CN114736409B - Polyimide film with side chain grafted with siloxane - Google Patents
Polyimide film with side chain grafted with siloxane Download PDFInfo
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Abstract
The invention discloses a polyimide film with side chain grafted siloxane and a preparation method thereof, comprising the steps of adding a copolymer with long side chain siloxane into a reaction system solvent, wherein the number of structural units of the side chain siloxane is 3-20, the content of a comonomer of the long side chain siloxane is 1-70%, and the added siloxane can be a siloxane oligomer with a terminal group of m-phenylenediamine or lumbar grafting m-phenylenediamine. After the diamine monomer connected with benzene rings is arranged on the main chain and the flexible siloxane is arranged on the side chain, a certain amount of siloxane is copolymerized, and the polyimide molecule still has high rigidity and heat resistance. The invention is beneficial to eliminating the internal stress of polyimide film during molding and repeated heating, has good heat shock resistance, is beneficial to reducing the dielectric constant of materials, and improves the gas permeability of the film, and is especially suitable for high-temperature film distillation environments or electrical equipment such as chips, batteries, motors and the like which need repeated temperature rise and fall and are in severe working environments.
Description
Technical Field
The invention belongs to the field of new polymer materials, and particularly relates to a polyimide film with side chain grafted siloxane and a preparation method thereof.
Background
Polyimide is a generic name of a class of high polymer materials with imide bonds in the main chain, and has the most excellent heat resistance in the existing high polymer engineering plastics. Wherein the heat-resistant temperature of the aromatic polyimide can reach more than 500 ℃ and can be used for a long time at more than 300 ℃. In addition, the polyimide material has extremely excellent comprehensive properties 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, polyimide materials still have many disadvantages, such as harsh solvent requirements and only being soluble in strongly polar protic solvents; the coupling of the curing process and the cyclization process occurs simultaneously, and obvious internal stress exists during film curing; the molecular motion capability is weak, and internal stress can be generated when repeatedly heated; the structure is compact, so that the gas permeability is poor, and the material cannot be directly used for high-temperature permeation; the molecule contains 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; the polar groups in the molecules also enable the molecules to have higher dielectric constants, which is unfavorable for the fields of wave transmission, power transmission and transformation and the like. Therefore, aiming at the application scene in the complex environment, the special polyimide variety with the characteristics of water repellency, water resistance, high-temperature ventilation, low dielectric constant and small residual internal stress is required to be developed on the premise of not losing the thermal performance of polyimide.
Polydimethylsiloxane is a high molecular elastomer material with excellent high-low temperature stability. According to different relative molecular masses, the liquid or elastomer silica gel with the appearance from low-viscosity liquid to extremely high-viscosity liquid 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, electrical insulation, low dielectric property 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 skin, medical film auxiliary materials, intelligent sensors, intelligent bandages, wound dressings and the like. The polyimide material can effectively improve the weather resistance, ventilation, dielectric and residual stress removal capacity of the polyimide material by introducing the polyimide material into a polyimide system through copolymerization. However, it is widely studied at present that common diamine monomers such as 4,4' -diaminodiphenyl ether (ODA) are partially replaced by amino-terminated siloxanes to undergo copolycondensation with dianhydride. However, the polyimide material modified by the main chain has obvious defects that the mechanical property of the material is obviously reduced after the main chain is introduced due to the high elasticity of the polydimethylsiloxane, and simultaneously, two components are connected in series on the same main chain, so that a microphase separation structure is not easy to form, and the optimization of the material performance is not facilitated.
