CN108659533B - High-heat-resistance ultralow-expansion polyimide film and preparation method and application thereof - Google Patents

High-heat-resistance ultralow-expansion polyimide film and preparation method and application thereof Download PDF

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CN108659533B
CN108659533B CN201810601000.5A CN201810601000A CN108659533B CN 108659533 B CN108659533 B CN 108659533B CN 201810601000 A CN201810601000 A CN 201810601000A CN 108659533 B CN108659533 B CN 108659533B
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polyimide film
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翟磊
白兰
范琳
何民辉
莫松
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Institute of Chemistry CAS
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    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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 a high heat-resistant ultralow-expansion polyimide film, a preparation method and application thereof, belongs to the technical field of polyimide, and solves the problem that the polyimide film in the prior art cannot achieve both low thermal expansion coefficient and good heat resistance, especially cannot achieve both high heat resistance and ultralow expansion coefficient in a wide temperature range. In the high heat-resistant ultralow-expansion polyimide film, the molecular main chain structure of the polyimide contains a linear rigid unit and a polar amide group; the preparation raw materials comprise aromatic dianhydride and diamine with an amide structure. The preparation method comprises the steps of dissolving aromatic diamine in an organic solvent, and adding aromatic dianhydride to obtain polyamide acid homogeneous phase solution; and coating the polyamic acid homogeneous solution, curing, stripping, drying and annealing to obtain the polyimide film. The high heat-resistant ultralow-expansion polyimide film, and the preparation method and the application thereof realize wide application in the fields of electronics, microelectronics, optical display, optical communication and the like, particularly in the field of flexible photoelectricity.

Description

High-heat-resistance ultralow-expansion polyimide film and preparation method and application thereof
Technical Field
The invention relates to the technical field of polyimide, in particular to a high-heat-resistance ultralow-expansion polyimide film and a preparation method and application thereof.
Background
In the fields of photoelectric display, optical communication, and the like, the flexibility, curling, weight reduction, thinning, and wearability of devices are the future development trends. At present, flexible Liquid Crystal Displays (LCDs), flexible organic electroluminescent devices (OLEDs), flexible solar cells, and the like have become hot spots of research. In order to realize the flexibility, lightness and thinness of the photoelectric device, a polymer film with excellent comprehensive performance is required to be searched to replace the traditional hard optical glass substrate.
Polyimide has the characteristics of outstanding heat resistance, mechanical property, insulating property and the like, and is widely applied to the fields of flexible electronics, microelectronics and photoelectricity. However, the conventional polyimide film has a relatively high thermal expansion coefficient, which is generally about 40-80 ppm/DEG C, and cannot meet the performance requirement of the high-precision flexible photoelectric display device on the single-digit thermal expansion of the substrate material. The high coefficient of thermal expansion of polyimide films can cause severe quality problems such as warpage, deformation and cracking of optoelectronic devices. Therefore, the heat resistance and thermal dimensional stability of polyimide-based board materials are greatly challenged.
The existing polyimide film has the problem that the low thermal expansion coefficient and the good heat resistance performance cannot be obtained at the same time, in particular the problem that the high heat resistance and the ultralow expansion coefficient (less than 5ppm/° C) cannot be obtained at a wide temperature range (30-350 ℃).
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a highly heat-resistant ultralow-expansion polyimide film, and a preparation method and an application thereof, so as to solve the problem that the existing polyimide film cannot achieve both low thermal expansion coefficient and good heat resistance, especially the problem that high heat resistance and ultralow expansion coefficient (<5 ppm/DEG C) cannot be achieved within a wide temperature range (30-350 ℃).
The high heat-resistant ultralow-expansion polyimide film provided by the invention is mainly realized by the following technical scheme:
a high heat-resistant ultralow-expansion polyimide film comprises a molecular main chain structure of polyimide, wherein the molecular main chain structure of the polyimide contains a linear rigid unit and a polar amide group; the polyimide film is prepared from the following raw materials: aromatic dianhydrides and diamines having an amide structure.
