CN113024807B - Deuterated fluorine-containing polyimide, polyimide precursor, polyimide film, preparation method and application - Google Patents
Deuterated fluorine-containing polyimide, polyimide precursor, polyimide film, preparation method and application Download PDFInfo
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Abstract
The invention discloses a deuterated fluorine-containing polyimide, a polyimide precursor, a polyimide film, a preparation method and application thereof, belonging to the technical field of high polymer materials, wherein the deuterated fluorine-containing polyimide comprises the following repeating units:
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to deuterated fluorine-containing polyimide, a polyimide precursor, a polyimide film, a preparation method and application thereof.
Background
In recent years, with the advent of an advanced information society, development of optical materials such as optical fibers and optical waveguides in the field of optical communications, and liquid crystal alignment films and protective films for color filters in the field of displays has been progressing. Conventional transparent substrate materials generally use a transparent polymer material and glass. Glass cannot meet the development requirements of flexible packaging technology because of its fragile nature, which makes it difficult to handle and process for large and thin applications, and difficult to bend freely. Other transparent polymer materials, such as polycarbonate, polyacrylate, polyethylene terephthalate, polyethersulfone and the like, although having excellent optical transparency, have poor heat resistance, and cannot meet the requirements of high-temperature processes such as electrode film deposition and annealing treatment in the processing process of photoelectric devices.
The colorless transparent polyimide film has excellent properties such as good heat resistance, high light transmittance, low linear thermal expansion coefficient and the like, and has excellent flexibility, and can be used as a transparent substrate material instead of glass. The conventional polyimide film is yellow and has poor optical transmittance, which severely limits the application of the polyimide film in the optical field. The yellow color of polyimide is believed to be caused by intramolecular and intermolecular Charge Transfer Complexes (CTCs) generated by electron withdrawing action in the carbonyl group of the dianhydride residue and electron donating action of the diamine residue alternating in the macromolecular backbone. Thus, the polyimide formed from the diamine having a higher electron donating ability and the dianhydride polymer having a higher electron withdrawing ability has a darker color. Changing the molecular structure reduces or eliminates the formation of charge transfer complexes and allows for the production of polyimide films that are light colored or even colorless. Methods for increasing the transparency of the films have therefore been proposed in succession, for example: fluorine-containing substituent groups or side groups, non-coplanar structures, asymmetric structures, alicyclic structures and other groups are introduced into polymer molecular chains. Studies on the preparation of fluorine-containing polyimides by introducing a fluorine-containing group have been attracting attention, and methods for improving transparency using a semi-alicyclic or full-alicyclic polyimide which does not form a charge transfer complex in principle have also been proposed. However, the introduction of either a fluorine-containing group or a semi-alicyclic structure results in a high linear thermal expansion coefficient of the polyimide film, and a large difference in linear thermal expansion coefficient between the polyimide film and the conductive material, resulting in problems such as an increase in warpage during the formation of a circuit board. In particular, there is a problem that a fine circuit used in a display or the like cannot be easily formed.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a deuterated fluorine-containing polyimide, so as to solve the problems mentioned in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a deuterated fluorine-containing polyimide comprising a repeating unit represented by the following formula I:
wherein X represents a fluorine-containing group having a valence of 4 to 4 having an alicyclic structure and having a carbon number of 4 to 40, and Y represents a deuterated group having a valence of 2 having an aromatic ring and having a carbon number of 6 to 40; the deuterated fluorine-containing polyimide is prepared from a fluorine-containing aliphatic dianhydride monomer and a deuterated aromatic diamine monomer through a polymerization reaction.
Preferably, the structural formula of the fluorine-containing aliphatic dianhydride monomer is any one of the following structural formulas X1-X24:
preferably, the structural formula of the deuterated aromatic diamine monomer is any one of the following structural formulas Y1-Y36:
wherein D (x) represents a benzene ring substituted by x deuterium atoms, and x is an integer of 1 to 4.
Another object of an embodiment of the present invention is to provide a polyimide precursor comprising partially or completely the deuterated fluorine-containing polyimide.
Another object of an embodiment of the present invention is to provide a method for preparing the polyimide precursor, which includes the following steps:
stirring a deuterated aromatic diamine monomer and a polar aprotic solvent under a protective atmosphere to obtain a diamine solution;
and slowly adding a fluorine-containing aliphatic dianhydride monomer into a diamine solution for condensation reaction to obtain the polyimide precursor.
