CN113881225B - Imide film and synthesis method thereof - Google Patents
Imide film and synthesis method thereof Download PDFInfo
- Publication number
- CN113881225B CN113881225B CN202111129127.XA CN202111129127A CN113881225B CN 113881225 B CN113881225 B CN 113881225B CN 202111129127 A CN202111129127 A CN 202111129127A CN 113881225 B CN113881225 B CN 113881225B
- Authority
- CN
- China
- Prior art keywords
- diamine
- dianhydride
- imide film
- imide
- slurry
- 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.)
- Active
Links
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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Abstract
The invention relates to an imide film and a synthesis method thereof. The imide film is prepared by reacting at least one alicyclic diamine and at least one aromatic dianhydride in an aprotic polar solvent to obtain slurry, preparing the obtained slurry into a uniform film by a coating or casting method, and then carrying out gradient heating for high Wen Ya amination to obtain a final product. The imide film has good optical performance and mechanical performance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials and synthetic methods thereof. In particular, the invention relates to an imide film and a synthesis method thereof.
Background
Imide refers to a class of polymers that contain imide rings in the backbone structure. Polyimides have received extensive attention and rapid development because of their excellent combination of properties. The synthesis of the imide is simple and convenient, has a plurality of synthesis ways, and can design the molecular structure and the synthesis scheme according to the requirements. Imide materials are processed in various ways, and can be applied to the aspects of resin, composite materials and the like in various forms such as prepolymer, cured film, powder and the like according to material requirements. The properties of the imide material generally depend on the choice of synthetic monomers and their proportions, the choice of reaction conditions and the choice of process parameters for the post-forming process. The relationship between the three is relatively complex. Typically, when only one condition is changed, the other conditions will also need to be changed accordingly to obtain a final product with better performance. Thus, the development of imide-based products remains a great challenge to the industry today.
From the viewpoint of monomer selection, the imide products known on the market are generally obtained from chain aliphatic diamines and aliphatic/aromatic dianhydrides; or from aromatic diamines and aliphatic/aromatic dianhydrides. The properties of the obtained products often suffer from the fact that, due to the limitations of the reactive monomers themselves, certain aspects are not satisfactory for the application. Thus, in recent years, many enterprises, research institutions and universities have been trying to prepare imide materials using different monomers.
CN105968355a discloses a method for preparing polyimide by using dicyclohexylmethane diamine and pyromellitic dianhydride as reaction raw materials. The method comprises the following steps: a) Dissolving or suspending dianhydride in a weak water-soluble solvent, and gradually adding diamine; or dissolving diamine in a weak water-soluble solvent, and gradually adding dianhydride; then heating and mixing to generate salt to generate a polyimide nylon salt suspension; b) The obtained polyimide nylon salt suspension is filtered, and then the polyimide powder is obtained by intramolecular dehydration of the dried polyimide nylon salt. The weak water-soluble solvent is a ketone solvent with the boiling point of 120-220 ℃, and the solubility in water is less than or equal to 15g/100g of water. The preparation of polyimide by this method requires the diamine and dianhydride to be reacted at about 100c, which is relatively energy-intensive. And the obtained product has higher intrinsic viscosity, which is unfavorable for further molding processing.
CN110862539a discloses a method for preparing polyimide by using 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane and pyromellitic dianhydride as reaction raw materials. The method comprises the following steps: step one, dewatering the monomer and the solvent; step two, synthesizing polyamide acid in an organic solvent system; step three, separating the polyamic acid from the organic solvent; step four, thermal imidization of polyamide acid; and fifthly, recycling the solvent. The invention has the advantages of simple operation, high separation rate of the product and the solvent, high recovery rate of the solvent, energy saving in the imidization process, and the like. However, the invention does not provide any experimental data to demonstrate whether the polyimide obtained by the process can have any synthetic advantages and performance improvements.
It follows that there is still a substantial portion of the prior art that is worthy of further improvement and enhancement. Therefore, there is still a need to study the effect of different reactive monomers on the properties of the final materials and develop a complete set of polymerization conditions and molding processes to obtain imide materials with more excellent properties.