The high-heat-resistance ultralow-expansion polyimide film disclosed by the invention has the following beneficial effects:
according to the invention, through the molecular structure design, a rigid unit is introduced into a polyimide molecular main chain, so that the molecular main chain of the polyimide is linear rigid, the stacking density of a molecular chain can be effectively improved, and the chain segments are favorably highly oriented in the imidization process, thereby improving the heat resistance of the polyimide film, wherein the heat resistance temperature is above 400 ℃. Meanwhile, the polar amide group is introduced into the main chain of the polyimide molecule, so that the main chain of the polyimide molecule has an amide structure, an intermolecular hydrogen bond effect is easy to form, the molecular chain is regular and arranged in an orientation manner, the movement of the molecular chain can be inhibited in the temperature rise process, and the thermal expansion coefficient of the polyimide film is reduced. The high heat-resistant ultralow-expansion polyimide film disclosed by the invention is low in thermal expansion coefficient and good in heat resistance, and particularly has good high heat resistance and ultralow expansion coefficient (less than 5 ppm/DEG C) in a wide temperature range (30-350 ℃).
On the basis of the scheme, the invention is further improved as follows:
further, the diamine having an amide structure is an aromatic diamine, and the aromatic diamine is N, N '-bis (4-aminophenyl) -terephthalamide, N' -bis (4-amino-2-methylphenyl) -terephthalamide, N '-bis (4-amino-2-methoxyphenyl) -terephthalamide, N' -bis (4-amino-3-methylphenyl) -terephthalamide, N '-bis (4-amino-3-methoxyphenyl) -terephthalamide, N' - (1, 4-phenylene) -bis (4-aminobenzamide), N '- (1, 1' -biphenyl) -4, one or more of 4 '-diaminobenzamide, N' -3,3 '-dimethyl- (1, 1' -biphenyl) -4,4 '-diaminobenzamide, N' -3,3 '-dimethoxy- (1, 1' -biphenyl) -4,4 '-diaminobenzamide, N' -2,2 '-dimethyl- (1, 1-biphenyl) -4, 4' -diaminobenzamide, and N, N '-2, 2' -dimethoxy- (1,1 '-biphenyl) -4, 4' -disubstituted aminobenzamide.
Since the aromatic diamine has a high polarity, the diamine having an amide structure in the present invention is selected as the aromatic diamine. Among a plurality of aromatic diamines, the aromatic diamine has stronger polarity, so that intermolecular hydrogen bond formed in a polyimide main chain has stronger action, the molecular chain arrangement is more regular, the movement of the molecular chain can be more effectively inhibited in the temperature rising process, and the thermal expansion coefficient of the polyimide film is further reduced. Therefore, the present invention selects one or more of the above aromatic diamines to introduce into the main chain of the polyimide molecule.
Further, the aromatic dianhydride is one or more of 1,2,4, 5-pyromellitic dianhydride (PMDA), 2,3,6, 7-naphthalenetetracarboxylic dianhydride (BNDA), 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (s-BPDA), 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride (s-BTDA), and 3,3 ', 4, 4' -diphenylsulfonetetracarboxylic dianhydride (DSDA).
A large number of experiments show that among a plurality of aromatic dianhydrides with linear rigidity, the aromatic dianhydride can effectively improve the stacking density of molecular chains and is more beneficial to high orientation of polyimide chain segments in the imidization process, so that the heat resistance of the polyimide film is further improved. Therefore, the present invention selects one or more of the above aromatic dianhydrides to be incorporated into the main chain of the polyimide molecule.
Further, the polyimide has the general formula I shown below:
Figure BDA0001693206860000031
in the general formula I, n is the number of polymer structural units, Ar is one of the following aromatic structures:
Figure BDA0001693206860000041
r is one of a general formula II or a general formula III shown as follows:
Figure BDA0001693206860000042
in the general formula II, X is H, CH3Or OCH3Y is H, CH3Or OCH3And at least one of X and Y is H;
in the general formula III, the structure of M is selected from any one of the following structures:
Figure BDA0001693206860000043
the invention also provides a preparation method of the high heat-resistant ultralow-expansion polyimide film, which is mainly realized by the following technical scheme:
a preparation method of a high heat-resistant ultralow-expansion polyimide film comprises the following steps:
step 1: under the protection of inert gas, dissolving aromatic diamine in an organic solvent, and adding aromatic dianhydride to obtain polyamide acid homogeneous phase solution;
step 2: coating the polyamide acid homogeneous phase solution on a substrate, curing, stripping and drying to obtain a polyimide film to be treated;
and step 3: and (3) flatly paving the polyimide film to be treated on the substrate, fixing, and annealing to obtain the polyimide film.