Preferably, the stirring temperature is 0-50 ℃, and the stirring speed is 50-500 rmp; the condensation reaction temperature is 0 to 50 ℃, preferably 5 to 30 ℃.
Another object of an embodiment of the present invention is to provide a polyimide precursor prepared by the above preparation method.
Another object of an embodiment of the present invention is to provide a polyimide film prepared from the polyimide precursor.
Another object of an embodiment of the present invention is to provide a method for preparing a polyimide film, including the following steps:
defoaming the polyimide precursor, coating the polyimide precursor on a substrate, and heating the substrate coated with the polyimide precursor to obtain a polyimide wet film;
and curing the polyimide wet film in a protective atmosphere to form a film, thus obtaining the polyimide film.
In the present invention, the molar ratio of the fluorine-containing aliphatic dianhydride monomer to the deuterated aromatic diamine monomer is preferably 0.90 to 1.10, and more preferably 0.95 to 1.05.
In the invention, the protective atmosphere is selected from helium, nitrogen or argon, and the flow rate is 0.2-5 mL/min.
In the present invention, as the polar aprotic solvent, an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, or N-methyl-2-pyrrolidone, a cyclic ester solvent such as γ -butyrolactone, γ -valerolactone, δ -valerolactone, γ -caprolactone, e-caprolactone, or α -methyl- γ -butyrolactone, a carbonate solvent such as ethylene carbonate or propylene carbonate, a glycol solvent such as triethylene glycol, a phenol solvent such as m-cresol, p-cresol, 3-chlorophenol, or 4-chlorophenol, acetophenone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, or dimethyl sulfoxide is preferably used. In addition, other common organic solvents, that is, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, mineral spirits, naphtha solvents, and the like can also be used. In addition, a plurality of these solvents may be used in combination. The solvent used in the preparation of the polyimide precursor may be used as it is as the solvent for the polyimide precursor.
In the present invention, the solution containing the polyimide precursor has a solid content of 5 to 40% by weight, preferably 10 to 35% by weight, and more preferably 10 to 30% by weight. When the solid content concentration is less than 5wt%, it is uneconomical and the performance after film formation is poor due to the use of a large amount of solvent; when the solid content concentration exceeds 40wt%, the viscosity at room temperature tends to be high, and handling and the like for application to a substrate tend to be difficult.
In the invention, the prepared polyimide precursor solution can be filled into a clean and dry filter for filtration, and the filtered polyimide precursor solution is defoamed by a defoaming machine, vacuum degassing, ultrasonic degassing and the like, or an unstable defoaming agent is added into the polyimide precursor solution and is uniformly stirred for defoaming, wherein the unstable defoaming agent is a defoaming agent which can be decomposed in a heating process, and the defoaming agent can be heated and decomposed in a subsequent heating process and can not remain in a polyimide film.
Alternatively, the degassed polyimide precursor solution may be applied to a substrate, the substrate coated with the polyimide precursor solution may be heated on a heating plate to remove most of the solvent, thereby obtaining a polyimide wet film, and the wet film may be subsequently cured to form a film by stepwise temperature rise in a muffle furnace filled with high-purity nitrogen gas, thereby obtaining a polyimide film.
In the present invention, the filter may be selected from gravity filter, vacuum filter, pressure filter, etc., and most preferably a pressure filter.
In the present invention, the coating method may be selected from spin coating, slit coating, spray coating, blade coating, roll coating, and the like.
In the present invention, the substrate is a substance that can form a coating film by applying a polyimide precursor solution on the surface, and the shape and material are not particularly limited as long as the substrate has a dense structure that is substantially impermeable to liquid and gas. For example: silicon crystal substrate, glass substrate, ceramic substrate, gallium arsenide substrate, stainless steel substrate, and the like.
In the invention, the temperature of the heating plate is preferably 50-150 ℃, and the heating time is preferably 10-30 min. When the temperature of the heating plate is between 50 and 150 ℃, the solvent evaporation rate is slow, and the vacancy generated after the solvent is separated can be filled by the polyimide precursor solution in the time period, if the temperature is too high, the solvent evaporation is too fast, and the vacancy can not be filled, so that the film has defects.
In the present invention, although the viscosity (rotational viscosity) of the polyimide varnish is not limited, the rotational viscosity may be preferably 1000 to 500000cp, more preferably 1000 to 200000cp, as measured by an E-type rotational viscometer at 25 ℃ and a shear rate of 20 sec-1. Further, thixotropy may be imparted as needed. When the viscosity is within the above-mentioned range, the varnish is easy to control in coating and film formation, and the varnish is excellent in leveling property, low in repellency, and thus a film excellent in properties can be obtained.