Disclosure of Invention
The invention aims to introduce high-quality-fraction polydimethylsiloxane into polyimide by using a side chain grafted siloxane method, and obtain a polyimide film material with a microphase separation structure by using the incompatibility of two components, so that the film has lower internal stress and thermal shock resistance, better gas permeability, lower dielectric property and better water and weather resistance while maintaining heat resistance, and is expected to be used in the fields of gas filtration in complex environments, power transmission line protection, batteries and the like.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation method of polyimide film with side chain grafted siloxane comprises the following steps:
(1) Diamine monomer and dianhydride monomer are mixed according to the mol ratio of 0.9-1.1:1, added into solvent for polymerization reaction, the reaction temperature is lower than 60 ℃, and stirred 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 lumbar m-phenylenediamine polysiloxane->
Wherein, the values of x and y are 3-22, and the values of x and y can be the same or different;
(2) Feeding the composite slurry prepared in the step (1) into an extrusion coater, coating polyimide resin liquid on a steel belt through an extrusion die head, and controlling the thickness of a film through a gap at an outlet of the electronic control die head; the thickness of the film was 18um; deaerating and predrying the coating film at 25 ℃ under reduced pressure for 30 minutes;
(3) Feeding the polyimide film formed by extrusion coating in the step (2) into an imidization furnace for imidization treatment, wherein the treatment conditions are as follows: 120 ℃ for 60 minutes, 150 ℃ for 60 minutes, 200 ℃ for 30 minutes, 250 ℃ for 30 minutes, 320 ℃ for 20 minutes, 400 ℃ for 10 minutes.
Preferably, the organic solvent is one or a combination of several 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 of the lumbar grafting m-phenylenediamine is prepared by the following method:
preferably, the dianhydride monomer is an aliphatic dianhydride monomer, an alicyclic dianhydride, an aromatic dianhydride monomer, or a derivative thereof.
Preferably, the dianhydride monomer is pyromellitic dianhydride (PMDA), 4 '-diphenyl ether dianhydride (ODPA), 3',4 '-Benzophenone Tetracarboxylic Dianhydride (BTDA), 4' - (hexafluoroisopropyl) diphthalic anhydride (6 FDA), 3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), 1,4,5, 8-naphthalene tetracarboxylic anhydride (NTDA), cyclobutane dianhydride (CBDA), 3, 4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), or the like, or a derivative based on the foregoing dianhydrides.
Preferably, the diamine monomer is an aliphatic diamine monomer, a cycloaliphatic 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' -diaminodiphenyl Methane (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 (6 FpDA), etc., or a derivative based on the above diamine.
As another object of the present invention, the present invention provides a polyimide film of side chain grafted siloxane prepared by the above method.
Compared with the prior art, the application has the following beneficial effects:
the polyimide with the side chain grafted with the long siloxane can ensure that the material has similar thermal degradation temperature to that of a non-grafted material, 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 disclosed in the patent can obtain a microphase separation structure under the conditions of lower copolymerization quantity and shorter side chain. The polyimide film has lower internal stress, better dimensional stability, better gas permeability, lower dielectric constant and better hydrophobicity due to the phase separation structure, so that the polyimide film is more suitable for application scenes with requirements of water resistance, insulation, ventilation and the like in environments such as humidity, high voltage and the like in complex environments.