The curing comprises the following steps: curing at 60-100 ℃ for 1-2 hours, curing at 180-250 ℃ for 1-2 hours, and curing at 300-350 ℃ for 0.5-1 hour.
A part of the beneficial effects of the preparation method of the high heat-resistant ultralow-expansion polyimide film of the present invention are the same as the beneficial effects of the high heat-resistant ultralow-expansion polyimide film, and are not repeated herein. The other part of the beneficial effects of the preparation method are as follows: the aggregation structure of the polyimide is further regulated and controlled through a curing and annealing process, the content of the ordered structure is increased, and the heat resistance and the thermal dimension stability of the polyimide film are improved. The high-temperature-resistant ultralow-expansion polyimide film prepared by the method has the characteristics of ultralow thermal expansion coefficient and the like in a wide temperature range (30-350 ℃), is flexible and controllable in structure, simple in preparation process, capable of realizing continuous production and good in industrial application value.
In step 1 of the above preparation method, the addition of the aromatic dianhydride is performed at a low temperature because the reaction between the aromatic diamine and the aromatic dianhydride is a polycondensation reaction, a large amount of heat is released during the reaction, and in order to proceed the reaction in the direction of the formation of the polyamic acid, it is necessary to offset the large amount of heat released during the reaction, and therefore, the addition of the aromatic dianhydride in the preparation method of the present invention is performed at a low temperature.
A large number of experiments show that the reaction is most favorably carried out in the direction of generating polyamic acid at the temperature of-10-15 ℃, so that the aromatic dianhydride is added under the low-temperature condition of-10-15 ℃ in the preparation method.
In step 3, the polyimide film to be treated is laid on the substrate and then fixed, so that a certain tensile stress is applied to the film, the thermal stress in the film is eliminated, the aggregation state structure of the polyimide is further regulated, the content of the ordered structure is increased, and the heat resistance and the thermal dimension stability of the polyimide film are improved.
In order to enable the polyamic acid to be completely cured, obtain a polyimide film having not only a low coefficient of thermal expansion, but also good heat resistance, particularly good high heat resistance over a wide temperature range (30-350 ℃), and an ultra-low coefficient of expansion (<5ppm/° c), the above preparation method is finally selected to be cured comprising the following steps, through repeated experiments at different curing temperatures and different curing times: curing at 60-100 ℃ for 1-2 hours, curing at 180-250 ℃ for 1-2 hours, and curing at 300-350 ℃ for 0.5-1 hour.
In the above preparation method, the substrate for coating in step 2 may be any one of a glass plate, a stainless steel plate, a silicon plate, or a polymer resin plate.
Further, the annealing treatment comprises the following steps: at the temperature of 250 ℃ and 300 ℃ for 0.5-1 hour, and at the temperature of 350 ℃ and 400 ℃ for 10-30 minutes.
In the preparation method, the prepared polyimide film is annealed at different temperatures and times, and a large number of experiments show that the polyimide film obtained after the treatment at the temperature of 250-300 ℃ for 0.5-1 hour and the treatment at the temperature of 350-400 ℃ for 10-30 minutes has good comprehensive performance and can not cause serious quality problems of warping, deformation, cracking and the like of a photoelectric device. Therefore, the present invention selects the above annealing process step to prepare the polyimide film.
Further, the solid content of the polyamic acid homogeneous solution is from 10 wt.% to 30 wt.%; the molar ratio of the aromatic diamine to the aromatic dianhydride is (0.95-1.05): 1.