For the film formed of the polyimide of the present invention, the thickness of the film is preferably 1 to 200. Mu.m, more preferably 1 to 100. Mu.m, more preferably 5 to 50 μm, particularly preferably 5 to 30 μm, although the thickness may vary depending on the use thereof. When the polyimide film is too thick, the light transmittance is low when the polyimide film is used in an application in which light passes through the polyimide film.
In the present invention, the specific stepwise temperature raising process of the muffle furnace is most preferably: raising the temperature from room temperature to 80-100 ℃ at a heating rate of 2.5-3.0 ℃/min, maintaining for 10-20 min, raising the temperature to 200-250 ℃ at a heating rate of 3-3.5 ℃/min, maintaining for 20-30 min, raising the temperature to 300-350 ℃ at a heating rate of 4-5 ℃/min, maintaining for 30-60 min, and naturally cooling to room temperature to obtain the polyimide film.
The polyimide precursor used in the present invention may contain various additives, if necessary. For example, a fine inorganic or organic filler such as fine powdery silica, boron nitride, alumina, and carbon black may be mixed therein, and other ingredients may be further mixed therein as necessary. As other ingredients, a plasticizer, a weather resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant (e.g., a dye and a pigment), a conductive agent (e.g., a metal powder), an antiblocking agent, a surface treatment agent, a viscosity modifier, a coupling agent, a surfactant, or the like may be appropriately blended therein, which may be determined according to the intended use or the desired properties. These components may be previously mixed into the polyimide precursor, or may be added and mixed into the polyimide precursor at the time of use.
Another object of an embodiment of the present invention is to provide a polyimide film prepared by the above preparation method.
Another object of an embodiment of the present invention is to provide an application of the above polyimide film in preparing a transparent substrate material for an optoelectronic device.
According to the technical scheme provided by the embodiment of the invention, the polyimide is prepared by adopting the fluorine-containing alicyclic dianhydride monomer and the deuterated aromatic diamine monomer, fluorine atoms are introduced on the basis of a semi-alicyclic structure, so that the transparency of the polyimide can be improved, C-D bonds in the deuterated structure replace C-H bonds in the traditional polyimide, charge transfer complexes generated in molecules and among molecular chains are reduced, the close accumulation of molecular chains is damaged, the transparency of the polyimide is further improved, and the linear thermal expansion coefficient of the polyimide film is also improved.
In addition, the deuterated fluorine-containing polyimide film prepared by the embodiment of the invention has uniform and moderate film thickness, few defects caused by solvent evaporation in the film and better mechanical property.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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.
Example 1
This embodiment provides a polyimide film having the structural formula:
the fluorine-containing aliphatic dianhydride monomer adopted in the embodiment is X2 in the summary of the invention, the deuterated aromatic diamine monomer is Y1 in the summary of the invention, and the feeding molar ratio of the dianhydride monomer to the diamine monomer is X2: y1=1, and the solid content of the polyimide precursor solution used for preparing the polyimide film was 15wt%.
Specifically, the preparation method of the polyimide film comprises the following steps:
s1, installing a four-mouth reaction bottle filled with high-purity nitrogen in a circulating water bath kettle, wherein the flow rate of the nitrogen is 1.0mL/min, raising the temperature of the water bath kettle to 25 ℃, putting diamine monomer Y1 (0.05mol, 5.6 g) and N-methylpyrrolidone (NMP, 103.95 g) into the reaction bottle through a dry glass funnel to dissolve the diamine monomer Y1 and the N-methylpyrrolidone when the temperature reaches 25 ℃, stirring for 10min, slowly adding dianhydride monomer X2 (0.05mol, 18.01g) into the diamine solution after the diamine monomer is completely dissolved, and flushing the funnel and the medicine residue on the wall of the reaction bottle with 20g of NMP. The reaction was continued at 25 ℃ for 12 hours to obtain a transparent polyimide precursor solution after the reaction was completed.
