CN114736409A - Polyimide film with siloxane grafted on side chain - Google Patents
Polyimide film with siloxane grafted on side chain Download PDFInfo
- Publication number
- CN114736409A CN114736409A CN202210407318.6A CN202210407318A CN114736409A CN 114736409 A CN114736409 A CN 114736409A CN 202210407318 A CN202210407318 A CN 202210407318A CN 114736409 A CN114736409 A CN 114736409A
- Authority
- CN
- China
- Prior art keywords
- siloxane
- dianhydride
- film
- minutes
- side chain
- 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
Images
Classifications
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- 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
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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)
- General Chemical & Material Sciences (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polyimide film with side chain grafted siloxane and a preparation method thereof, which comprises the steps of adding a copolymer with long side chain siloxane into a reaction system solvent, wherein the number of siloxane side chain structural units is 3-20, the content of long side chain siloxane comonomer is 1% -70%, and the added siloxane can be a siloxane oligomer with a terminal group of m-phenylenediamine or a waist-linked m-phenylenediamine group. The diamine monomer connected with the benzene ring is arranged on the main chain, and the flexible siloxane is arranged on the side chain, so that the polyimide molecule still has high rigidity and heat resistance after a certain amount of siloxane is copolymerized. The invention is beneficial to eliminating the internal stress of the polyimide film during molding and repeated heating, has good thermal shock resistance, is beneficial to reducing the dielectric constant of the material, simultaneously improves the gas permeation capability of the film, and is especially suitable for high-temperature film distillation environment or applied to electrical equipment such as chips, batteries, motors and the like which need to be repeatedly lifted and lowered and are in severe working environment.
Description
Technical Field
The invention belongs to the field of new polymer materials, and particularly relates to a polyimide film with siloxane grafted on a side chain and a preparation method thereof.
Background
Polyimide is a generic name for a class of high molecular polymer materials having imide bonds in the main chain, and is most excellent in heat resistance among conventional high molecular engineering plastics. Wherein, the heat-resistant temperature of the aromatic polyimide can reach more than 500 ℃, and the aromatic polyimide can be used for a long time at more than 300 ℃. In addition, the polyimide material has excellent comprehensive performances such as mechanical stability and chemical stability, and is expected to be widely applied to the fields of batteries, motors, high-voltage power transmission, aerospace and the like. However, the polyimide material still has many defects, for example, the solvent requirement is harsh, and the polyimide material can only be dissolved in a strong polar protic solvent; the curing process and the cyclization process are coupled and occur simultaneously, and obvious internal stress exists during film curing; the molecular motion ability is weak, and internal stress can be generated when the molecules are repeatedly heated; the structure is compact, so that the gas permeability is poor, and the material cannot be directly used for high-temperature transmission materials; the molecules contain a large amount of polar amide groups, so that the material has strong hydrophilicity, insufficient water resistance, high surface tension and insufficient oil stain resistance; polar groups in the molecules also enable the molecules to have higher dielectric constants, and are not beneficial to being used in the fields of wave transmission, power transmission and transformation and the like. Therefore, for application scenes in complex environments, a special polyimide variety with hydrophobic water resistance, high-temperature ventilation, low dielectric constant and less residual internal stress needs to be developed on the premise of not losing the thermal performance of polyimide.
Polydimethylsiloxane is a high-molecular elastomer material with excellent high and low temperature stability. According to the difference of relative molecular mass, the liquid or elastomer silica gel with the appearance from low-viscosity liquid to extremely high viscosity has the characteristics of excellent heat resistance, weather resistance, waterproofness, low surface tension, proper heat conductivity, high gas permeability, high light transmittance, physiological inertia, chemical stability, electric insulativity, low dielectric and the like, is a high polymer material with excellent comprehensive performance, and is expected to be applied to the fields of artificial muscles, electronic skins, medical film accessories, intelligent sensors, intelligent bandages, wound dressings and the like. The introduction of the copolymerization into a polyimide system can effectively improve the weather resistance, air permeability, dielectric property and residual stress removal capability of the polyimide material. However, it has been widely studied to partially replace the common diamine monomer such as 4,4' -diaminodiphenyl ether (ODA) with amino-terminated siloxane to co-polymerize with dianhydride. However, the polyimide material modified by the main chain has the obvious defects, the mechanical property of the material can be obviously reduced after the main chain is introduced due to the high elasticity of the polydimethylsiloxane, and meanwhile, the two components are connected in series on the same main chain to form a microphase separation structure difficultly, so that the optimization of the material property is not facilitated.