Drawings
FIG. 1 is an infrared spectrum of example 1;
FIGS. 2A-C are atomic force microscope topography of the microphase separated structures of the thin films of example 1, example 2 and example 5, respectively.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention adopts m-phenylenediamine (a) and lumbar grafting m-phenylenediamine (b) at the tail ends as comonomers for introducing long-chain siloxane. Wherein x is the number of repeating units of the polydimethylsiloxane, which can be 3-22, and y is the number of repeating units of the other segment of the lumbar polydimethylsiloxane, which can be 3-22, 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 condensation reaction of chlorosiloxane with phenol (formula a) or addition reaction of silicon hydrogen bond with vinyl (formula b):
(a)
(b)
further, diamine monomers with different siloxane side chains are used as copolymerization units to participate in the synthesis process of dianhydride monomers and diamine monomers, so that the polyimide film containing direct and waist-grafted siloxane long side chains is obtained. The reaction equation for polyimide is as follows:
wherein Ar is dianhydride monomer, which can be aliphatic, alicyclic, aromatic and its derivative, especially when it is aromatic dianhydride, polyimide has high heat resistance. For example, the dianhydride monomer may be pyromellitic dianhydride (PMDA), 4 '-biphenyl ether dianhydride (ODPA), 3',4 '-Benzophenone Tetracarboxylic Dianhydride (BTDA), 4' - (hexafluoroisopropyl) diphthalic anhydride (6 FDA), 3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA), 1,4,5, 8-naphthalene tetracarboxylic anhydride (NTDA), cyclobutane dianhydride (CBDA), 3, 4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), or the like, or a derivative based on the above dianhydride, a partial dianhydride monomer structural formula is as follows:
wherein Ar' is diamine monomer, which can be aliphatic, alicyclic and aromatic diamine and its derivative diamine, especially when diamine monomer is aromatic diamine, polyimide has high heat resistance. For example, the diamine monomer may be one or a combination of several of 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (PPD), 4' -diaminodiphenyl Methane (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 (6 FpDA), etc., or a derivative based on the above diamine, and a partial diamine monomer has the following structural formula:
to obtain a high molecular weight polyimide, the molar ratio of the total amount of the two diamine monomers to the dianhydride monomer should be 0.9 to 1.1:1. Diamine monomer containing long side chain siloxane accounts for 1% -70% of the total amount of diamine monomer. Polyimide films with different siloxane side chain lengths, different siloxane connection modes and different siloxane diamine monomer content have obviously different properties, and can be adjusted according to actual application conditions to obtain an optimal ratio.
Further, the optional organic solvent is one or a combination of several 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 higher (when the siloxane content is more than 50 percent), weak polar solvents such as Toluene (tolene), xylene (Xylene), chloroform (Chloroform), dichloromethane (DCM) and the like can be added into the strong polar solvents, so that the solubility of the system is improved, the boiling point of the blend solvent is reduced, and the curing process is accelerated.
Further, the polymerization reaction is still a two-step reaction, first, a solvent-soluble polyamic acid is prepared, and then polyimide is obtained by thermal imidization. The preparation process of polyamide acid includes adding dianhydride and diamine monomer and mixed solvent at low temperature, and the exothermic reaction is adopted in the reaction, so that the polymerization temperature is controlled to be no higher than 60 deg.c during the material feeding and reaction process to avoid fast temperature raising. Because of the long side chain siloxane, adding a small amount of nonpolar solvent such as chloroform, toluene and the like can increase the reaction stability to prevent the early gelation phenomenon, and the high molecular weight polymer is obtained, and meanwhile, the chain length of the siloxane is not required to be controlled to be too long, or a waist-connected polysiloxane side chain is adopted.
Further, the polyimide film is thermally imidized and cured by a gradual heating procedure, and the temperature is gradually increased from 80 ℃ to more than 400 ℃ through one or more steps. In the heating process, the cyclizing is prevented from being too fast and a large amount of heat is released, and the blending addition of the nonpolar solvent can improve the uniformity of film formation and can make the solvent volatilization process milder. The addition of the weak polar solvent can enhance the nucleophilicity of amino groups on amide bonds, improve the ring closing efficiency and improve the quality of polyimide films.
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 content of the long side chain siloxane, the larger the steric hindrance of the molecule during polycondensation reaction, and the longer the reaction time is required, which also brings about better microphase separation degree and film gas permeability. The waist joint mode has better microphase separation effect than the straight-chain connection mode, and has smaller influence on the activity of polycondensation reaction.