And S2, filling the polyimide precursor solution into a pressure filter for filtration, putting the filtered slurry into a defoaming machine for defoaming for 2 hours, and then coating the defoamed slurry on a glass plate through a coating machine. And (2) placing the glass plate with the polyimide precursor solution on a heating plate at 80 ℃ for heating for 20min to remove part of the solvent, then placing the glass plate in a muffle furnace filled with high-purity nitrogen, heating from room temperature to 100 ℃ at the heating rate of 3 ℃/min, maintaining for 10min, heating to 250 ℃ at the heating rate of 3.5 ℃/min, maintaining for 20min, heating to 350 ℃ at the heating rate of 5 ℃/min, maintaining for 30min, and finally naturally cooling to room temperature to obtain the transparent polyimide film.
Example 2
This embodiment provides a polyimide film having a structural formula:
the fluorine-containing aliphatic dianhydride monomer adopted in the embodiment is X5 in the summary of the invention, the deuterated aromatic diamine monomer is Y5 in the summary of the invention, and the feeding molar ratio of the dianhydride monomer to the diamine monomer is X5: y5=1, and the solid content of the polyimide precursor solution used for preparing the polyimide film was 15wt%.
Specifically, the preparation method of the polyimide film comprises the following steps:
s1, installing a four-mouth reaction bottle filled with high-purity nitrogen in a circulating water bath kettle, raising the temperature of the water bath kettle to 25 ℃, adding diamine monomer Y5 (0.05mol, 9.61g) and N-methylpyrrolidone (NMP, 146.6 g) into the reaction bottle through a dry glass funnel for dissolving after the temperature reaches 25 ℃, stirring for 10min, slowly adding dianhydride monomer X5 (0.05mol, 19.79g) into a diamine solution, and washing the funnel and the medicine residue on the wall of the reaction bottle by 20g of NMP after the diamine monomer is dissolved completely. The reaction was continued at 25 ℃ for 12 hours to obtain a transparent polyimide precursor solution after the reaction was completed.
And S2, filling the polyimide precursor solution into a pressure filter for filtration, putting the filtered slurry into a defoaming machine for defoaming for 2 hours, and then coating the defoamed slurry on a glass plate through a coating machine. And (2) placing the glass plate with the polyimide precursor solution on a heating plate at 80 ℃ for heating for 20min to remove part of the solvent, then placing the glass plate in a muffle furnace filled with high-purity nitrogen, heating from room temperature to 100 ℃ at the heating rate of 3 ℃/min, maintaining for 10min, heating to 250 ℃ at the heating rate of 3.5 ℃/min, maintaining for 20min, heating to 350 ℃ at the heating rate of 5 ℃/min, maintaining for 30min, and finally naturally cooling to room temperature to obtain the transparent polyimide film.
Example 3
This embodiment provides a polyimide film having a structural formula:
the fluorine-containing aliphatic dianhydride monomer adopted in the embodiment is X7 in the summary of the invention, the deuterated aromatic diamine monomer is Y6 in the summary of the invention, and the feeding molar ratio of the dianhydride monomer to the diamine monomer is X7: y6=1, and the solid content of the polyimide precursor solution used for preparing the polyimide film was 15wt%.
Specifically, the preparation method of the polyimide film comprises the following steps:
s1, installing a four-mouth reaction bottle filled with high-purity nitrogen in a circulating water bath kettle, wherein the flow rate of the nitrogen is 0.8mL/min, raising the temperature of the water bath kettle to 25 ℃, when the temperature reaches 25 ℃, putting diamine monomer Y6 (0.05mol, 10.41g) and NMP (194.88 g) into the reaction bottle through a dry glass funnel for dissolving, stirring for 10min, slowly adding dianhydride monomer X7 (0.05mol, 27.51g) into a diamine solution after the diamine monomer is dissolved, and flushing the funnel and the drug residue on the wall of the reaction bottle by 20g of NMP. The reaction was continued at 25 ℃ for 12 hours to obtain a transparent polyimide precursor solution after the reaction was completed.
And S2, filling the polyimide precursor solution into a pressure filter for filtering, putting the filtered slurry into a defoaming machine for defoaming for 2 hours, and coating the defoamed slurry on a glass plate through a coating machine. Placing the glass plate with the polyimide precursor solution on a heating plate at 80 ℃ to heat for 20min to remove part of the solvent, then placing the glass plate in a muffle furnace filled with high-purity nitrogen, heating the glass plate from room temperature to 100 ℃ at the heating rate of 3 ℃/min, maintaining the temperature for 10min, heating the glass plate to 250 ℃ at the heating rate of 3.5 ℃/min, maintaining the temperature for 20min, heating the glass plate to 350 ℃ at the heating rate of 5 ℃/min, maintaining the temperature for 30min, and finally naturally cooling the glass plate to the room temperature to obtain the transparent polyimide film.