Disclosure of Invention
The invention aims to introduce polydimethylsiloxane with high mass fraction into polyimide by using a method of grafting siloxane on a side chain, obtain a polyimide film material with a microphase separation structure by using incompatibility of two components, keep heat resistance, simultaneously enable the film to have lower internal stress and thermal shock resistance, better gas permeability, lower dielectric property and better water and weather resistance, and is expected to be used in the fields of gas filtration, power transmission line protection, batteries and the like in a complex environment.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a polyimide film with side chain grafted with siloxane comprises the following steps:
(1) mixing a diamine monomer and a dianhydride monomer according to a molar ratio of 0.9-1.1: 1, adding the mixture into a solvent for polymerization reaction at a reaction temperature of less than 60 ℃, and stirring for 12 hours to prepare slurry;
wherein the diamine monomer comprises diamine monomer containing long side chain siloxane accounting for 1-70% of the total amount of the diamine monomer, and the diamine monomer is m-phenylenediamine terminated polysiloxane
Or waist-linked m-phenylenediamine polysiloxane
Wherein, the value ranges of x and y are both 3-22, and the values of x and y can be the same or different;
(2) sending the composite slurry prepared in the step (1) into an extrusion coating machine, coating polyimide resin liquid onto a steel belt through an extrusion die head, and controlling the thickness of the film through a gap at the outlet of the electronic control die head; the thickness of the film was 18 um; the coating film was deaerated and predried under reduced pressure at 25 ℃ for 30 minutes;
(3) sending the polyimide film subjected to extrusion coating film formation in the step (2) into an imidizing furnace for imidization treatment, wherein the treatment conditions are as follows: 60 minutes at 120 ℃, 60 minutes at 150 ℃, 30 minutes at 200 ℃, 30 minutes at 250 ℃, 20 minutes at 320 ℃ and 10 minutes at 400 ℃.
Preferably, the organic solvent is one or more of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), N-Dimethylformamide (DMF), N-Diethylformamide (DEF), Dimethylacetamide (DMAC), and Dimethylsulfoxide (DMSO).
Preferably, the m-phenylenediamine-terminated polysiloxane is prepared by the following method:
the polysiloxane with the waist-connected m-phenylenediamine is prepared by the following method:
preferably, the dianhydride monomer is an aliphatic dianhydride monomer, an alicyclic dianhydride, an aromatic dianhydride monomer, and derivatives thereof.
Preferably, the dianhydride monomer is one or a combination of several of pyromellitic dianhydride (PMDA), 4,4 '-diphenyl ether dianhydride (ODPA), 3',4,4 '-Benzophenone Tetracarboxylic Dianhydride (BTDA), 4,4' - (hexafluoroisopropyl) diphthalic anhydride (6FDA), 3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), 1,4,5, 8-naphthalene tetracarboxylic anhydride (NTDA), cyclobutane dianhydride (CBDA), 3,4, 4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), or the like, or a derivative based on the above dianhydrides.
Preferably, the diamine monomer is an aliphatic diamine monomer, an alicyclic diamine monomer, an aromatic diamine monomer, and derivatives thereof.
Preferably, the diamine monomer is one or a combination of several of 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD), 4' -diaminodiphenylmethane (MDA), 4 '-diamino-2, 2' -dimethyl-1, 1 '-biphenyl (m-TB), Benzidine (Benzidine), 2' -bis (trifluoromethyl) diaminobiphenyl (TFMB), 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 2-bis (4-aminophenyl) hexafluoropropane (6FpDA), or the like, or a derivative based on the foregoing diamines.
As another object of the present invention, there is provided a side-chain-grafted siloxane polyimide film prepared by the above method.
Compared with the prior art, the method has the following beneficial effects:
the polyimide with the long siloxane grafted on the side chain can ensure that the material has thermal degradation temperature close to that of non-grafted materials, and the thermal stability of the material is not greatly sacrificed. Meanwhile, the obtained polyimide material, especially the film material, has a remarkable phase separation structure, especially the waist-connected polysiloxane side chain proposed by the patent, and a microphase separation structure can be obtained under the conditions of lower copolymerization amount and shorter side chain. The phase separation structure enables the polyimide film to have lower internal stress, better dimensional stability, better gas permeability, lower dielectric constant and more excellent hydrophobicity, and the film is more suitable for application scenes with the requirements of water resistance, insulation, ventilation and the like in complex environments such as humid environment, high voltage environment and the like.
Drawings
FIG. 1 is an infrared spectrum of example 1;
FIGS. 2A-C are Atomic Force Microscope (AFM) profiles of the microphase-separated thin film structures of examples 1, 2 and 5, respectively.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention adopts m-phenylenediamine (a) at the end and m-phenylenediamine (b) connected with waist as comonomers for introducing long-chain siloxane. Wherein x is the number of repeating units of polydimethylsiloxane and can be between 3 and 22, y is the number of repeating units of another segment of the waist-connected polydimethylsiloxane and can be between 3 and 22, and x and y can take different values. Side chain silane compounds and derivatives thereof having similar chemical structures may also be added to the system.
