plate is soaked in deionized water, removing obtains PI THIN COMPOSITE
Film.
The TSP-POSS/PI laminated film that obtained TSP-POSS content is 10wt% uses 2 × 2cm2The sample of size
It carries out AO and corrodes simulated experiment, be 4.02 × 10 in atomic oxygen flux20atom/cm2When, mass loss 0.00021g is former
Sub- oxygen attack rate is 0.09197 × 10-24cm3/atom。
Infrared spectroscopy is as shown in Fig. 1；
UV transmission spectrum is as shown in Fig. 3.
Specific data are as shown in table 1.
3 TSP-POSS content of embodiment is the TSP-POSS/PI laminated film (m=15) of 15wt%
It takes PI resin 10g to be dissolved in 42.1g DMAc, is configured to PI solution A；TSP-POSS 1.7647g is taken to be dissolved in
TSP-POSS solution B is configured in 5g DMAc；It filters, stands de- after solution A is sufficiently mixed under mechanical stirring with solution B
The TSP-POSS/PI compound resin solution that solid content is 20wt% is made in bubble, and it is compound that TSP-POSS content accounts for TSP-POSS/PI
The 15wt% of film total amount.The solution matched is evenly applied on clean glass plate by automatic film applicator, is placed in 100 grades
In clean temperature programmed control drying box, elevated cure according to the procedure below: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/
1h；180℃/1h；250℃/1h.Cooled to room temperature.Glass plate is soaked in deionized water, removing obtains PI THIN COMPOSITE
Film.
The TSP-POSS/PI laminated film that obtained TSP-POSS content is 15wt% uses 2 × 2cm2The sample of size
It carries out AO and corrodes simulated experiment, be 4.02 × 10 in atomic oxygen flux20atom/cm2When, mass loss 0.00045g is former
Sub- oxygen attack rate is 0.19708 × 10-24cm3/atom。
Infrared spectroscopy is as shown in Fig. 1；
UV transmission spectrum is as shown in Fig. 3.
Specific data are as shown in table 1.
4 TSP-POSS content of embodiment is the TSP-POSS/PI laminated film (m=20) of 20wt%
It takes PI resin 10g to be dissolved in 40.0g DMAc, is configured to PI solution A；TSP-POSS 2.5000g is taken to be dissolved in
TSP-POSS solution B is configured in 10g DMAc；It filters, stands de- after solution A is sufficiently mixed under mechanical stirring with solution B
The TSP-POSS/PI compound resin solution that solid content is 20wt% is made in bubble, and it is compound that TSP-POSS content accounts for TSP-POSS/PI
The 20wt% of film total amount.The solution matched is evenly applied on clean glass plate by automatic film applicator, is placed in 100 grades
In clean temperature programmed control drying box, elevated cure according to the procedure below: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/
1h；180℃/1h；250℃/1h.Cooled to room temperature.Glass plate is soaked in deionized water, removing obtains PI THIN COMPOSITE
Film.
The TSP-POSS/PI laminated film that obtained TSP-POSS content is 20wt% uses 2 × 2cm2The sample of size
It carries out AO and corrodes simulated experiment, be 4.02 × 10 in atomic oxygen flux20atom/cm2When, mass loss 0.00019g is former
Sub- oxygen attack rate is 0.08321 × 10-24cm3/atom。
Infrared spectroscopy is as shown in Fig. 1；
UV transmission spectrum is as shown in Fig. 3.
Specific data are as shown in table 1.
5 TSP-POSS content of embodiment is the TSP-POSS/PI laminated film (m=25) of 25wt%
It takes PI resin 10g to be dissolved in 43.3g DMAc, is configured to PI solution A；TSP-POSS 3.3333g is taken to be dissolved in
TSP-POSS solution B is configured in 10g DMAc；It filters, stands de- after solution A is sufficiently mixed under mechanical stirring with solution B
The TSP-POSS/PI compound resin solution that solid content is 20wt% is made in bubble, and it is compound that TSP-POSS content accounts for TSP-POSS/PI
The 25wt% of film total amount.The solution matched is evenly applied on clean glass plate by automatic film applicator, is placed in 100 grades
In clean temperature programmed control drying box, elevated cure according to the procedure below: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/
1h；180℃/1h；250℃/1h.Cooled to room temperature.Glass plate is soaked in deionized water, removing obtains PI THIN COMPOSITE
Film.