Furthermore, due to the compatibilization effect of the long side chain siloxane, the system is particularly suitable for adding inorganic or organic filling materials to realize the synergistic modification effect, such as improving the rigidity of the film by nano alumina, improving the dielectric property of the film by nano silicon dioxide, improving the heat conduction property of the film by nano boron nitride, improving the antistatic and conductive properties of the film by carbon black, graphene and carbon nano tubes, and the like. Other compounding ingredients may be added according to the application or desired properties, and for example, surfactants, mold release agents, heat stabilizers, lubricants, antistatic agents, brighteners, colorants such as dyes or pigments, conductive agents such as metal powders, surface treatment agents, viscosity modifiers, coupling agents, weather-proofing agents, antioxidants, etc. may be added, and these compounding ingredients may be polymerized together by dissolving them in a monomer in advance, or may be added after obtaining a polyamic acid solution.
Further, the addition of the long side chain polysiloxane increases the fluidity of the polyamic acid solution, and the high fluidity thereof can be used to prepare films and coatings on a substrate using various coating and coating processes and finally to realize the preparation of polyimide films or coatings, for example, film or coating methods such as spray coating, roll coating, spin coating, bar coating, ink-jet, screen printing, slit coating and the like can be suitably employed.
The special physical property experiment performed on the polyimide film in the invention verifies the physical properties such as water resistance, circulation stability and the like, and comprises the following steps: (1) Soaking a polyimide film in deionized water for 24 hours for a water absorption experiment, and measuring weight change before and after water absorption after the polyimide film is soaked in the deionized water for 24 hours; (2) The thermal cycle experiment is carried out, corresponding polyamic acid solution is coated on the surface of a silicon wafer, epoxy resin is used for embedding after solidification, and after repeated circulation for 100 times (30 minutes at (-65 ℃ for 30 minutes) to 30 minutes at 150 ℃) is carried out between high and low temperature, the crack condition of a PI film and a substrate silicon wafer is observed; (3) thermal shock experiment: and placing the chip coated with the polyamide acid resin in a frame, carrying out severe high-low temperature change (-196 ℃ for 2 minutes to 150 ℃ for 2 minutes), observing the bending angle change of the chip, and comparing the bending relative values of the chip and the PMDA-ODA standard sample to obtain the internal stress relative values.
The following detailed description refers to the accompanying drawings.
Example 1
A glass reaction vessel having a volume of 500mL and containing 300g of NMP and 100g of toluene as a solvent was charged under the protection of an inert gas with a stirrer, 0.05mol of a linear siloxane polymer (a) having a chain length of x=10 and 0.2mol of PPD and 0.25mol of BPDA were added thereto, and the mixture was stirred at room temperature to be completely dissolved, and reacted at 50℃for 10 hours to obtain a polyamic acid solution composition having a solution viscosity of 52.0 Pa.s, and no flocculate and insoluble matter were formed in the reaction product. The polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with the substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.7.
Feeding the polyimide resin solution into an extrusion coater, coating the polyimide resin solution onto a steel belt through an extrusion die head, and controlling the thickness of a film through a gap at an outlet of the electronic control die head; the thickness of the film is 18um, the film is defoamed and pre-dried for 30 minutes at 25 ℃ under reduced pressure, then the film is put into a hot air dryer for heating treatment under the condition of normal pressure nitrogen, wherein the heating treatment comprises 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 is smooth and has no air holes. The thermal decomposition temperature of the obtained polyimide film is 460 ℃, the tensile strength is 120MPa, and the water absorption of the film is 0.8% after 24 hours.
As shown in FIGS. 1 and 2A, the peak of polyimide and side chain silane can be seen in the figures, without other hetero peaks, of 1785cm -1 For C=O asymmetric stretching peak, 1726cm -1 For a symmetrical stretching peak of c=o 1375cm -1 Is imide C-N stretching vibration peak, 1259cm -1 Is CH in silane 3 Vibration peak of 1095cm -1 And 1021cm -1 Is Si-O-Si stretching vibration peak of 803cm -1 The polyimide copolymerized with the siloxane having a long side chain has been synthesized, as a Si-C stretching vibration peak.