The two monomers can be obtained directly or by simple chemical reactions, such as the condensation of chlorosiloxanes with phenols (formula a) or the addition of silicon hydrogen bonds with vinyl groups (formula b):
(a)
(b)
furthermore, diamine monomers with different siloxane side chains are used as copolymerization units to participate in the synthesis process of dianhydride monomers and diamine monomers, and the polyimide film containing direct and waist-connected siloxane long side chains is obtained. The reaction equation for polyimides is as follows:
wherein Ar is dianhydride monomer which can be aliphatic, alicyclic, aromatic and derivatives thereof, and particularly when the dianhydride is aromatic, the polyimide has high heat resistance. For example, the dianhydride monomer may be one or a combination of several of pyromellitic dianhydride (PMDA), 4,4 '-diphenyl ether dianhydride (ODPA), 3',4,4 '-Benzophenone Tetracarboxylic Dianhydride (BTDA), 4,4' - (hexafluoroisopropyl) diphthalic anhydride (6FDA), 3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA), 1,4,5, 8-naphthalene tetracarboxylic anhydride (NTDA), cyclobutane dianhydride (CBDA), 3,4, 4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), or derivatives based on the foregoing dianhydrides, and a part of the dianhydride monomer has the following structural formula:
wherein Ar' is diamine monomer, which can be aliphatic, alicyclic and aromatic diamine and its derivative, especially when the diamine monomer is aromatic diamine, the polyimide has high heat resistance. For example, the diamine monomer may be one or a combination of 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD), 4' -diaminodiphenylmethane (MDA), 4 '-diamino-2, 2' -dimethyl-1, 1 '-biphenyl (m-TB), Benzidine (Benzidine), 2' -bis (trifluoromethyl) diaminobiphenyl (TFMB), 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 2-bis (4-aminophenyl) hexafluoropropane (6FpDA), or a derivative based on the above diamines, and a part of the diamine monomer has the following structural formula:
to obtain high molecular weight polyimide, the molar ratio of the total amount of the two diamine monomers to the dianhydride monomer should be 0.9-1.1: 1. The diamine monomer containing long side chain siloxane accounts for 1-70% of the total diamine monomer. Polyimide films with different siloxane side chain lengths, different siloxane connection modes and different siloxane-containing diamine monomer contents have obviously different properties, and can be adjusted according to actual application conditions to obtain the optimized proportion.
Further, the organic solvent may be selected from one or more of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), N-Dimethylformamide (DMF), N-Diethylformamide (DEF), Dimethylacetamide (DMAC), and Dimethylsulfoxide (DMSO). When the siloxane content is high (when the siloxane content is more than 50%), a weak polar solvent such as Toluene (Toluene), Xylene (Xylene), Chloroform (Chloroform), Dichloromethane (DCM) and the like can be added into the strong polar solvent, so that the boiling point of the blending solvent is reduced while the solubility of the system is increased, and the curing process is accelerated.
Further, the polymerization reaction is still a two-step reaction, and first, a solvent-soluble polyamic acid is prepared, and then, polyimide is obtained by thermal imidization. The preparation process of polyamic acid includes adding dianhydride, diamine monomer and mixed solvent at low temperature, and has exothermic reaction, polymerization temperature not higher than 60 deg.c controlled strictly during the feeding and reaction process and fast temperature rise. Due to the long side chain siloxane, the addition of a small amount of nonpolar solvent such as chloroform, toluene and the like can increase the reaction stability to prevent premature gelation, obtain high molecular weight polymer, and control the chain length of the siloxane is not suitable to be too long, or adopt a waist-connected polysiloxane side chain.
Further, the polyimide film is subjected to thermal imidization and curing by adopting a gradual temperature rise program, and the temperature is gradually raised to more than 400 ℃ from 80 ℃ through one step or multiple steps. In the heating process, too fast cyclization and a large amount of heat release are prevented, and the uniformity of film formation can be improved by blending and adding a nonpolar solvent, and the solvent volatilization process can be milder. The addition of the weak polar solvent can enhance the nucleophilic ability of amino on amido bond, improve the ring closing efficiency and improve the quality of the polyimide film.
Further, the specific reaction conditions should be adjusted in consideration of the length of the side chain, the manner of side chain attachment, and the content of the long-side chain polysiloxane. The longer the side chain length or the higher the long side chain siloxane content, the greater the steric hindrance of the molecule during the polycondensation reaction, and the longer the reaction time required, which also leads to a better degree of microphase separation and film gas permeability. The waist connection mode has better microphase separation effect than the straight chain connection mode, and has smaller influence on the polycondensation reaction activity.