Disclosure of Invention
The invention provides an imide film and a synthesis method thereof, which are used for overcoming the technical defects of overhigh reaction temperature, high product viscosity or ambiguous relation between reaction conditions and product performance in the prior art. The imide film is prepared by reacting at least one alicyclic diamine and at least one aromatic dianhydride in an aprotic polar solvent to obtain slurry, preparing the obtained polyamide slurry into a uniform film by a coating or casting method, and then imidizing at high temperature to obtain a final film product. The imide film material obtained by the method has the characteristics of no color, high transparency, excellent mechanical properties and the like.
The imide film is prepared by reacting at least one alicyclic diamine and at least one aromatic dianhydride in an aprotic polar solvent to obtain polyamide acid slurry, preparing the obtained slurry into a uniform film by a coating or casting method, and then carrying out high-temperature imidization; wherein the at least one cycloaliphatic diamine is as shown in structure (1):
wherein the R group is C n H 2n Or O, n is an integer of 1 to 10, R 1 And R is 2 Selected from alkyl, carboxyl, halogen and independently of each other.
In a preferred embodiment, wherein said at least one cycloaliphatic diamine is as shown in structure (1):
wherein the R group is C n H 2n ，R 1 And R is 2 Selected from alkyl groups and independent of each other.
In a more preferred embodiment, wherein said at least one cycloaliphatic diamine is as shown in structure (1):
wherein the R group is CH 2 ，R 1 And R is 2 Selected from C 1 -C 4 Alkyl groups and are independent of each other.
The cycloaliphatic diamines described herein may be selected from, but are not limited to, dicyclohexylmethane diamine, dicyclohexylethane diamine, dicyclohexylpropane diamine, dicyclohexylbutane diamine, 3 '-dimethyl-4, 4' -diaminodicyclohexylmethane, 3 '-diethyl-4, 4' -diaminodicyclohexylethane, 3 '-diethyl-4, 4' -diaminodicyclohexylpropane, 3 '-diethyl-4, 4' -diaminodicyclohexylbutane, 3 '-diethyl-4, 4' -diaminodicyclohexylmethane 3,3 '-dipropyl-4, 4' -diaminodicyclohexylmethane, 3 '-dibutyl-4, 4' -diaminodicyclohexylmethane, bis (4-aminocyclohexyl) ether, bis (3-methyl-4-aminocyclohexyl) ether, bis (3-ethyl-4-aminocyclohexyl) ether, bis (3-propyl-4-aminocyclohexyl) ether, and bis (3-butyl-4-aminocyclohexyl) ether, and combinations thereof.
In addition, other aliphatic diamine or other cycloaliphatic diamine can be additionally added. The aliphatic diamine or other cycloaliphatic diamine includes, but is not limited to, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 2-methyl-1, 5-pentanediamine (MPD), 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 2-methyl-1, 8-octanediamine, 2, 4-trimethylhexanediamine, 2, 4-trimethylhexanediamine, 5-methyl-1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 2-butyl-2-ethyl-1, 5-pentanediamine, 1, 12-dodecanediamine, 1, 13-tridecanediamine, 1, 14-tetradecanediamine, 1, 16-hexadecanediamine, 1, 18-octadecanediamine, 1, 6-hexanediamine, 2-methyl-1, 5-pentanediamine, 1, 9-nonanediamine, 2-methyl-1, 8-octanediamine, 1, 10-decanediamine and 1, 12-dodecanediamine, 2-methyl-1, 5-pentanediamine, 2-cyclohexane oxide, 2-cyclohexane-2, 2-diaminopropane, 3-cyclohexane, and the like.
If other diamines are added in the present invention, the proportion of other diamines relative to the total diamines is not more than 15% by mole, preferably not more than 10% by mole, more preferably not more than 5% by mole.
As the aromatic tetracarboxylic dianhydride, any known aromatic tetracarboxylic dianhydride can be used in the present invention. Which may be selected from, but is not limited to, pyromellitic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-dihydro-1, 3-dioxo-5-isobenzofuran carboxylic acid-1, 4-phenylene ester, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2-bis (4- (3, 4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2-bis (4- (3, 4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2 '-bis (trifluoromethyl) -4,4' -bis (3, 4-dicarboxyphenoxy) biphenyl dianhydride, and the like, and combinations thereof.