The TSP-POSS/PI laminated film that obtained TSP-POSS content is 25wt% uses 2 × 2cm2The sample of size
It carries out AO and corrodes simulated experiment, be 4.02 × 10 in atomic oxygen flux20atom/cm2When, mass loss 0.00007g is former
Sub- oxygen attack rate is 0.03066 × 10-24cm3/atom。
Infrared spectroscopy is as shown in Fig. 1；
UV transmission spectrum is as shown in Fig. 3.
Specific data are as shown in table 1.
Comparative example 1 is free of the pure PI film (m=0) of TSP-POSS
It takes PI resin 10g to be dissolved in 40.0g DMAc, is configured to the PI resin solution that solid content is 20wt%.It will match
Solution be evenly applied to by automatic film applicator on clean glass plate, be placed in 100 grades of clean temperature programmed control drying boxes, press
According to following procedure elevated cure: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/1h；180℃/1h；250℃/1h.It is natural
It is cooled to room temperature.Glass plate is soaked in deionized water, removing obtains PI laminated film.
Obtained PI film uses 2 × 2cm2The sample of size carries out AO and corrodes simulated experiment, is in atomic oxygen flux
4.02×1020atom/cm2When, mass loss 0.00122g, atomic oxygen erosion rate is 0.53431 × 10-24cm3/atom。
Infrared spectroscopy is as shown in Fig. 1；
UV transmission spectrum is as shown in Fig. 3.
Specific data are as shown in table 1.
Comparative example 2 poly- (pyromellitic acid anhydride-diaminodiphenyl ether) (PMDA-ODA, Kapton type film)
CommercializationFilm is cut into 2 × 2cm2The sample of size carries out AO and corrodes simulated experiment, in elemental oxygen
Flux is 4.02 × 1020atom/cm2When, mass loss 0.00685g, atomic oxygen erosion rate is 3.0 × 10-24cm3/
atom。
Infrared spectroscopy is as shown in Fig. 2；
UV transmission spectrum is as shown in Fig. 4.
Specific data are as shown in table 1.
3 TSP-POSS content of comparative example is the TSP-POSS/Kapton laminated film of 5wt%
The TSP-POSS that 5wt% is added in the polyamic acid solution of PMDA-ODA stirs the solution movement matched
0.5h, standing and defoaming are evenly applied on clean glass plate by automatic film applicator, and it is dry to be placed in 100 grades of clean temperature programmed controls
In dry case, elevated cure according to the procedure below: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/1h；180℃/1h；250
℃/1h；300℃/1h.Cooled to room temperature.Glass plate is soaked in deionized water, removing obtains PI laminated film.
Obtained TSP-POSS content is the TSP-POSS/Kapton laminated film of 5wt%, uses 2 × 2cm2Size
Sample carries out AO and corrodes simulated experiment, is 4.02 × 10 in atomic oxygen flux20atom/cm2When, mass loss is
0.00245g, atomic oxygen erosion rate are 1.07299 × 10-24cm3/atom。
Infrared spectroscopy is as shown in Fig. 2；
UV transmission spectrum is as shown in Fig. 4.
Specific data are as shown in table 1.
4 TSP-POSS content of comparative example is the TSP-POSS/Kapton laminated film of 10wt%
The TSP-POSS that 10wt% is added in the polyamic acid solution of PMDA-ODA stirs the solution movement matched
0.5h, standing and defoaming are evenly applied on clean glass plate by automatic film applicator, and it is dry to be placed in 100 grades of clean temperature programmed controls
In dry case, elevated cure according to the procedure below: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/1h；180℃/1h；250
℃/1h；300℃/1h.Cooled to room temperature.Glass plate is soaked in deionized water, removing obtains PI laminated film.
Obtained TSP-POSS content is the TSP-POSS/Kapton laminated film of 10wt%, uses 2 × 2cm2Size
Sample carries out AO and corrodes simulated experiment, is 4.02 × 10 in atomic oxygen flux20atom/cm2When, mass loss is
0.00126g, atomic oxygen erosion rate are 0.55182 × 10-24cm3/atom。
Infrared spectroscopy is as shown in Fig. 2；
UV transmission spectrum is as shown in Fig. 4.