Furthermore, due to the compatibilization effect of the long side chain siloxane, the system is particularly suitable for being added with an inorganic or organic filling material to realize the synergistic modification effect, such as nano aluminum oxide for improving the film rigidity, nano silicon dioxide for improving the film dielectric property, nano boron nitride for improving the film heat-conducting property, carbon black, graphene and carbon nano tubes for improving the antistatic and conductive properties of the film, and the like. Other compounding ingredients may be added depending on the application and the required performance, and for example, a surfactant, a release agent, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a coloring agent such as a dye or a pigment, a conductive agent such as a metal powder, a surface treatment agent, a viscosity modifier, a coupling agent, a weather resistant agent, an antioxidant, and the like may be added.
Further, the addition of long side chain polysiloxane increases the fluidity of polyamic acid solution, and various film and coating preparations using different coating and coating processes on a substrate can be used with its high fluidity to finally realize the preparation of polyimide film or coating, and for example, a film or coating method such as spray method, roll coating method, spin coating method, bar coating method, ink jet method, screen printing method, slit coating method, and the like can be suitably used.
The special physical property experiment carried out on the polyimide film in the invention verifies the physical properties such as water resistance, cycling stability and the like, and comprises the following steps: (1) soaking for 24 hours for a water absorption experiment, namely soaking the polyimide film in deionized water for 24 hours, and measuring the weight change before and after water absorption; (2) in the thermal cycle experiment, the corresponding polyamic acid solution is coated on the surface of a silicon wafer, is embedded by epoxy resin after being cured, and is repeatedly cycled for 100 times at high and low temperatures (30 minutes at minus 65 ℃ to 30 minutes at 150 ℃), and the crack condition of the PI film and the substrate silicon wafer is observed; (3) thermal shock experiments: the polyamic acid resin-coated chip was placed in a frame, subjected to severe high and low temperature changes (-196 ℃ for 2 minutes-150 ℃ for 2 minutes), observed for changes in the bending angle of the chip, and compared with the bending relative value in a PMDA-ODA standard sample to obtain the internal stress relative value.
The following detailed description is to be read with reference to specific embodiments and the drawings.
Example 1
In a glass reaction vessel having a volume of 500mL with a stirrer and under protection of an inert gas, 300g of NMP and 100g of toluene as a solvent were charged, 0.2mol of PPD and 0.25mol of BPDA were added thereto, and 0.05mol of the linear siloxane polymer (a) having a chain length x of 10 was dissolved by stirring at room temperature, and the reaction was carried out at 50 ℃ for 10 hours with stirring to obtain a polyamic acid solution composition having a solution viscosity of 52.0Pa · s, and no flocs or insoluble matter was formed in the reaction product. The polyamic acid coating thermal cycle experiment shows that the polyamic acid coating has good fit with the substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.7.
Sending the polyimide resin solution into an extrusion coating machine, coating the polyimide resin solution on a steel belt through an extrusion die head, and controlling the thickness of a film through a gap at the outlet of the extrusion die head by electronic control; the thickness of the film was 18um, the film was defoamed and predried at 25 ℃ for 30 minutes under reduced pressure, and then placed in a hot air dryer under normal pressure nitrogen atmosphere for heat treatment including 60 minutes at 120 ℃, 60 minutes at 150 ℃, 30 minutes at 200 ℃, 30 minutes at 250 ℃, 20 minutes at 320 ℃ and 10 minutes at 400 ℃, and the polyimide film was smooth and free of air holes. The obtained polyimide film has the thermal decomposition temperature of 460 ℃, the tensile strength of 120MPa and the 24-hour water absorption capacity of 0.8 percent.
As shown in FIGS. 1 and 2A, the peaks of both polyimide and side chain silane can be seen in the figure without other hetero-peaks, wherein 1785cm-1Is C ═ O asymmetric stretching peak, 1726cm-1Is C ═ O symmetric telescopic peak, 1375cm-1Is an imide C-N stretching vibration peak of 1259cm-1Is CH in silane3Vibration peak of-1095 cm-1And 1021cm-1Is the stretching vibration peak of Si-O-Si, 803cm-1The peak of Si-C stretching vibration indicates that polyimide copolymerized with long side chain siloxane has been synthesized.
Example 2
A glass reaction vessel having a volume of 500mL with a stirrer and an inert gas blanket was charged with 300g of DMF and 100g of chloroform as solvents, 0.2mol of ODA and 0.25mol of PMDA were added thereto, 0.05mol of the silicone-grafted polymer (b) having a chain length of x 10 and y 10 was added thereto, the mixture was completely dissolved by stirring at room temperature, and the mixture was reacted for 10 hours with stirring at 50 ℃ to obtain a polyamic acid solution composition having a solution viscosity of 48.0 pas, and no floc or insoluble matter was formed in the reaction product. The polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good fit with the substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.72.