In addition, the present invention may incorporate additional cycloaliphatic tetracarboxylic dianhydrides. It may be selected from, but not limited to, cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 2,3,5, 6-cyclohexane tetracarboxylic dianhydride, 5- (2, 5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic dianhydride, and the like.
If other dianhydrides are added in the present invention, the proportion of other dianhydrides to the total dianhydride is not more than 15% by mole, preferably not more than 10% by mole, more preferably not more than 5% by mole.
In the present invention, the molar ratio of tetracarboxylic dianhydride to diamine is in the range of 0.8 to 1.2. When the molecular weight is within this range, the molecular weight can be increased, and the mechanical properties are excellent. The molar ratio is preferably 0.9 to 1.1, more preferably 0.92 to 1.07.
In the present invention, a blocking agent comprising a monoamine derivative or a carboxylic acid derivative may be added for blocking. Examples of the blocking agent composed of monoamine derivatives include aniline, o-toluidine, m-toluidine, p-toluidine, 2, 3-dimethylaniline, 2, 6-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, o-nitroaniline, p-nitroaniline, m-nitroaniline, o-aminophenol, p-aminophenol, m-aminophenol, o-anisidine, p-anisidine, o-ethoxyaniline, p-ethoxyaniline, o-aminobenzaldehyde, p-aminobenzaldehyde, m-aminobenzaldehyde, o-aminobenzonitrile, p-aminobenzonitrile, m-aminobenzonitrile, aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenyl, 3-aminophenyl ether, 4-aminophenyl ether, 2-aminobenzophenone, 4-aminobenzophenone, 2-aminodiphenyl sulfide, 3-aminodiphenyl sulfide, 4-aminodiphenyl sulfide, 2-amino sulfone, 2-amino-4-diphenyl sulfone, 3-amino-4-1-naphthylamine, 2-1-5-naphthylamine, 2-1-naphthylamine, 2-5-naphthylamine Aromatic monoamines such as 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene. Among them, derivatives of aniline are preferably used. These may be used alone or in combination of 2 or more. As the blocking agent composed of carboxylic acid derivatives, carboxylic anhydride derivatives are mainly mentioned. Examples of the carboxylic anhydride derivatives include aromatic dicarboxylic anhydrides such as phthalic anhydride, 2, 3-benzophenone dicarboxylic anhydride, 3, 4-benzophenone dicarboxylic anhydride, 2, 3-dicarboxyphenyl ether anhydride, 3, 4-dicarboxyphenyl ether anhydride, 2, 3-biphenyl dicarboxylic anhydride, 3, 4-biphenyl dicarboxylic anhydride, 2, 3-dicarboxyphenyl sulfone anhydride, 3, 4-dicarboxyphenyl sulfone anhydride, 2, 3-dicarboxybiphenyl sulfide anhydride, 3, 4-dicarboxybiphenyl sulfide anhydride, 1, 2-naphthalene dicarboxylic anhydride, 2, 3-naphthalene dicarboxylic anhydride, 1, 8-naphthalene dicarboxylic anhydride, 1, 2-anthracene dicarboxylic anhydride, 2, 3-anthracene dicarboxylic anhydride, and 1, 9-anthracene dicarboxylic anhydride. Among these aromatic dicarboxylic anhydrides, phthalic anhydride is preferably used. These may be used alone or in combination of 2 or more.
In the invention, a proper amount of cross-linking agent can be added. The optional crosslinking agent is an aziridine crosslinking agent, an azide crosslinking agent, an isocyanate crosslinking agent, an epoxy crosslinking agent, a diamine crosslinking agent, or a triamine crosslinking agent. When a crosslinking agent is used, the content of the crosslinking agent (relative to the total amount of diamine and dianhydride) is 0.1 to 10% by mole, preferably 0.5 to 8% by mole, and more preferably 1 to 5% by mole.
Another aspect of the present invention relates to a method for producing an imide film. In the present invention, the diamine and dianhydride reactive monomers may be reacted in an aprotic organic solvent. The aprotic organic solvent includes, but is not limited to, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, γ -butyrolactone, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, ethyl acetate, toluene, methyl ethyl ketone, and mixtures of any solvents. Preferably, the present invention employs an aprotic polar organic solvent including N, N-dimethylformamide and N, N-dimethylacetamide.