Specific data are as shown in table 1.
5 TSP-POSS content of comparative example is the TSP-POSS/Kapton laminated film of 15wt%
The TSP-POSS that 15wt% is added in the polyamic acid solution of PMDA-ODA stirs the solution movement matched
0.5h, standing and defoaming are evenly applied on clean glass plate by automatic film applicator, and it is dry to be placed in 100 grades of clean temperature programmed controls
In dry case, elevated cure according to the procedure below: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/1h；180℃/1h；250
℃/1h；300℃/1h.Cooled to room temperature.Glass plate is soaked in deionized water, removing obtains PI laminated film.
Obtained TSP-POSS content is the TSP-POSS/Kapton laminated film of 15wt%, uses 2 × 2cm2Size
Sample carries out AO and corrodes simulated experiment, is 4.02 × 10 in atomic oxygen flux20atom/cm2When, mass loss is
0.00088g, atomic oxygen erosion rate are 0.3854 × 10-24cm3/atom。
Infrared spectroscopy is as shown in Fig. 2；
UV transmission spectrum is as shown in Fig. 4.
Specific data are as shown in table 1.
6 TSP-POSS content of comparative example is the TSP-POSS/Kapton laminated film of 20wt%
The TSP-POSS that 20wt% is added in the polyamic acid solution of PMDA-ODA stirs the solution movement matched
0.5h, standing and defoaming are evenly applied on clean glass plate by automatic film applicator, and it is dry to be placed in 100 grades of clean temperature programmed controls
In dry case, elevated cure according to the procedure below: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/1h；180℃/1h；250
℃/1h；300℃/1h.Cooled to room temperature.Glass plate is soaked in deionized water, removing obtains PI laminated film.
Obtained TSP-POSS content is the TSP-POSS/Kapton laminated film of 20wt%, uses 2 × 2cm2Size
Sample carries out AO and corrodes simulated experiment, is 4.02 × 10 in atomic oxygen flux20atom/cm2When, mass loss is
0.00062g, atomic oxygen erosion rate are 0.27153 × 10-24cm3/atom。
Infrared spectroscopy is as shown in Fig. 2；
UV transmission spectrum is as shown in Fig. 4.
Specific data are as shown in table 1.
7 TSP-POSS content of comparative example is the TSP-POSS/Kapton laminated film of 25wt%
The TSP-POSS that 25wt% is added in the polyamic acid solution of PMDA-ODA, by the solution matched by applying automatically
Film machine is evenly applied on clean glass plate, is placed in 100 grades of clean temperature programmed control drying boxes, heating is solid according to the procedure below
Change: 50 DEG C/0.5h；80℃/3h；120℃/1h；150℃/1h；180℃/1h；250℃/1h；300℃/1h.It naturally cools to
Room temperature.Glass plate is soaked in deionized water, removing obtains PI film.
Obtained TSP-POSS content is the POSS/Kapton laminated film of 25wt%, uses 2 × 2cm2The sample of size
It carries out AO and corrodes simulated experiment, be 4.02 × 10 in atomic oxygen flux20atom/cm2When, mass loss 0.00049g is former
Sub- oxygen attack rate is 0.2146 × 10-24cm3/atom。
Infrared spectroscopy is as shown in Fig. 2；
UV transmission spectrum is as shown in Fig. 4.
Specific data are as shown in table 1.