Example 4
This embodiment provides a polyimide film having a structural formula:
the fluorine-containing aliphatic dianhydride monomer adopted in the embodiment is X8 in the invention content, the deuterated aromatic diamine monomer is Y8 in the invention content, and the feeding molar ratio of the dianhydride monomer to the diamine monomer is X8: y8=1, and the solid content of the polyimide precursor solution used for preparing the polyimide film was 15wt%.
Specifically, the preparation method of the polyimide film comprises the following steps:
s1, installing a four-mouth reaction bottle filled with high-purity nitrogen in a circulating water bath kettle, wherein the flow rate of the nitrogen is 1.0mL/min, raising the temperature of the water bath kettle to 25 ℃, when the temperature reaches 25 ℃, putting diamine monomer Y8 (0.05mol, 8.21g) and NMP (189.21 g) into the reaction bottle through a dry glass funnel for dissolving, stirring for 10min, slowly adding dianhydride monomer X8 (0.05mol, 28.71g) into a diamine solution after the diamine monomer is dissolved, and flushing the funnel and the drug residue on the wall of the reaction bottle by 20g of NMP. The reaction was continued at 25 ℃ for 12 hours to obtain a transparent polyimide precursor solution after the reaction was completed.
And S2, filling the polyimide precursor solution into a pressure filter for filtration, putting the filtered slurry into a defoaming machine for defoaming for 2 hours, and then coating the defoamed slurry on a glass plate through a coating machine. Placing the glass plate with the polyimide precursor solution on a heating plate at 80 ℃ to heat for 20min to remove part of the solvent, then placing the glass plate in a muffle furnace filled with high-purity nitrogen, heating the glass plate from room temperature to 100 ℃ at the heating rate of 3 ℃/min, maintaining the temperature for 10min, heating the glass plate to 250 ℃ at the heating rate of 3.5 ℃/min, maintaining the temperature for 20min, heating the glass plate to 350 ℃ at the heating rate of 5 ℃/min, maintaining the temperature for 30min, and finally naturally cooling the glass plate to the room temperature to obtain the transparent polyimide film.
Example 5
This embodiment provides a polyimide film having the structural formula:
the fluorine-containing aliphatic dianhydride monomer adopted in the embodiment is X10 in the summary of the invention, the deuterated aromatic diamine monomer is Y10 in the summary of the invention, and the feeding molar ratio of the dianhydride monomer to the diamine monomer is X10: y10=1, and the solid content of the polyimide precursor solution used for preparing the polyimide film was 20wt%.
Specifically, the preparation method of the polyimide film comprises the following steps:
s1, installing a four-mouth reaction bottle filled with high-purity nitrogen in a circulating water bath kettle, wherein the flow rate of the nitrogen is 1.0mL/min, raising the temperature of the water bath kettle to 25 ℃, when the temperature reaches 25 ℃, putting diamine monomer Y10 (0.05mol, 15.02g) and NMP (155.76 g) into the reaction bottle through a dry glass funnel for dissolving, stirring for 10min, slowly adding dianhydride monomer X10 (0.05mol, 28.92g) into a diamine solution after the diamine monomer is dissolved, and flushing the funnel and the drug residue on the wall of the reaction bottle by 20g of NMP. The reaction was continued at 25 ℃ for 12 hours to obtain a transparent polyimide precursor solution after the reaction was completed.
And S2, filling the polyimide precursor solution into a pressure filter for filtering, putting the filtered slurry into a defoaming machine for defoaming for 2 hours, and coating the defoamed slurry on a glass plate through a coating machine. Placing the glass plate with the polyimide precursor solution on a heating plate at 80 ℃ to heat for 20min to remove part of the solvent, then placing the glass plate in a muffle furnace filled with high-purity nitrogen, heating the glass plate from room temperature to 100 ℃ at the heating rate of 3 ℃/min, maintaining the temperature for 10min, heating the glass plate to 250 ℃ at the heating rate of 3.5 ℃/min, maintaining the temperature for 20min, heating the glass plate to 350 ℃ at the heating rate of 5 ℃/min, maintaining the temperature for 30min, and finally naturally cooling the glass plate to the room temperature to obtain the transparent polyimide film.