In general, the concentration of the reaction system may be arbitrarily changed within a wide range. However, the inventors of the present invention have found that in the present invention, if the mass fraction of diamine and dianhydride in the whole reaction system (i.e., the sum of all the reactants, solvents, additives, etc.) is in the range of more than 18% and less than 30%, the resultant reaction product finally gives an imide film having characteristics of colorless, high transparency, excellent mechanical properties, etc. Preferably, the diamine and dianhydride account for more than 20% and less than 25% of the total reaction system by mass.
In the present invention, the diamine and dianhydride react first to form an imide precursor. The imide precursor may be prepared by the following method: the dianhydride and diamine are added to the polar aprotic solvent at a total mass fraction ratio of greater than 18% and less than 30% (more preferably greater than 20% and less than 25%) under nitrogen. Polymerization at a suitable temperature gives a polyamide syrup having a viscosity of 2000-150000cp (more preferably 3000-100000 cp). End capping agents and cross-linking agents may also be added during the reaction.
The reaction temperature for the reaction of diamines and dianhydrides to form the polyamic acid slurry in the prior art typically uses room temperature, i.e., 20-25 ℃. However, the inventors of the present invention have found that if the reaction temperature is controlled in the range of 0 to 20 ℃, more preferably in the range of 5 to 15 ℃, the obtained polyamide acid slurry precursor can be further processed to obtain an imide film excellent in performance.
The obtained imide film has the characteristics of better colorless property, high transparency, excellent mechanical property and the like when being improved by the technology.
In the present invention, the weight average molecular weight of the polyamide acid slurry is preferably 5000 to 100000. The weight average molecular weight herein means a molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard. The weight average molecular weight is more preferably 10000 to 60000, most preferably 15000 to 50000.
Then defoaming the polyamic acid slurry for 0.5-24h, coating the slurry on the surface of a silicon wafer or glass, and then carrying out gradient heating to carry out high Wen Ya amination to obtain the polyimide film. Wherein the gradient heating mode is preferably heating at a heating rate of 1-10 ℃/min for 2-10h at a temperature ranging from 60 ℃ to 500 ℃.
Compared with the prior crosslinking technology, the technical scheme provided by the invention has the following advantages: 1) The high-temperature reaction is not needed in the process of generating the polyamic acid slurry, so that the energy is saved. 2) By controlling the mass fraction of the reactants and the reaction temperature, the obtained polyamide acid slurry can be processed later to produce an imide film with better colorless, high transparency, excellent mechanical properties and the like.
Detailed Description
The following specific examples are given for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
The testing method comprises the following steps:
the viscosity test method of polyamide acid comprises the following steps:
the logarithmic viscosity of the polyamide acid slurry obtained in the production example was measured at 25℃using a candela-Finsk viscometer. The logarithmic viscosity (μ) was determined by the following formula.
μ＝ln(t s /t 0 )/C
t 0 : circulation time of solvent
t s : flow time of polymer dilute solution
C:0.5g/dL
The light transmittance testing method comprises the following steps:
the total light transmittance of the film was measured in percent (%) using a spectrophotometer (COH-400, japan electric color Co., ltd.) over the entire wavelength range of 400 to 700 nm.
Y value (YI) test method:
the yellowness (Yellow Index): YI value) of the optical films obtained in examples and comparative examples was measured using an ultraviolet-visible near-infrared spectrophotometer "V-670" manufactured by Japan Specification (Co., ltd.). After background measurement is performed in a state where no sample is present, an optical film is set in a sample holder, and the light transmittance with respect to 300 to 800nm is measured to obtain a tristimulus value (X, Y, Z), and the YI value is calculated based on the following formula.
YI＝100×(1.2769X-1.0592Z)/Y
Young's modulus test method and tensile strength test method:
the tensile elastic moduli of the optical films obtained in the examples and comparative examples were measured by performing a tensile test under conditions of a test speed of 5 m/min and a load cell of 5kN using an electromechanical universal tester (manufactured by INSTRON corporation) in accordance with jis k 7127.