The performance of 1 TSP-POSS/Kapton laminated film of table
Data shown in contrast table 1 can be seen that the TSP-POSS/PI THIN COMPOSITE added after TSP-POSS in Examples 1 to 5
The anti-atomic oxygen performance of film is obviously improved, and the atomic oxygen erosion rate of the film wherein prepared in embodiment 5 is minimum, i.e., anti-
Elemental oxygen performance is best, shows that dual elemental oxygen process for protecting provided by the invention has good implementation result.Compare implementation
The light transmittance of 1~5 film of example is not it can be found that the introducing of TSP-POSS makes a significant impact the transparency of laminated film, table
It is bright to realize the compound of molecular level.PI film in comparative example 1 without TSP-POSS shows intrinsic anti-atomic oxygen characteristic,
Atomic oxygen erosion rate is compared in comparative example 2Film, atomic oxygen erosion rate be only its 1/5th.Comparative example 3
~7, i.e., in not anti-atomic oxygenAfter adding TSP-POSS in substrate, the anti-atomic oxygen performance of laminated film is also obtained
Improvement is arrived, but implementation result is weaker than Examples 1 to 5.It can be seen that TSP-POSS/PI laminated film tool provided by the invention
There are excellent anti-atomic oxygen performance and optical transparence, is a kind of film haveing excellent performance in terms of aerospace applications.
The present invention is not limited to above-mentioned preferred forms, anyone obtain under the inspiration of the present invention other it is any with
The identical or similar product of the present invention, is within the scope of the present invention.
Claims (10)
1. a kind of compound anti-atomic oxygen Kapton, it is characterised in that: intrinsic anti-atomic oxygen PI polymer shown in Formulas I with
The resin solution that TSP-POSS shown in Formula II is proportionally combined and the laminated film prepared by the resin solution；
Mass percent TSP-POSS shared in TSP-POSS/PI laminated film total amount is m%, in which: 0 m≤30 <
Integer.
2. a kind of compound anti-atomic oxygen Kapton according to claim 1, it is characterised in that: intrinsic antigen
Oxygen PI polymer is one kind film of PI containing phosphorous, and by the double phthalic anhydrides of 4,4'- [hexafluoroisopropyli,ene] and 2,5- is bis-
The synthesis of { [4- amino-benzene oxygen] phenyl } diphenyl phosphine oxide.
3. a kind of preparation method of compound anti-atomic oxygen Kapton according to claim 1, it is characterised in that:
Laminated film can be prepared as steps described below:
Step 1: diphenyl phosphine oxide is dissolved in non-proton intensive polar solvent, homogeneous phase solution is formed after stirring, and dicarboxylic acid anhydride is added
Monomer reacts 0.5-1 hours at 15-25 DEG C in temperature, obtains polyamic acid solution；
Step 2: being heated to 180-200 DEG C for toluene, isoquinolin are added in above-mentioned polyamic acid solution, react 20-25 hours
After obtain soluble PI solution；
PI resin is obtained step 3: above-mentioned solubility PI solution is deposited in dehydrated alcohol, by resin separation, washing, is done
Soluble PI resin, i.e. compound described in Formulas I, polyimide resin are obtained after dry；
Step 4: the PI resin of 1-25% by weight percentage, which is dissolved in non-proton intensive polar solvent, is made PI solution；
Step 5: it is molten that the TSP-POSS of weight percent 1-60% is dissolved in non-proton intensive polar solvent obtained TSP-POSS
Liquid；
Step 6: TSP-POSS solution obtained in PI solution made from the 4th step and the 5th step is mixedly configured into again by 1:1
Resin solution；
Step 7: the compound resin solution matched is evenly applied on clean glass plate, it is placed in 100 grades of clean temperature programmed controls
In drying box, it is gradually warmed up solidification, cooled to room temperature；Glass plate is soaked in deionized water, it is compound that removing obtains PI
Film.
4. a kind of preparation method of compound anti-atomic oxygen Kapton according to claim 3, it is characterised in that:
PI resin 10-20% by weight percentage, which is dissolved in non-proton intensive polar solvent, in 4th step is made PI solution.
5. a kind of preparation method of compound anti-atomic oxygen Kapton according to claim 3, it is characterised in that:
It is molten to be dissolved in non-proton intensive polar solvent obtained TSP-POSS by TSP-POSS 20-30% by weight percentage in 5th step
Liquid.
6. a kind of preparation method of compound anti-atomic oxygen Kapton, feature according to claim 3,4 and 5
Be: the non-proton intensive polar solvent is selected from N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide
One of or mixed in any proportion by its any two or three.
7. a kind of preparation method of compound anti-atomic oxygen Kapton according to claim 3, it is characterised in that:
In 6th step, the mixed method of PI solution and TSP-POSS solution includes mechanical mixing method and ultrasonic dispersion.