Sending the steel strip to an extrusion coating machine, coating the polyimide resin liquid on the steel strip through an extrusion die head, and controlling the thickness of the film through a gap at the outlet of the extrusion die head by electronic control; the thickness of the film was 18um, the film was defoamed and predried at 25 ℃ for 30 minutes under reduced pressure, and then placed in a hot air dryer under normal pressure nitrogen atmosphere for heat treatment including 60 minutes at 120 ℃, 60 minutes at 150 ℃, 30 minutes at 200 ℃, 30 minutes at 250 ℃, 20 minutes at 320 ℃ and 10 minutes at 400 ℃, and the polyimide film was smooth and free of air holes. The obtained polyimide film has a thermal decomposition temperature of 470 ℃, a tensile strength of 130MPa and a 24-hour water absorption capacity of 0.8 percent. The atomic force microscope topography of the film microphase separation structure is shown in FIG. 2B.
Example 3
Except that a linear siloxane (a) of x ═ 20 was used and NMP was used with p-xylene 3: 1 (mass ratio) polyimide films were produced in the same manner as in example 1, except that the solvents were mixed. The obtained polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good fit with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.72. The thermal decomposition temperature of the polyimide film is 450 ℃, the tensile strength is 105MPa, and the 24-hour water absorption capacity of the film is 0.8 percent.
Example 4
Except that a waisted siloxane (b) of x-5, y-15 was used and DMAc with chloroform 3: 1 (mass ratio) polyimide film was formed in the same manner as in example 1. The obtained polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good bonding with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.70. The thermal decomposition temperature of the polyimide film is 465 ℃, the tensile strength is 118MPa, and the 24-hour water absorption capacity of the film is 0.8 percent.
Example 5
A polyimide film was formed in the same manner as in example 1, except that 0.1mol of linear siloxane (a) having 0.1mol of PPD and 0.2mol of BPDA and x equal to 20 was used. The obtained polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good fit with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.71. The thermal decomposition temperature of the polyimide film is 430 ℃, the tensile strength is 98MPa, and the 24-hour water absorption capacity of the film is 0.8 percent. The atomic force microscope topography of the thin film microphase separation structure is shown in FIG. 2C.
Example 6
A polyimide film was formed in the same manner as in example 1, except that 0.1mol of the lumbar siloxane (b) was used, i.e., oda0.1mol, pmda0.2mol, x was 5, and y was 15. The obtained polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good bonding with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.70. The thermal decomposition temperature of the polyimide film is 435 ℃, the tensile strength is 108MPa, and the water absorption capacity of the film is 0.8 percent after 24 hours.
Example 7
A polyimide film was formed in the same manner as in example 1, except that 0.1mol of PPD, 0.2mol of BPDA, and 0.1mol of a linear siloxane (a) in which x is 20 was used. The obtained polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good fit with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.72. The thermal decomposition temperature of the polyimide film is 430 ℃, the tensile strength is 98MPa, and the 24-hour water absorption capacity of the film is 0.8 percent.
Example 8
A polyimide film was formed in the same manner as in example 1, except that 0.1mol of the lumbar siloxane (b) was used, i.e., oda0.1mol, pmda0.2mol, x was 5, and y was 15. The obtained polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good bonding with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.69. The thermal decomposition temperature of the polyimide film is 435 ℃, the tensile strength is 108MPa, and the 24-hour water absorption capacity of the film is 0.8 percent.
Example 9
A polyimide film was formed in the same manner as in example 1, except that 0.05mol of a linear siloxane (a) having x of 20, 0.05mol of a lumbar siloxane (b) having x of 5 and y of 15, oda0.1mol and pmda0.2mol were used. The obtained polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good bonding with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.69. The polyimide film has the thermal decomposition temperature of 430 ℃, the tensile strength of 100MPa and the 24-hour water absorption capacity of 0.8 percent.
Example 10
A polyimide film was formed in the same manner as in example 1, except that oda0.1mol and pmda0.2mol were used, and two different long-chain branched siloxanes were used in combination, including 0.05mol of linear siloxane (a) having x equal to 20, 0.05mol of lumbar siloxane (b) having x equal to 5 and y equal to 15. The obtained polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good bonding with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.70. The thermal decomposition temperature of the polyimide film is 430 ℃, the tensile strength is 98MPa, and the 24-hour water absorption capacity of the film is 0.8 percent.