[ example 1 ]
Preparation of polyamic acid slurry: 6.3111g of dicyclohexylmethane diamine are added under nitrogen to a 250mL three-necked flask equipped with mechanical stirring, followed by 48.36g of anhydrous dimethylacetamide (DMAc). Then stirring was started at a speed of 250rpm. After the dicyclohexylmethane diamine was completely dissolved, the solution temperature was adjusted to 10 ℃. 6.5436g of pyromellitic dianhydride was then added to the reaction system uniformly over 30 minutes. The concentration of the reaction system at this time was about 21% by weight. The mixture was then reacted at 10℃for 24h. Stopping stirring, performing reduced pressure filtration, and vacuumizing and defoaming the filtrate obtained by filtration to obtain thick uniform polyamic acid slurry, wherein the viscosity of the slurry is 82000cp.
Preparation of imide film: the resulting amide acid slurry was knife-coated onto a glass plate having an area of 25cm×25cm, and then the coated amide acid slurry was heated to 270 ℃ at a heating rate of 10 ℃/min, and heating was continued at this temperature for 2 hours. Then, it was cooled to room temperature to obtain an imide film having a thickness of 25. Mu.m.
[ example 2 ]
Preparation of polyamic acid slurry: 7.1526g of 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane are introduced under nitrogen into a 250mL three-necked flask equipped with mechanical stirring, and 51.52g of anhydrous dimethylacetamide (DMAc) are then added. Then stirring was started at a speed of 250rpm. After the dicyclohexylmethane diamine was completely dissolved, the solution temperature was adjusted to 10 ℃. 6.5436g of pyromellitic dianhydride was then added to the reaction system uniformly over 30 minutes. The concentration of the reaction system at this time was about 21% by weight. The mixture was then reacted at 10℃for 24h. Stopping stirring, performing reduced pressure filtration, and vacuumizing and defoaming the filtrate obtained by filtration to obtain thick uniform polyamide acid slurry, wherein the viscosity of the slurry is 39000cp.
Preparation of imide film: the resulting amide acid slurry was knife-coated onto a glass plate having an area of 25cm×25cm, and then the coated amide acid slurry was heated to 270 ℃ at a heating rate of 10 ℃/min, and heating was continued at this temperature for 2 hours. Then, it was cooled to room temperature to obtain an imide film having a thickness of 25. Mu.m.
Comparative example 1
Preparation of polyamic acid slurry: 6.3111g of dicyclohexylmethane diamine was added under nitrogen to a 250mL three-necked flask equipped with mechanical stirring, followed by 94.27g of anhydrous dimethylacetamide (DMAc). Then stirring was started at a speed of 250rpm. After the dicyclohexylmethane diamine was completely dissolved, the solution temperature was adjusted to 10 ℃. 6.5436g of pyromellitic dianhydride was then added to the reaction system uniformly over 30 minutes. The concentration of the reaction system at this time was about 12% by weight. The mixture was then reacted at 10℃for 24h. Stopping stirring, performing reduced pressure filtration, and vacuumizing and defoaming the filtrate obtained by filtration to obtain viscous uniform polyamide acid slurry, wherein the viscosity of the slurry is 6100cp.
Preparation of imide film: the resulting amide acid slurry was knife-coated onto a glass plate having an area of 25cm×25cm, and then the coated amide acid slurry was heated to 270 ℃ at a heating rate of 10 ℃/min, and heating was continued at this temperature for 2 hours. Then, it was cooled to room temperature to obtain an imide film having a thickness of 25. Mu.m.
Comparative example 2
Preparation of polyamic acid slurry: 6.3111g of dicyclohexylmethane diamine are added under nitrogen to a 250mL three-necked flask equipped with mechanical stirring, followed by 48.36g of anhydrous dimethylacetamide (DMAc). Then stirring was started at a speed of 250rpm. After the dicyclohexylmethane diamine was completely dissolved, the solution temperature was adjusted to 10 ℃. 6.5436g of pyromellitic dianhydride was then added to the reaction system uniformly over 30 minutes. The concentration of the reaction system at this time was about 21% by weight. The mixture was then reacted at 25℃for 24h. Stopping stirring, performing reduced pressure filtration, and vacuumizing and defoaming the filtrate obtained by filtration to obtain viscous uniform polyamic acid slurry, wherein the viscosity of the slurry is 26000cp.