Example 2
A glass reaction vessel having a volume of 500mL and containing 300g of DMF and 100g of chloroform as a solvent was charged under the protection of an inert gas with a stirrer, 0.05mol of a siloxane lumbar polymer (b) having a chain length of x=10 and y=10 and 0.2mol of ODA and 0.25mol of PMDA were added thereto, and the mixture was stirred at room temperature to be completely dissolved, and the reaction was stirred at 50℃for 10 hours to obtain a polyamic acid solution composition having a solution viscosity of 48.0 Pa.s, and no flocculate and insoluble matter were formed in the reaction product. The polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with the substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.72.
Feeding the polyimide resin solution into an extrusion coater, coating the polyimide resin solution onto a steel belt through an extrusion die head, and controlling the thickness of a film through a gap at an outlet of the electronic control die head; the thickness of the film is 18um, the film is defoamed and pre-dried for 30 minutes at 25 ℃ under reduced pressure, then the film is put into a hot air dryer for heating treatment under the condition of normal pressure nitrogen, wherein the heating treatment comprises 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 is smooth and has no air holes. The thermal decomposition temperature of the obtained polyimide film is 470 ℃, the tensile strength is 130MPa, and the water absorption of the film is 0.8% after 24 hours. The morphology diagram of the atomic force microscope of the thin film microphase separation structure is shown in fig. 2B.
Example 3
Except that x=20 linear siloxane (a) was used and NMP with p-xylene 3: a polyimide film was produced in the same manner as in example 1, except that the solvent mixture was 1 (mass ratio). The obtained polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion 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 water absorption capacity of the film is 0.8% after 24 hours.
Example 4
Except that x=5, y=15 lumbar siloxane (b) was used and DMAc with chloroform 3: a polyimide film was formed in the same manner as in example 1, except that the solvent mixture was 1 (mass ratio). The obtained polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.70. The polyimide film has a thermal decomposition temperature of 465 ℃ and a tensile strength of 118MPa, and the water absorption of the film for 24 hours is 0.8%.
Example 5
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 linear siloxane (a) having x=20 were used. The obtained polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.71. The polyimide film has a thermal decomposition temperature of 430 ℃, a tensile strength of 98MPa and a water absorption capacity of 0.8% in 24 hours. The morphology diagram of the atomic force microscope 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) having an oda of 0.1mol, a pmda of 0.2mol, x=5, and y=15 was used. The obtained polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.70. The polyimide film has a thermal decomposition temperature of 435 ℃, a tensile strength of 108MPa and a water absorption of 0.8% 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 linear siloxane (a) having x=20 were used. The obtained polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.72. The polyimide film has a thermal decomposition temperature of 430 ℃, a tensile strength of 98MPa and a water absorption capacity of 0.8% in 24 hours.
Example 8
A polyimide film was formed in the same manner as in example 1, except that 0.1mol of the lumbar siloxane (b) having an oda of 0.1mol, a pmda of 0.2mol, x=5, and y=15 was used. The obtained polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.69. The polyimide film has a thermal decomposition temperature of 435 ℃, a tensile strength of 108MPa and a water absorption of 0.8% after 24 hours.
Example 9
A polyimide film was formed in the same manner as in example 1, except that 0.05mol of the linear siloxane (a) having x=20, 0.05mol of the lumbar siloxane (b) having x=5, and y=15, and 0.1mol of the oda, the pmda, and the pmda were used. The obtained polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.69. The polyimide film has a thermal decomposition temperature of 430 ℃, a tensile strength of 100MPa and a water absorption of 0.8% after 24 hours.
Example 10
A polyimide film was formed in the same manner as in example 1, except that 0.1mol of oda and 0.2mol of pmda were used, and two different long-chain branched siloxanes were simultaneously used, including 0.05mol of linear siloxane (a) of x=20 and 0.05mol of lumbar siloxane (b) of x=5 and y=15. The obtained polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.70. The polyimide film has a thermal decomposition temperature of 430 ℃, a tensile strength of 98MPa and a water absorption capacity of 0.8% in 24 hours.