8. a kind of preparation method of compound anti-atomic oxygen Kapton according to claim 7, it is characterised in that:
In 6th step, the mixed method of PI solution and TSP-POSS solution is mechanical mixing method.
9. a kind of preparation method of compound anti-atomic oxygen Kapton according to claim 3, it is characterised in that:
It is gradually warmed up solidification in 7th step, compound resin solution elevated cure according to the procedure below: the 0.5h under 50 DEG C of environment；?
3h under 80 DEG C of environment；The 1h under 120 DEG C of environment；The 1h under 150 DEG C of environment；The 1h under 180 DEG C of environment；The 1h under 250 DEG C of environment；
The 1h under 300 DEG C of environment.
10. a kind of application of compound anti-atomic oxygen Kapton according to claim 1, it is characterised in that: institute
It states polyimide composite film and is covered on the exposed transparent space flight equipment outer surface in space, can effectively improve its antigen
Oxygen performance.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811063980.4A CN109337365B (en) | 2018-09-12 | 2018-09-12 | Composite atomic oxygen resistant polyimide film and application |
| CN202110350124.2A CN113122000B (en) | 2018-09-12 | 2018-09-12 | Preparation method of composite atomic oxygen resistant polyimide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811063980.4A CN109337365B (en) | 2018-09-12 | 2018-09-12 | Composite atomic oxygen resistant polyimide film and application |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110350124.2A Division CN113122000B (en) | 2018-09-12 | 2018-09-12 | Preparation method of composite atomic oxygen resistant polyimide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109337365A true CN109337365A (en) | 2019-02-15 |
| CN109337365B CN109337365B (en) | 2021-05-14 |
Family
ID=65304892
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110350124.2A Active CN113122000B (en) | 2018-09-12 | 2018-09-12 | Preparation method of composite atomic oxygen resistant polyimide film |
| CN201811063980.4A Active CN109337365B (en) | 2018-09-12 | 2018-09-12 | Composite atomic oxygen resistant polyimide film and application |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110350124.2A Active CN113122000B (en) | 2018-09-12 | 2018-09-12 | Preparation method of composite atomic oxygen resistant polyimide film |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN113122000B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111205645A (en) * | 2020-03-20 | 2020-05-29 | 无锡创彩光学材料有限公司 | Polyimide film with high transparency and high surface hardness and preparation method thereof |
| CN114015233A (en) * | 2021-12-01 | 2022-02-08 | 中国地质大学（北京） | Polyimide material and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114717751B (en) * | 2021-12-09 | 2023-06-20 | 中国地质大学（北京） | Atomic oxygen-resistant polyimide nanofiber membrane and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531678A (en) * | 2009-04-22 | 2009-09-16 | 中国科学院化学研究所 | Phosphine-containing aromatic diamine compound, preparation method and application thereof |
| CN103435827A (en) * | 2013-08-29 | 2013-12-11 | 西北工业大学 | Preparation method of aerospace hyperbranched polysiloxane polyimide transparent hybrid thin films |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4016844B2 (en) * | 2003-01-27 | 2007-12-05 | 宇部興産株式会社 | Polyimide film for spacecraft thermal control materials |
| CN102731809A (en) * | 2012-06-04 | 2012-10-17 | 西北工业大学 | Preparation method of atomic oxygen-resistant polyimide hybrid films containing POSS (polyhedral oligomeric silsesquioxanes) structures |
-
2018
- 2018-09-12 CN CN202110350124.2A patent/CN113122000B/en active Active
- 2018-09-12 CN CN201811063980.4A patent/CN109337365B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531678A (en) * | 2009-04-22 | 2009-09-16 | 中国科学院化学研究所 | Phosphine-containing aromatic diamine compound, preparation method and application thereof |
| CN103435827A (en) * | 2013-08-29 | 2013-12-11 | 西北工业大学 | Preparation method of aerospace hyperbranched polysiloxane polyimide transparent hybrid thin films |
Non-Patent Citations (3)
| Title |
|---|