Preparation of imide film: the resulting amide acid slurry was knife-coated onto a glass plate having an area of 25cm×25cm, and then the coated amide acid slurry was heated to 270 ℃ at a heating rate of 10 ℃/min, and heating was continued at this temperature for 2 hours. Then, it was cooled to room temperature to obtain an imide film having a thickness of 25. Mu.m.
[ comparative example 3 ]
Preparation of polyamic acid slurry: 7.1526g of 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane are introduced under nitrogen into a 250mL three-necked flask equipped with mechanical stirring, followed by 100.44g of anhydrous dimethylacetamide (DMAc). Then stirring was started at a speed of 250rpm. After the dicyclohexylmethane diamine was completely dissolved, the solution temperature was adjusted to 10 ℃. 6.5436g of pyromellitic dianhydride was then added to the reaction system uniformly over 30 minutes. The concentration of the reaction system at this time was about 12% by weight. The mixture was then reacted at 25℃for 24h. Stopping stirring, performing reduced pressure filtration, and vacuumizing and defoaming the filtrate obtained by filtration to obtain thick uniform polyamide acid slurry, wherein the viscosity of the slurry is 2800cp.
Preparation of imide film: the resulting amide acid slurry was knife-coated onto a glass plate having an area of 25cm×25cm, and then the coated amide acid slurry was heated to 270 ℃ at a heating rate of 10 ℃/min, and heating was continued at this temperature for 2 hours. Then, it was cooled to room temperature to obtain an imide film having a thickness of 25. Mu.m.
[ comparative example 4 ]
Preparation of polyamic acid slurry: 7.1526g of 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane are introduced under nitrogen into a 250mL three-necked flask equipped with mechanical stirring, and 51.52g of anhydrous dimethylacetamide (DMAc) are then added. Then stirring was started at a speed of 250rpm. After the dicyclohexylmethane diamine was completely dissolved, the solution temperature was adjusted to 10 ℃. 6.5436g of pyromellitic dianhydride was then added to the reaction system uniformly over 30 minutes. The concentration of the reaction system at this time was about 21% by weight. The mixture was then reacted at 25℃for 24h. Stopping stirring, performing reduced pressure filtration, and vacuumizing and defoaming the filtrate obtained by filtration to obtain thick uniform polyamide acid slurry, wherein the viscosity of the slurry is 3900cp.
Preparation of imide film: the resulting amide acid slurry was knife-coated onto a glass plate having an area of 25cm×25cm, and then the coated amide acid slurry was heated to 270 ℃ at a heating rate of 10 ℃/min, and heating was continued at this temperature for 2 hours. Then, it was cooled to room temperature to obtain an imide film having a thickness of 25. Mu.m.
The imide films obtained in the above examples and comparative examples were tested for light transmittance, Y value, young's modulus and tensile modulus according to the test methods described above. The test results are shown in the following table.
Table 1:
it follows that the imide films obtained when the diamines used in the present invention are employed and under the reaction and processing conditions defined in the present invention exhibit excellent overall properties.
Claims (3)
1. An imide film which is obtained by reacting at least one alicyclic diamine and at least one aromatic dianhydride in an aprotic polar solvent to obtain a polyamic acid slurry, then forming the obtained slurry into a uniform film by a coating or casting method, and then imidizing at a high temperature, characterized in that
Wherein at least one cycloaliphatic diamine is selected from dicyclohexylmethane diamine or 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane;
wherein at least one aromatic dianhydride is selected from pyromellitic dianhydride;
wherein the total mass fraction of diamine and dianhydride is 21%;
the reaction time is 24 hours;
the imidization condition is that the temperature is increased to 270 ℃ at the heating rate of 10 ℃/min, and the heating is continued for 2h at the temperature;
wherein the reaction temperature of the diamine and the dianhydride to form the polyamic acid slurry is in the range of 0-20 ℃.