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 PMDA were used, the reaction was carried out at 50℃for 6 hours with stirring to obtain a PMDA-terminated prepolymer, 0.05mol of x=20 linear siloxane (a) was added, and the reaction was carried out for 6 hours to obtain a high molecular weight polyimide copolymer. The obtained polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.71. The polyimide film has a thermal decomposition temperature of 420 ℃, a tensile strength of 105MPa and a water absorption of 0.8% after 24 hours.
Example 12
A polyimide film was formed in the same manner as in example 1 except that 0.1mol of lumbar siloxane (b) having an x=20 was added, 0.2mol of BPDA0.2mol was used, the mixture was stirred and reacted at 50℃for 6 hours to obtain a PMDA-terminated long side chain siloxane prepolymer, and PPD was added thereto for 6 hours to obtain a high molecular weight polyimide copolymer. The obtained polyamic acid coating thermal cycle experiment shows that the polyimide coating thermal cycle has good adhesion with a substrate and no crack, and the thermal shock experiment shows that the relative internal stress is 0.68. The polyimide film has a thermal decomposition temperature of 418 ℃, a tensile strength of 103MPa and a water absorption of 0.8% after 24 hours.
Comparative example 1
400g of NMP as a solvent was charged into a glass reaction vessel having a volume of 500mL and a stirrer, and 0.25mol of PPD and 0.25mol of BPDA were added thereto under stirring at room temperature to dissolve them completely, and the reaction was carried out at 50℃for 10 hours under stirring to obtain a polyamic acid solution composition having a solution viscosity of 52.0 Pa.s, and no flocculate and insoluble matter were formed in the reaction product. The polyamic acid coating thermal cycle experiment shows that obvious crack is generated between the polyamic acid coating thermal cycle experiment and the substrate, and the thermal shock experiment shows that the relative internal stress is 0.85.
Feeding the polyimide resin solution into an extrusion coater, coating the polyimide resin solution onto a steel belt through an extrusion die head, and controlling the thickness of a film through a gap at an outlet of the electronic control die head; the thickness of the film is 18um, the film is defoamed and pre-dried for 30 minutes at 25 ℃ under reduced pressure, then the film is put into a hot air dryer for heating treatment under the condition of normal pressure nitrogen, wherein the heating treatment comprises 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 is smooth and has no air holes. The thermal decomposition temperature of the obtained polyimide film is 480 ℃, the tensile strength is 220MPa, and the water absorption capacity of the film is 2.1% after 24 hours.
Comparative example 2
400g of NMP as a solvent was charged into a glass reaction vessel having a volume of 500mL and a stirrer, and 0.25mol of PMDA and 0.25mol of ODA were added thereto under stirring at room temperature to dissolve them completely, and the reaction was carried out at 50℃for 10 hours under stirring to obtain a polyamic acid solution composition having a solution viscosity of 52.0 Pa.s, and no flocculate and insoluble matter were formed in the reaction product. The polyamic acid coating thermal cycle experiment shows that obvious cracking is generated between the polyamic acid coating thermal cycle experiment and the substrate, and the thermal shock experiment shows that the relative internal stress is 1.
Feeding the polyimide resin solution into an extrusion coater, coating the polyimide resin solution onto a steel belt through an extrusion die head, and controlling the thickness of a film through a gap at an outlet of the electronic control die head; the thickness of the film is 18um, the film is defoamed and pre-dried for 30 minutes at 25 ℃ under reduced pressure, then the film is put into a hot air dryer for heating treatment under the condition of normal pressure nitrogen, wherein the heating treatment comprises 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 is smooth and has no air holes. The thermal decomposition temperature of the obtained polyimide film is 460 ℃, the tensile strength is 200MPa, and the water absorption capacity of the film is 3.5% after 24 hours.