In experiments, when the solid content of the polyamic acid homogeneous solution is too low, the film forming effect is poor or even no film is formed when the polyamic acid homogeneous solution is coated on a substrate; and when the solid content of the polyamic acid homogeneous solution is too high, the solution is too viscous, and the finally prepared polyimide film has poor comprehensive performance. Therefore, in the above production method, the solid content of the polyamic acid homogeneous solution is controlled to 10 wt.% to 30 wt.%.
Further, in step 3, the means for fixing the polyimide film to be processed on the substrate is a means capable of applying a tensile stress to the film. The means for applying tensile stress to the film is illustratively a metal support frame or a glass block.
Further, the organic solvent is one or more of N-methylpyrrolidone (NMP), N '-dimethylacetamide (DMAc), N' -Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclopentanone, and γ -butyrolactone.
The aromatic diamine and the aromatic dianhydride selected by the invention have high solubility in the organic solvent, and molecular chains can be fully stretched, so that the polyamide acid homogeneous phase solution obtained after mixing is uniform and stable, the subsequent preparation steps are convenient to carry out, and the prepared polyimide film has excellent comprehensive performance. Therefore, in the above preparation method, the organic solvent is selected from one or more of N-methylpyrrolidone (NMP), N '-dimethylacetamide (DMAc), N' -Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclopentanone, and γ -butyrolactone.
The high heat-resistant ultralow-expansion polyimide film disclosed by the invention is used as a substrate material and is applied to the fields of electronics, microelectronics, optical display and optical communication.
The high heat-resistant ultralow-expansion polyimide film disclosed by the invention is low in thermal expansion coefficient, good in heat resistance (the heat-resistant temperature is more than 400 ℃), and particularly good in high heat resistance and ultralow expansion coefficient (<5ppm/° C) in a wide temperature range (30-350 ℃), so that the high heat-resistant ultralow-expansion polyimide film disclosed by the invention can be widely applied to the fields of electronics, microelectronics, optical display, optical communication and the like, particularly the field of flexible photoelectricity, such as flexible solar cells, flexible organic electroluminescent displays and the like.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is an infrared spectrum of a polyimide film prepared in examples 1 to 3.
Reference numerals:
1-infrared spectral curve of example 1; 2-infrared spectral curve of example 2; 3-infrared spectral curve of example 3.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The following examples select representative aromatic diamine and aromatic dianhydride monomers to prepare high temperature resistant ultra-low expansion polyimide films with different main chain structures, the diamine and/or dianhydride monomers in the examples are replaced by other diamine and/or dianhydride monomers described in the disclosure of the invention, and the prepared homopolymerization type or copolymerization type polyimide films have the same and similar effects as the embodiments by adopting the preparation method and conditions described in the disclosure of the invention.
In the present invention, the percentage content and the percentage concentration are both the mass percentage content and the mass percentage concentration unless otherwise specified. The starting materials are commercially available from published sources unless otherwise specified. In the embodiment, the thickness of the polyimide film can be regulated and controlled by adjusting the type of the coating roller and the solid content of the polyamic acid homogeneous solution.
Example 1
(1) Under the protection of inert gas, 17.30 g (0.05 mol) of N, N '-bis (4-aminophenyl) -terephthalamide and 110 g of N-methylpyrrolidone (NMP) are added into a three-neck flask which is provided with a mechanical stirring device, a nitrogen inlet and a nitrogen outlet and a thermometer, and stirred at room temperature until the N, N' -bis (4-aminophenyl) -terephthalamide and the NMP are completely dissolved; the system is cooled to-10 ℃ and 10.91 g (0.05 mol) of 1,2,4, 5-pyromellitic dianhydride is added, and the mixture is stirred for 24 hours at low temperature after being completely dissolved, so that homogeneous polyamic acid homogeneous solution with the viscosity of 20000cP and the solid content of about 20 wt.% is obtained.
(2) And (2) filtering and vacuum defoaming the polyamide acid homogeneous solution obtained in the step (1), coating the polyamide acid homogeneous solution on a dry glass plate with a smooth and flat surface, placing the glass plate in an oven, and heating and curing the glass plate in a nitrogen atmosphere, wherein the heating and curing are performed at 60 ℃/2 hours, 180 ℃/1 hour and 350 ℃/1 hour. And then cooling to room temperature, soaking the substrate in deionized water, automatically stripping the film, and drying in an oven.