Example 11
A polyimide film was formed in the same manner as in example 1 except that 0.15mol of oda and 0.2mol of pmda0 were used, and the mixture was stirred at 50 ℃ for 6 hours to obtain a PMDA-terminated prepolymer, 0.05mol of a linear siloxane (a) with x being 20 was further added to obtain a high molecular weight polyimide copolymer after 6 hours of reaction. The obtained polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good fit with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.71. The polyimide film had a thermal decomposition temperature of 420 ℃ and a tensile strength of 105MPa, and the film had a water absorption of 0.8% per 24 hours.
Example 12
A polyimide film was formed in the same manner as in example 1 except that 0.1mol of a 20-x lumbar siloxane (b) was added, and the mixture was stirred at 50 ℃ for 6 hours to react with 0.2mol of bpdaa to obtain a PMDA-terminated long-side-chain siloxane prepolymer, and 0.1mol of ppd was added to react for 6 hours to obtain a high-molecular-weight polyimide copolymer. The obtained polyamic acid coating thermal cycle experiment shows that the polyamic acid coating thermal cycle experiment has good fit with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.68. The thermal decomposition temperature of the polyimide film is 418 ℃, the tensile strength is 103MPa, and the 24-hour water absorption capacity of the film is 0.8 percent.
Comparative example 1
400g of NMP as a solvent was added to a glass reaction vessel having a volume of 500mL with a stirrer and under protection of an inert gas, 0.25mol of PPD and 0.25mol of BPDA were added thereto and completely dissolved by stirring at room temperature, and a reaction was carried out at 50 ℃ for 10 hours with stirring to obtain a polyamic acid solution composition having a solution viscosity of 52.0 pas without formation of flocs and insoluble matter in the reaction product. The thermal cycle test of polyamic acid coating shows that obvious cracking is generated between the polyamic acid coating and the substrate, and the thermal shock test shows that the relative internal stress is 0.85.
Sending the steel strip to an extrusion coating machine, coating the polyimide resin liquid on the steel strip through an extrusion die head, and controlling the thickness of the film through a gap at the outlet of the extrusion die head by electronic control; the film thickness was 18um, the coated film was deaerated and pre-dried at 25 ℃ for 30 minutes under reduced pressure, and then placed in a hot air dryer under a normal pressure nitrogen atmosphere to be subjected to heat treatment including 60 minutes at 120 ℃, 60 minutes at 150 ℃, 30 minutes at 200 ℃, 30 minutes at 250 ℃, 20 minutes at 320 ℃ and 10 minutes at 400 ℃, and the polyimide film was flat, smooth and free of air holes. The obtained polyimide film had a thermal decomposition temperature of 480 ℃ and a tensile strength of 220MPa, and a water absorption capacity of 2.1% for 24 hours.
Comparative example 2
400g of NMP as a solvent was added to a glass reaction vessel having a volume of 500mL with a stirrer and under protection of an inert gas, 0.25mol of PMDA and 0.25mol of ODA were added thereto and completely dissolved by stirring at room temperature, and a reaction was carried out at 50 ℃ for 10 hours with stirring to obtain a polyamic acid solution composition having a solution viscosity of 52.0 pas without formation of flocs and insoluble matter in the reaction product. The thermal cycle experiment of polyamic acid coating shows that obvious cracking is generated between the polyamic acid coating and a substrate, and the thermal shock experiment shows that the relative internal stress is 1.
Sending the polyimide resin solution into an extrusion coating machine, coating the polyimide resin solution on a steel belt through an extrusion die head, and controlling the thickness of a film through a gap at the outlet of the extrusion die head by electronic control; the film thickness was 18um, the coated film was deaerated and pre-dried at 25 ℃ for 30 minutes under reduced pressure, and then placed in a hot air dryer under a normal pressure nitrogen atmosphere to be subjected to heat treatment including 60 minutes at 120 ℃, 60 minutes at 150 ℃, 30 minutes at 200 ℃, 30 minutes at 250 ℃, 20 minutes at 320 ℃ and 10 minutes at 400 ℃, and the polyimide film was flat, smooth and free of air holes. The obtained polyimide film had a thermal decomposition temperature of 460 ℃, a tensile strength of 200MPa, and a water absorption capacity of 3.5% for 24 hours.
Comparative example 3
400g of DMF as a solvent was added to a glass reaction vessel having a volume of 500mL with a stirrer and an inert gas blanket, 0.25mol of PMDA and 0.25mol of PPD were added thereto and completely dissolved by stirring at room temperature, and the reaction was carried out at 50 ℃ for 10 hours with stirring to obtain a polyamic acid solution composition having a solution viscosity of 52.0 pas, and no floc or insoluble matter was formed in the reaction product. The thermal cycle test of polyamic acid coating shows that obvious cracking is generated between the polyamic acid coating and the substrate, and the thermal shock test shows that the relative internal stress is 0.9.