| YAN ZHANG等: "Trisilanolphenyl-POSS nano-hybrid poly(biphenyl dianhydride-p-phenylenediamine) polyimide composite films: miscibility and structure-property relationship", 《JOURNAL OF POLYMER RESEARCH》 * |
| 李卓等: "含磷聚酰亚胺薄膜在原子氧环境中的降解研究", 《航天器环境工程》 * |
| 李卓等: "抗原子氧聚酰亚胺的研究与应用进展", 《高分子通报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111205645A (en) * | 2020-03-20 | 2020-05-29 | 无锡创彩光学材料有限公司 | Polyimide film with high transparency and high surface hardness and preparation method thereof |
| CN114015233A (en) * | 2021-12-01 | 2022-02-08 | 中国地质大学（北京） | Polyimide material and preparation method and application thereof |
| CN114015233B (en) * | 2021-12-01 | 2022-07-05 | 中国地质大学（北京） | Polyimide material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109337365B (en) | 2021-05-14 |
| CN113122000A (en) | 2021-07-16 |
| CN113122000B (en) | 2022-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7037534B2 (en) | Polyimide film with voids and its manufacturing method | |
| CN109337365A (en) | A kind of compound anti-atomic oxygen Kapton and the preparation method and application thereof | |
| CN110105570B (en) | Polyimide material with high heat resistance and low thermal expansion coefficient and preparation method thereof | |
| CN106164132A (en) | Novel polyimide compositions | |
| US20100063244A1 (en) | Polymeric coating for protecting objects | |
| CN110698670B (en) | Carborane modified polyimide film and preparation method thereof | |
| TWI728163B (en) | Polyimide, polyimide solution, polyimide, polyimide film, laminate and flexible device, and manufacturing method of polyimide film | |
| CN102167824A (en) | Polyimide film and preparation method and applications thereof | |
| US20020016408A1 (en) | Polyimide silicone resin, its solution composition, and polyimide silicone resin film | |
| CN103435827B (en) | A kind of preparation method of space hyperbranched polyorganosiloxane polyimide transparent hybrid film | |
| CN110684238A (en) | Microcapsule capable of being self-repaired repeatedly at room temperature, preparation method and application | |
| CN109679094B (en) | Polyimide precursor, polyimide, laminate, and flexible device | |
| CN109535713A (en) | A kind of cenosphere/composite polyimide material and its preparation method and application | |
| CN107757015A (en) | A kind of surface silicon oxidation polyimides co siloxane films and preparation method thereof | |
| CN111116950A (en) | High-performance polyimide film and preparation method thereof | |
| CN115160566A (en) | Polyimide, slurry, film, preparation method of polyimide, slurry, film and flexible display device | |
| CN113149455A (en) | Preparation method of coated glass for solar photovoltaic module | |
| WO1996034303A1 (en) | Material for forming color-filter protecting film and color-filter protecting film | |
| CN106366791B (en) | A kind of backboard that can delay failure under dry wet alternating environment | |
| CN114015233B (en) | Polyimide material and preparation method and application thereof | |
| CN102617875A (en) | Preparation method for transparent polyimide/silicon dioxide hybrid film | |
| CN113136032A (en) | Space atomic oxygen-resistant optically transparent thermosetting shape memory polyimide, and preparation method and application thereof | |
| CN115975463B (en) | Wind power blade protective coating and preparation method thereof | |
| CN114702783B (en) | Transparent glass fiber mobile phone cover plate and preparation method thereof | |
| CN111378278A (en) | High-temperature-resistant thermal control film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Jingang Inventor after: Zhang Yan Inventor after: Wu Xiao Inventor after: Guo Chenyu Inventor after: Jiang Ganglan Inventor after: Qi Lin Inventor before: Liu Jingang Inventor before: Zhang Yan Inventor before: Wu Xiao Inventor before: Guo Chenyu Inventor before: Jiang Lanlan Inventor before: Qi Lin |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210802 Address after: 314000, No. 9, building 2, Hangzhou bay new economic Park, Jiaxing City, port area, Jiaxing City, Zhejiang Province Patentee after: Jiaxing ruihuatai Film Technology Co.,Ltd. Address before: 100083 No. 29, Haidian District, Beijing, Xueyuan Road Patentee before: China University of Geosciences (Beijing) |