(3) Flatly paving the dried film obtained in the step (2) on a substrate, fixing the film by adopting a metal support frame, placing the film in a high-temperature oven, and gradually heating the film to 250 ℃/1 hour and 350 ℃/10 minutes to finish annealing treatment of the film; then cooling to room temperature to prepare the final polyimide film.
The main properties of the polyimide film prepared in this example are shown in table 1. Infrared analysis data (FT-IR, cm-1) of the film were as follows: 3307, 1775, 1710, 1648, 1511, 1370, 1312, 1242, 719.
Example 2
(1) Under the protection of inert gas, 17.79 g (0.0475 mol) of N, N ' -bis (4-amino-2-methylphenyl) -terephthalamide and 290 g of N, N ' -dimethylacetamide (DMAc) are added into a three-neck flask with a mechanical stirring device, a nitrogen inlet and a nitrogen outlet and a thermometer, and stirred at room temperature until the N, N ' -dimethylacetamide (DMAc) is completely dissolved; the system is cooled to the temperature of minus 5 ℃, 14.71 g (0.05 mol) of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride is added, and the mixture is stirred for 15 hours at low temperature after being completely dissolved, so that homogeneous polyamic acid homogeneous solution with the viscosity of 13000cP and the solid content of about 10 wt.% is obtained.
(2) Filtering and vacuum defoaming the polyamic acid homogeneous solution obtained in the step (1), coating the polyamic acid homogeneous solution on a dry glass plate with a smooth and flat surface, placing the glass plate in an oven, and heating and curing the glass plate in a nitrogen atmosphere, wherein the heating and curing are specifically 80 ℃/1.5 hours, 200 ℃/2 hours and 350 ℃/1 hour. And then cooling to room temperature, soaking the substrate in deionized water, automatically stripping the film, and drying in an oven.
(3) Flatly paving the dried film obtained in the step (2) on a substrate, fixing the film by adopting a metal support frame, placing the film in a high-temperature oven, and gradually heating the film to 250 ℃/1 hour and 350 ℃/20 minutes to finish annealing treatment of the film; then cooling to room temperature to prepare the final polyimide film.
The main properties of the polyimide film prepared in this example are shown in table 1. Infrared analysis data (FT-IR, cm-1) of the film were as follows: 3289, 2924, 1771, 1709, 1658, 1613, 1503, 1367, 1305, 1090, 736.
Example 3
(1) 18.17 g (0.0525 mol) of N, N' - (1, 4-phenylene) -bis (4-aminobenzamide) and 150 g of N-methylpyrrolidone (NMP) are added to a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet and outlet and a thermometer under the protection of inert gas, and stirred at room temperature until completely dissolved; the system is cooled to 0 ℃ at low temperature, 14.71 g (0.05 mol) of 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is added, and the mixture is stirred at low temperature for 12 hours after being completely dissolved, so that homogeneous polyamic acid homogeneous solution with viscosity of 16500cP and solid content of about 18 wt.% is obtained.
(2) Filtering and vacuum defoaming the polyamic acid homogeneous phase solution obtained in the step (1), coating the polyamic acid homogeneous phase solution on a dry stainless steel plate with a smooth and flat surface, placing the dry stainless steel plate in an oven, and heating and curing the solution in a nitrogen atmosphere, wherein the heating and curing are performed at 100 ℃/1 hour, 250 ℃/1 hour and 350 ℃/0.5 hour. And then cooling to room temperature, soaking the substrate in deionized water, automatically stripping the film, and drying in an oven.
(3) Flatly paving the dried film obtained in the step (2) on a substrate, fixing the film by adopting a glass block, placing the film in a high-temperature oven, and gradually heating the film to 300 ℃/0.5 hour and 400 ℃/15 minutes to finish annealing treatment of the film; then cooling to room temperature to prepare the final polyimide film.
The main properties of the polyimide film prepared in this example are shown in table 1. Infrared analysis data (FT-IR, cm-1) of the film were as follows: 3321, 1773, 1708, 1647, 1606, 1512, 1361, 1311, 1064, 735.