Comparative example 3
A glass reaction vessel having a volume of 500mL was charged with 400g of DMF as a solvent under the protection of an inert gas and stirred at room temperature to dissolve PMDA 0.25mol and PPD 0.25mol completely, and the reaction was stirred at 50℃for 10 hours to obtain a polyamic acid solution composition having a solution viscosity of 52.0 Pa.s, and no flocculate and insoluble matter were formed in the reaction product. The polyamic acid coating thermal cycle experiment shows that obvious cracking is generated between the polyamic acid coating thermal cycle experiment and the substrate, and the thermal shock experiment shows that the relative internal stress is 0.9.
Feeding the polyimide resin solution into an extrusion coater, coating the polyimide resin solution onto a steel belt through an extrusion die head, and controlling the thickness of a film through a gap at an outlet of the electronic control die head; the thickness of the film is 18um, the film is defoamed and pre-dried for 30 minutes at 25 ℃ under reduced pressure, then the film is put into a hot air dryer for heating treatment under the condition of normal pressure nitrogen, wherein the heating treatment comprises 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 is smooth and has no air holes. The thermal decomposition temperature of the obtained polyimide film is 460 ℃, the tensile strength is 120MPa, and the water absorption capacity of the film is 2.5% after 24 hours.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. The preparation method of the polyimide film with side chain grafted siloxane is characterized by comprising the following steps:
(1) Diamine monomer and dianhydride monomer are mixed according to the mol ratio of 0.9-1.1:1, added into solvent for polymerization reaction, the reaction temperature is lower than 60 ℃, and stirred 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 containing long side chain siloxane is m-phenylenediamine terminated polysiloxane
Or lumbar m-phenylenediamine polysiloxane->
，
Wherein, the values of x and y are 3-22, and the values of x and y can be the same or different;
(2) Feeding the composite slurry prepared in the step (1) into an extrusion coater, coating polyimide resin liquid on a steel belt through an extrusion die head, and controlling the thickness of a film through a gap at an outlet of the electronic control die head; the thickness of the film was 18um; deaerating and predrying the coating film at 25 ℃ under reduced pressure for 30 minutes;
(3) Feeding the polyimide film formed by extrusion coating in the step (2) into an imidization 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 ℃,10 minutes at 400 ℃;
the m-phenylenediamine terminated polysiloxane is prepared by the following method:
the polysiloxane of the lumbar grafting m-phenylenediamine is prepared by the following method:
2. the method for preparing a polyimide film with side chain grafted siloxane according to claim 1, wherein the solvent is one or a combination of several 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 a polyimide film of side-chain grafted siloxane according to claim 1, wherein the dianhydride monomer is an aliphatic dianhydride monomer, an alicyclic dianhydride monomer, an aromatic dianhydride monomer or derivatives thereof.
4. The method for preparing a polyimide film with side chain grafted siloxane according to claim 3, wherein the dianhydride monomer is pyromellitic dianhydride (PMDA), 4 '-biphenyl ether dianhydride (ODPA), 3',4 '-Benzophenone Tetracarboxylic Dianhydride (BTDA), 4' - (hexafluoroisopropyl) diphthalic anhydride (6 FDA), 3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), 1,4,5, 8-naphthalene tetracarboxylic anhydride (NTDA), cyclobutane dianhydride (CBDA), 3, 4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), or a derivative based on the foregoing dianhydrides.
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| EP0474054B1 (en) * | 1990-08-27 | 1995-12-06 | E.I. Du Pont De Nemours And Company | Flexible multi-layer polyimide film laminates and preparation thereof |
| US5473041A (en) * | 1993-05-25 | 1995-12-05 | Dow Corning Corporation | Polyimide having organopolysiloxane side chain |
| JP3226377B2 (en) * | 1993-05-25 | 2001-11-05 | ダウ・コ−ニング・コ−ポレ−ション | Method for producing polyimide having organopolysiloxane side chain |
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