Example 6
This embodiment provides a polyimide film having the structural formula:
in this example, the fluorine-containing aliphatic dianhydride monomer in example 1 was replaced with X12 in the summary of the invention, and the deuterated aromatic diamine monomer was replaced with Y14 in the summary of the invention, and the molar ratio was X12: y14=1:1, and a transparent polyimide precursor solution having a solid content of 20wt% was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Example 7
This embodiment provides a polyimide film having a structural formula:
in this example, the fluorine-containing aliphatic dianhydride monomer in example 1 was replaced with X13 in the summary of the invention, and the deuterated aromatic diamine monomer was replaced with Y15 in the summary of the invention, and the molar ratio thereof was X13: y15=1:1, and a transparent polyimide precursor solution having a solid content of 20% by weight was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Example 8
This embodiment provides a polyimide film having a structural formula:
in this example, the fluorine-containing aliphatic dianhydride monomer in example 1 was replaced with X17 in the summary of the invention, and the deuterated aromatic diamine monomer was replaced with Y19 in the summary of the invention, and the molar ratio was X17: y19=1:1, and a transparent polyimide precursor solution having a solid content of 20wt% was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Example 9
This embodiment provides a polyimide film having a structural formula:
in this example, the fluorine-containing aliphatic dianhydride monomer in example 1 was replaced with X19 in the summary of the invention, and the deuterated aromatic diamine monomer was replaced with Y20 in the summary of the invention, and the molar ratio was X19: y20=1:1, and a transparent polyimide precursor solution having a solid content of 25% by weight was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Example 10
This embodiment provides a polyimide film. In this example, the fluorine-containing aliphatic dianhydride monomer in example 1 was replaced with X20 in the summary of the invention, and the deuterated aromatic diamine monomer was replaced with Y22 in the summary of the invention, and the molar ratio was X20: y22=1:1, and a transparent polyimide precursor solution having a solid content of 25% by weight was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Example 11
This embodiment provides a polyimide film having a structural formula:
in this example, the fluorine-containing aliphatic dianhydride monomer in example 1 was replaced with X21 in the summary of the invention, and the deuterated aromatic diamine monomer was replaced with Y25 in the summary of the invention, and the molar ratio was X21: y25=1:1, and a transparent polyimide precursor solution having a solid content of 25% by weight was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Example 12
This embodiment provides a polyimide film having the structural formula:
in this example, the fluorine-containing aliphatic dianhydride monomer in example 1 was replaced with X23 in the summary of the invention, and the deuterated aromatic diamine monomer was replaced with Y31 in the summary of the invention, and the molar ratio thereof was X23: y31=1:1, and a transparent polyimide precursor solution having a solid content of 25% by weight was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Example 13
This embodiment provides a polyimide film. In this example, the fluorine-containing aliphatic dianhydride monomer in example 1 was replaced with X24 in the summary of the invention, and the deuterated aromatic diamine monomer was replaced with Y36 in the summary of the invention, and the molar ratio thereof was X24: y36=0.9:1, the solvent NMP was replaced with ethyl acetate, and a transparent polyimide precursor solution having a solid content of 20wt% was prepared in the same manner as in example 1 and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Example 14
This embodiment provides a polyimide film. In this example, the fluorine-containing aliphatic dianhydride monomer in example 1 was replaced with X15 in the summary of the invention, and the deuterated aromatic diamine monomer was replaced with Y14 in the summary of the invention, and the molar ratio was X15: y14=1.1:1, the solvent NMP was replaced with tetrahydrofuran, and a transparent polyimide precursor solution having a solid content of 20wt% was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Comparative example 1
The comparative example provides a polyimide film having the structural formula:
this comparative example replaces the fluorine-containing aliphatic dianhydride monomer of example 1 with X1 in the summary of the invention and the deuterated aromatic diamine monomer with a non-deuterated aromatic diamine monomer Y1-0 (the only difference between the non-deuterated aromatic diamine monomer Y1-0 and the structure of Y1 in the summary of the invention is that no deuterium substituent D (X) is present), in a molar ratio of X1: y1-0=1:1, and a transparent polyimide precursor solution having a solid content of 15% by weight was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Comparative example 2