Example 4
(1) Under the protection of inert gas, 21.11 g (0.05 mol) of N, N ' - (1,1 ' -biphenyl) -4,4 ' -diaminobenzamide and 210 g of N, N ' -Dimethylformamide (DMF) are added into a three-neck flask which is provided with a mechanical stirring device, a nitrogen inlet and a nitrogen outlet and a thermometer, and stirred at room temperature until the N, N ' -diaminobenzamide and the DMF are completely dissolved; the system is cooled to 5 ℃ and 16.10 g (0.05 mol) of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride is added, and the mixture is stirred for 30 hours at low temperature after being completely dissolved, so that homogeneous polyamic acid homogeneous solution with viscosity of 12800cP and solid content of about 15 wt.% is obtained.
(2) And (2) filtering and vacuum defoaming the polyamic acid homogeneous solution obtained in the step (1), coating the polyamic acid homogeneous solution on a dry stainless steel plate with a smooth and flat surface, placing the dry stainless steel plate in an oven, and heating and curing the solution in a nitrogen atmosphere, wherein the heating and curing are specifically 80 ℃/2 hours, 200 ℃/1 hour and 330 ℃/1 hour. And then cooling to room temperature, soaking the substrate in deionized water, automatically stripping the film, and drying in an oven.
(3) Flatly paving the dried film obtained in the step (2) on a substrate, fixing the film by adopting a metal support frame, placing the film in a high-temperature oven, gradually heating to 250 ℃/0.5 hour, and finishing film annealing treatment at 380 ℃/30 minutes; then cooling to room temperature to prepare the final polyimide film.
The main properties of the polyimide film prepared in this example are shown in table 1.
Example 5
(1) Under the protection of inert gas, 22.90 g (0.0475 mol) of N, N '-3, 3' -dimethoxy- (1,1 '-biphenyl) -4, 4' -diaminobenzamide and 206 g of N, N '-Dimethylformamide (DMF) are added into a three-neck flask which is provided with a mechanical stirring device, a nitrogen inlet and a nitrogen outlet and a thermometer, and stirred at room temperature until the N, N' -diaminobenzamide and the DMF are completely dissolved; the system is cooled to 15 ℃ and 13.41 g (0.05 mol) of 2,3,6, 7-naphthalene tetracarboxylic dianhydride (BNDA) is added, and the mixture is stirred for 20 hours at low temperature after being completely dissolved, so that homogeneous polyamic acid homogeneous solution with the viscosity of 13700cP and the solid content of about 15 wt.% is obtained.
(2) And (2) filtering and vacuum defoaming the polyamic acid homogeneous solution obtained in the step (1), coating the polyamic acid homogeneous solution on a dry polymer resin plate with a smooth and flat surface, placing the polyamic acid homogeneous solution in an oven, and heating and curing the polyamic acid homogeneous solution in a nitrogen atmosphere at a temperature of 90 ℃/2 hours, 220 ℃/1 hour and 350 ℃/1 hour. And then cooling to room temperature, soaking the substrate in deionized water, automatically stripping the film, and drying in an oven.
(3) Flatly paving the dried film obtained in the step (2) on a substrate, fixing the film by adopting a metal support frame, placing the film in a high-temperature oven, and gradually heating to 280 ℃/1 hour and 350 ℃/20 minutes to finish annealing treatment of the film; then cooling to room temperature to prepare the final polyimide film.
The main properties of the polyimide film prepared in this example are shown in table 1.
Example 6
(1) 22.60 g (0.05 mol) of N, N '-2, 2' -dimethyl- (1, 1-biphenyl) -4,4 '-diaminobenzamide and 95 g of N, N' -dimethylacetamide (DMAc) are added into a three-neck flask with a mechanical stirring, a nitrogen inlet and outlet and a thermometer under the protection of inert gas, and stirred at room temperature until the N, N '-diaminobenzamide and the N, N' -dimethylacetamide (DMAc) are completely dissolved; the system is cooled to 8 ℃ and 17.90 g (0.05 mol) of 3,3 ', 4, 4' -diphenylsulfone tetracarboxylic dianhydride is added, and the mixture is stirred at low temperature for 36 hours after being completely dissolved, so that a homogeneous polyamic acid homogeneous solution with 18300cP and about 30 wt.% of solid content is obtained.