2. The imide film of claim 1 wherein the molar ratio of dianhydride to diamine is in the range of 0.8 to 1.2.
3. The imide film of claim 1 wherein the aprotic polar solvent is selected from the group consisting of N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, γ -butyrolactone, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, ethyl acetate, toluene, methyl ethyl ketone, and mixtures of any solvents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111129127.XA CN113881225B (en) | 2021-09-26 | 2021-09-26 | Imide film and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111129127.XA CN113881225B (en) | 2021-09-26 | 2021-09-26 | Imide film and synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113881225A CN113881225A (en) | 2022-01-04 |
| CN113881225B true CN113881225B (en) | 2023-09-29 |
Family
ID=79006760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111129127.XA Active CN113881225B (en) | 2021-09-26 | 2021-09-26 | Imide film and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113881225B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926218A (en) * | 2022-12-05 | 2023-04-07 | 宁波博雅聚力新材料科技有限公司 | Aromatic imide film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585923A (en) * | 2009-03-10 | 2009-11-25 | 东华大学 | Polyimide film with high visible light permeability and preparation thereof |
| CN110862539A (en) * | 2019-11-22 | 2020-03-06 | 哈尔滨工业大学 | Green preparation method of polyimide |
-
2021
- 2021-09-26 CN CN202111129127.XA patent/CN113881225B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585923A (en) * | 2009-03-10 | 2009-11-25 | 东华大学 | Polyimide film with high visible light permeability and preparation thereof |
| CN110862539A (en) * | 2019-11-22 | 2020-03-06 | 哈尔滨工业大学 | Green preparation method of polyimide |
Non-Patent Citations (2)
| Title |
|---|
| 徐樑华 等.《聚丙烯腈基碳纤维》.国防工业出版社,2018,(第1版),第202页. * |
| 陈祥宝.《先进复合材料技术导论》.航空工业出版社,2017,(第1版),第78页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113881225A (en) | 2022-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2000313804A (en) | Substantially colorless transparent polyimide coat and film | |
| CN110591359A (en) | Colorless transparent polyimide film | |
| CN111704735B (en) | Polyimide optical film material with ultralow thermal expansion coefficient and high strength and preparation method thereof | |
| KR101831598B1 (en) | Polyimide resin composition and Film thereof | |
| EP0053927B1 (en) | Polyimide manufacture | |
| CN113185693B (en) | Polyamide acid solution and preparation method thereof, polyimide and polyimide film | |
| JPH10310639A (en) | Colorless transparent polyimide and production thereof | |
| TW201641497A (en) | New tetracarboxylic dianhydride, and polyimide and polyimide copolymer that are obtained from the new tetracarboxylic dianhydride | |
| CN113881225B (en) | Imide film and synthesis method thereof | |
| CN112646183A (en) | Polyimide material and preparation method and application thereof | |
| KR102251518B1 (en) | Polyamic acid, And Polyimide Resin And Polyimide Film | |
| JP6980228B2 (en) | Thermocrosslinkable polyimide, its thermosetting material and interlayer insulating film | |
| KR20180035546A (en) | Polyamic acid, Polyimide, Polyimide Film and Display Device Comprising Thereof and mothod of preparing the Polyamic acid | |
| KR100228722B1 (en) | Novel soluble polyimide resin having alkoxy substituent and its preparation process | |
| CN114573811B (en) | Imide slurry, synthesis method thereof and composition containing imide slurry | |
| CN109666142A (en) | Polyamic acid solution and preparation method and application | |
| CN114085378B (en) | Polyamide acid solution and preparation method thereof, polyimide film and preparation method and application thereof | |
| JPH08225645A (en) | Colorless clear polyimide molding and production thereof | |
| CN114685787B (en) | Polyimide film with synergistic crosslinking structure and preparation method and application thereof | |
| CN116855072A (en) | Soluble polyimide and preparation method and application thereof | |
| JP6994712B2 (en) | Soluble transparent polyimide polymerized in γ-butyrolactone solvent | |
| CN111269421A (en) | Polyamide acid, polyimide film and film preparation method | |
| CN111234223A (en) | Transparent photosensitive polyimide film and preparation method thereof | |
| CN113754886B (en) | Hyperbranched polyimide and preparation method thereof | |
| CN114456381B (en) | Method for preparing polyimide film by unidirectional stretching |
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 |