The comparative example provides a polyimide film having the structural formula:
this comparative example replaced the fluorine-containing aliphatic dianhydride monomer in example 1 with X5 in the summary of the invention, and the deuterated aromatic diamine monomer with the non-deuterated aromatic diamine monomer Y5-0 (the only difference between the non-deuterated aromatic diamine monomer Y5-0 and the structure of Y5 in the summary of the invention is that no deuterium substituent D (X) is present), in a molar ratio of X5: y5-0=1:1, and a transparent polyimide precursor solution having a solid content of 15wt% was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Comparative example 3
This comparative example provides a polyimide film having the structural formula:
this comparative example replaces the fluorine-containing aliphatic dianhydride monomer of example 1 with X7 in the summary of the invention and the deuterated aromatic diamine monomer with a non-deuterated aromatic diamine monomer Y6-0 (the only difference between the non-deuterated aromatic diamine monomer Y6-0 and the Y6 structure in the summary of the invention is that no deuterium substituent D (X) is present), in a molar ratio of X7: y6-0=1:1, and a transparent polyimide precursor solution having a solid content of 15% by weight was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Comparative example 4
The comparative example provides a polyimide film having the structural formula:
this comparative example replaced the fluorine-containing aliphatic dianhydride monomer in example 1 with X12 in the summary of the invention, and the deuterated aromatic diamine monomer with the non-deuterated aromatic diamine monomer Y14-0 (the only difference between the structure of the non-deuterated aromatic diamine monomer Y14-0 and the structure of Y14 in the summary of the invention is that no deuterium substituent D (X) is present), in a molar ratio of X12: y14-0=1:1, and a transparent polyimide precursor solution having a solid content of 15wt% was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Comparative example 5
This comparative example provides a polyimide film having the structural formula:
this comparative example replaces the fluorine-containing aliphatic dianhydride monomer of example 1 with X17 in the summary of the invention and the deuterated aromatic diamine monomer with a non-deuterated aromatic diamine monomer Y15-0 (the only difference between the non-deuterated aromatic diamine monomer Y15-0 and the Y15 structure in the summary of the invention is that no deuterium substituent D (X) is present), in a molar ratio of X17: y15-0=1:1, and a transparent polyimide precursor solution having a solid content of 15% by weight was prepared in the same manner as in example 1, and cured to form a film in the same manner, to finally obtain a transparent polyimide film.
Experimental example:
the experimental example provides a polyimide film performance test method as follows:
1) 450nm transmittance and average transmittance:
the light transmittance at 450nm and the average light transmittance from 380nm to 780nm of a polyimide film having a thickness of about 10 μm were measured using an ultraviolet-visible spectrophotometer (model TU-1810 PC). The transmittance at 450nm and the average transmittance from 380nm to 780nm of a polyimide film having a thickness of 10 μm were calculated from the transmittance measured at 450nm and the total transmittance measured using the lambert-beer formula under the assumption that the reflectance was 10%.
Log 10 ((T 1 +10)/100)＝10/T×(Log 10 ((T 1 '+10)/100))
Log 10 ((T 2 +10)/100)＝10/T×(Log 10 ((T 2 '+10)/100))
T 1 : light transmittance at 450nm for a 10 μm thick polyimide film, based on the assumption that the reflectance is 10%;
T 1 ': light transmittance at 450 nm;
T 2 : average light transmittance of a polyimide film 10 μm thick based on the assumption that the reflectance is 10%;
T 2 ': average light transmittance (%) from 380nm to 780 nm;
t: thickness (μm) of the polyimide film;
2) Haze:
the haze value (%) of the polyimide film obtained was measured using a haze meter (model TH-100). In measuring the haze of a film, the incident light flux (S) is measured 1 ) And a transmitted light flux (S) 2 ) Instrument scattered luminous flux (S) 3 ) And the scattered luminous flux (S) of the sample 4 ). The calculation formula is as follows: h (%) = [ (S) 4 /S 2 )-(S 3 /S 1 )]*100％。
3) Coefficient of linear thermal expansion (CTE):
a polyimide film about 10 μm thick was cut into a rectangular shape of 13mm by 4mm, and used as a test piece. The test piece was placed in the middle of a jig having a length of 10mm, tested using a TMA4000 thermomechanical expansion analyzer from Perkin Elmer, with a load of about 0.15N applied, and the test piece was heated from 30 ℃ to 400 ℃ in the first stage at a temperature rise rate of 10 ℃/min to 150 ℃ for 30min, in the second stage at a temperature rise rate of 5 ℃/min to 30 ℃ in the third stage at a temperature rise rate of 5 ℃/min, for the main measurement. The linear thermal expansion coefficient thereof was measured at 50 ℃ to 200 ℃.