Sending the steel strip to an extrusion coating machine, coating the polyimide resin liquid on the steel strip through an extrusion die head, and controlling the thickness of the film through a gap at the outlet of the extrusion die head by electronic control; the thickness of the film was 18um, the film was defoamed and predried at 25 ℃ for 30 minutes under reduced pressure, and then placed in a hot air dryer under normal pressure nitrogen atmosphere for heat treatment including 60 minutes at 120 ℃, 60 minutes at 150 ℃, 30 minutes at 200 ℃, 30 minutes at 250 ℃, 20 minutes at 320 ℃ and 10 minutes at 400 ℃, and the polyimide film was smooth and free of air holes. The obtained polyimide film has the thermal decomposition temperature of 460 ℃, the tensile strength of 120MPa and the 24-hour water absorption capacity of 2.5 percent.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of a polyimide film with side chain grafted with siloxane is characterized by comprising the following steps:
(1) mixing a diamine monomer and a dianhydride monomer according to a molar ratio of 0.9-1.1: 1, adding the mixture into a solvent for polymerization reaction at a reaction temperature of less than 60 ℃, and stirring for 12 hours to prepare slurry;
wherein the diamine monomer comprises diamine monomer containing long side chain siloxane accounting for 1-70% of the total amount of the diamine monomer, and the diamine monomer is m-phenylenediamine terminated polysiloxane
Or polysiloxane waist-linked with m-phenylenediamine
Wherein, the value ranges of x and y are both 3-22, and the values of x and y can be the same or different;
(2) sending the composite slurry prepared in the step (1) into an extrusion coating machine, coating polyimide resin liquid onto a steel belt through an extrusion die head, and controlling the thickness of the film through a gap at the outlet of the electronic control die head; the thickness of the film was 18 um; the coating film was deaerated and predried under reduced pressure at 25 ℃ for 30 minutes;
(3) sending the polyimide film subjected to extrusion coating film formation in the step (2) into an imidizing furnace for imidization treatment, wherein the treatment conditions are as follows: 60 minutes at 120 ℃, 60 minutes at 150 ℃, 30 minutes at 200 ℃, 30 minutes at 250 ℃, 20 minutes at 320 ℃ and 10 minutes at 400 ℃.
2. The method of claim 1, wherein the organic solvent is one or more selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), N-Dimethylformamide (DMF), N-Diethylformamide (DEF), Dimethylacetamide (DMAC), and Dimethylsulfoxide (DMSO).
3. The method for preparing polyimide film with side chain grafted siloxane as claimed in claim 1, wherein the m-phenylenediamine terminated polysiloxane is prepared by the following method:
the polysiloxane with the waist-connected m-phenylenediamine is prepared by the following method:
4. the method of claim 1, wherein the dianhydride monomer is selected from the group consisting of aliphatic dianhydride monomers, alicyclic dianhydride, aromatic dianhydride monomers, and derivatives thereof.
5. The method of claim 4, wherein the dianhydride monomer is one or more selected from pyromellitic dianhydride (PMDA), 4,4 '-diphenyl ether dianhydride (ODPA), 3',4,4 '-Benzophenone Tetracarboxylic Dianhydride (BTDA), 4,4' - (hexafluoroisopropyl) diphthalic anhydride (6FDA), 3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), 1,4,5, 8-naphthalene tetracarboxylic anhydride (NTDA), cyclobutane dianhydride (CBDA), 3,4, 4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), and derivatives thereof.
6. The method of claim 1, wherein the diamine monomer is selected from the group consisting of aliphatic diamine monomers, alicyclic diamine monomers, aromatic diamine monomers, and derivatives thereof.
7. The method of claim 6, wherein the diamine monomer is one or more selected from the group consisting of 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD), 4' -diaminodiphenylmethane (MDA), 4 '-diamino-2, 2' -dimethyl-1, 1 '-biphenyl (m-TB), Benzidine (Benzidine), 2' -bis (trifluoromethyl) diaminobiphenyl (TFMB), 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 2-bis (4-aminophenyl) hexafluoropropane (6FpDA), and derivatives thereof.