4) Glass transition temperature (Tg):
a polyimide film about 10 μm thick was prepared as a test sample piece, cut into a rectangular sample of 15mm × 5mm with a knife washed with acetone, and the test piece was heated from room temperature to 500 ℃ at a heating rate of 5 ℃/min in a nitrogen stream using a dynamic thermo-mechanical analyzer (DMA, model Q800) manufactured by usa. The temperature corresponding to the peak value of the damping coefficient (Tan delta) in the energy curve is measured, i.e. the glass transition temperature of the film for this purpose.
5) Tensile Strength (Strength), tensile Modulus (Modulus), elongation at break (Elongation):
a polyimide film having a thickness of 10 μm was prepared as a test sample, cut into a dumbbell shape having a size of 50mm × 4mm by a press die, and the film sample was stretched by a universal testing machine (model: AG-I, shimadzu, kyoto, japan) at a distance of 3mm between clamps and a stretching rate of 2mm/min, and converted into a stress-strain curve from the tensile data to determine tensile strength, tensile modulus and elongation at break from the curve.
The polyimide films obtained in the above examples 1 to 12 and comparative examples 1 to 5 were subjected to the performance test according to the above method, and the test results are shown in the following tables 1 and 2:
TABLE 1
TABLE 2
Examples 1 to 12 are each a polyimide synthesized from a fluorine-containing alicyclic dianhydride monomer and a deuterated aromatic diamine monomer, and comparative examples 1 to 5 are each a polyimide synthesized from a fluorine-containing alicyclic dianhydride monomer and a non-deuterated aromatic diamine monomer. From the test results in tables 1 and 2, it can be found that the deuterated polyimide film has better optical properties, low haze, high transparency, and light transmittance of 450nm of more than 85% compared with the non-deuterated polyimide film. The introduction of fluorine-containing groups in the structure and the semi-alicyclic structure enable the linear thermal expansion coefficient of the polyimide film to be higher, and test results prove that the linear thermal expansion coefficient of the film can be effectively reduced by the deuterated structure, and the glass transition temperature is slightly increased.
It should be noted that, in this specification, the various examples and comparative examples are described in a progressive manner, each example and comparative example focuses on the difference from the other examples and comparative examples, and the same and similar parts between the various examples and comparative examples can be referred to each other.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. A deuterated fluorine-containing polyimide is characterized by comprising a repeating unit shown as the following formula I:
wherein X represents a fluorine-containing group having a valence of 4 to 4 having an alicyclic structure and having a carbon number of 4 to 40, and Y represents a deuterated group having a valence of 2 having an aromatic ring and having a carbon number of 6 to 40; the deuterated fluorine-containing polyimide is prepared by polymerization reaction of a fluorine-containing aliphatic dianhydride monomer and a deuterated aromatic diamine monomer;
the structural formula of the fluorine-containing aliphatic dianhydride monomer is any one of the following structural formulas X2, X5, X7, X8, X10, X12, X13, X17, X19, X20, X21 and X23:
the structural formula of the deuterated aromatic diamine monomer is any one of the following structural formulas Y1, Y5, Y6, Y8, Y10, Y14, Y15, Y19, Y20, Y22, Y25 and Y31:
wherein D (x) represents a benzene ring substituted with x deuterium atoms, and x is an integer of 1 to 4.
2. A polyimide precursor comprising partially or fully a deuterated fluorine-containing polyimide as recited in claim 1.
3. A method for preparing the polyimide precursor according to claim 2, comprising the steps of:
stirring a deuterated aromatic diamine monomer and a polar aprotic solvent under a protective atmosphere to obtain a diamine solution;
and slowly adding a fluorine-containing aliphatic dianhydride monomer into a diamine solution for condensation reaction to obtain the polyimide precursor.
4. A polyimide precursor obtained by the production method according to claim 3.
5. A polyimide film produced from the polyimide precursor according to claim 2 or 4.
6. The preparation method of the polyimide film is characterized by comprising the following steps:
defoaming the solution containing the polyimide precursor according to claim 2 or 4, coating the solution on a substrate, and heating the substrate coated with the polyimide precursor to obtain a polyimide wet film;
and curing the polyimide wet film in a protective atmosphere to form a film, thus obtaining the polyimide film.
7. A polyimide film obtained by the production method according to claim 6.
8. Use of the polyimide film according to claim 5 or 7 for producing a transparent substrate material for an optoelectronic device.
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