8. A side-chain-grafted siloxane polyimide film prepared according to the method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210407318.6A CN114736409B (en) | 2022-04-19 | 2022-04-19 | Polyimide film with side chain grafted with siloxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210407318.6A CN114736409B (en) | 2022-04-19 | 2022-04-19 | Polyimide film with side chain grafted with siloxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114736409A true CN114736409A (en) | 2022-07-12 |
| CN114736409B CN114736409B (en) | 2023-06-30 |
Family
ID=82281124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210407318.6A Active CN114736409B (en) | 2022-04-19 | 2022-04-19 | Polyimide film with side chain grafted with siloxane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114736409B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5298331A (en) * | 1990-08-27 | 1994-03-29 | E. I. Du Pont De Nemours And Company | Flexible multi-layer polyimide film laminates and preparation thereof |
| JPH06329797A (en) * | 1993-05-25 | 1994-11-29 | Dow Corning Corp | Preparation of polyimide with organopolysiloxane side chain |
| US5473041A (en) * | 1993-05-25 | 1995-12-05 | Dow Corning Corporation | Polyimide having organopolysiloxane side chain |
| CN103524768A (en) * | 2013-10-30 | 2014-01-22 | 宏威高新材料有限公司 | Novel electronic-grade polyimide film with low linear expansion coefficient and production method thereof |
| CN104860977A (en) * | 2015-05-18 | 2015-08-26 | 衢州学院 | Silicon-containing aromatic diamine and preparation method thereof |
| CN107189436A (en) * | 2017-07-20 | 2017-09-22 | 中国科学院长春应用化学研究所 | A kind of polyimide nano foam and preparation method thereof |
-
2022
- 2022-04-19 CN CN202210407318.6A patent/CN114736409B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5298331A (en) * | 1990-08-27 | 1994-03-29 | E. I. Du Pont De Nemours And Company | Flexible multi-layer polyimide film laminates and preparation thereof |
| JPH06329797A (en) * | 1993-05-25 | 1994-11-29 | Dow Corning Corp | Preparation of polyimide with organopolysiloxane side chain |
| US5473041A (en) * | 1993-05-25 | 1995-12-05 | Dow Corning Corporation | Polyimide having organopolysiloxane side chain |
| CN103524768A (en) * | 2013-10-30 | 2014-01-22 | 宏威高新材料有限公司 | Novel electronic-grade polyimide film with low linear expansion coefficient and production method thereof |
| CN104860977A (en) * | 2015-05-18 | 2015-08-26 | 衢州学院 | Silicon-containing aromatic diamine and preparation method thereof |
| CN107189436A (en) * | 2017-07-20 | 2017-09-22 | 中国科学院长春应用化学研究所 | A kind of polyimide nano foam and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114736409B (en) | 2023-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108659533B (en) | High-heat-resistance ultralow-expansion polyimide film and preparation method and application thereof | |
| CN105153445B (en) | A kind of method by reactive end-capped with phthalic anhydride resin-made for Kapton | |
| CN109734908B (en) | Polyamide acid and preparation method thereof, polyimide and preparation method of polyimide film | |
| US20100279131A1 (en) | Polyimide film with improved thermal stability | |
| KR102246218B1 (en) | Polyamic acid composition, method for preparing the same and polyimide film comprising the same | |
| CN108794748B (en) | Polyimide film with low dielectric constant and preparation method thereof | |
| CN111019129A (en) | Low-thermal expansion coefficient soluble polyimide resin powder and preparation method thereof | |
| CN112955497A (en) | Ultrathin polyimide film with improved dimensional stability and preparation method thereof | |
| CN113667120B (en) | Polyimide and preparation method thereof | |
| CN103113587A (en) | Flexible hyperbranched semi-interpenetrating fluorinated polysiloxane polyimide film and preparation method thereof | |
| TW200412213A (en) | Polyimide substrates having enhanced flatness, isotropy and thermal dimensional stability, and methods and compositions relating thereto | |
| CN113185693B (en) | Polyamide acid solution and preparation method thereof, polyimide and polyimide film | |
| CN112980014A (en) | Blended polyimide film, preparation method thereof and application thereof in flexible display substrate | |
| CN114891209A (en) | Organosilicon modified polyimide film with low dielectric constant and preparation method thereof | |
| CN114685986A (en) | Polyimide film and preparation method and application thereof | |
| CN108587163B (en) | High-transparency low-expansion polyimide film and preparation method and application thereof | |
| CN114072451B (en) | Polyamic acid composition, method for preparing the same, and polyimide containing the same | |
| CN109054018B (en) | Polyamide acid solution and preparation method thereof | |
| CN114736409B (en) | Polyimide film with side chain grafted with siloxane | |
| CN114230791B (en) | Intrinsic low-dielectric fluorine-containing polyimide film and preparation method thereof | |
| CN115584022A (en) | Polyimide film material containing cage type silsesquioxane and preparation method thereof | |
| KR102246227B1 (en) | Polyamic acid composition, method for preparing the same and polyimide film comprising the same | |
| JPH09227697A (en) | Preparation of heat-resistant polyimide film through gel | |
| KR0141287B1 (en) | Preparation of poly (urethane-imide)block copolymer | |
| CN115109255B (en) | Polyimide, crosslinkable polyimide film, crosslinked polyimide film, and preparation method and application 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 |