(2) And (2) filtering and vacuum defoaming the polyamic acid homogeneous solution obtained in the step (1), coating the polyamic acid homogeneous solution on a dry polymer resin plate with a smooth and flat surface, placing the polyamic acid homogeneous solution in an oven, and heating and curing the polyamic acid homogeneous solution in a nitrogen atmosphere, wherein the heating and curing are performed at 100 ℃/1.5 hours, 200 ℃/1.5 hours and 300 ℃/1 hour. And then cooling to room temperature, soaking the substrate in deionized water, automatically stripping the film, and drying in an oven.
(3) Flatly paving the dried film obtained in the step (2) on a substrate, fixing the film by adopting a glass block, placing the film in a high-temperature oven, and gradually heating the film to 300 ℃/1 hour and 400 ℃/10 minutes to finish annealing treatment of the film; then cooling to room temperature to prepare the final polyimide film.
The main properties of the polyimide film prepared in this example are shown in table 1.
Example 7
(1) Under the protection of inert gas, 8.66 g (0.025 mol) of N, N '-bis (4-aminophenyl) -terephthalamide and 10.55 g (0.025 mol) of N, N' - (1,1 '-biphenyl) -4, 4' -diaminobenzamide and 90 g of N-methylpyrrolidone/cyclopentanone (volume ratio 1:1) were added to a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet and a thermometer, and stirred at room temperature until completely dissolved; the system is cooled to 10 ℃ and 10.91 g (0.05 mol) of 1,2,4, 5-pyromellitic dianhydride is fully dissolved and stirred for 20 hours at low temperature to obtain homogeneous polyamic acid homogeneous solution with viscosity of 16400cP and solid content of about 25 wt.%.
(2) Filtering and vacuum defoaming the polyamic acid homogeneous solution obtained in the step (1), coating the polyamic acid homogeneous solution on a dry stainless steel plate with a smooth and flat surface, placing the dry stainless steel plate in an oven, and heating and curing the solution in a nitrogen atmosphere, wherein the heating and curing are performed at 100 ℃/1 hour, 230 ℃/2 hours and 350 ℃/0.5 hour. And then cooling to room temperature, soaking the substrate in deionized water, automatically stripping the film, and drying in an oven.
(3) Flatly paving the dried film obtained in the step (2) on a substrate, fixing the film by adopting a glass block, placing the film in a high-temperature oven, and gradually heating to 260 ℃/40 minutes and 400 ℃/20 minutes to finish film annealing treatment; then cooling to room temperature to prepare the final polyimide film.
The main properties of the polyimide film prepared in this example are shown in table 1.
Example 8
(1) 22.51 g (0.05 mol) of a mixed solution of N, N ' -3,3 ' -dimethyl- (1,1 ' -biphenyl) -4,4 ' -diaminobenzamide and 140 g of N, N ' -dimethylformamide/gamma-butyrolactone (volume ratio is 2:1) are added into a three-neck flask which is provided with a mechanical stirring device, a nitrogen inlet and a nitrogen outlet and a thermometer under the protection of inert gas, and the mixed solution is stirred at room temperature until the mixed solution is completely dissolved; cooling the system to 0 ℃, adding 6.55 g (0.03 mol) of 1,2,4, 5-pyromellitic dianhydride and 5.88 g (0.02 mol) of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, completely dissolving, and stirring at low temperature for 18 hours to obtain a homogeneous polyamic acid homogeneous solution with viscosity of 15800cP and solid content of about 20 wt.%.
(2) And (2) filtering and vacuum defoaming the polyamide acid homogeneous phase solution obtained in the step (1), coating the polyamide acid homogeneous phase solution on a dry stainless steel plate with a smooth and flat surface, placing the stainless steel plate in an oven, and heating and curing the polyamide acid homogeneous phase solution in a nitrogen atmosphere, wherein the heating and curing are 60 ℃/2 hours, 180 ℃/1.5 hours and 320 ℃/1 hour. And then cooling to room temperature, soaking the substrate in deionized water, automatically stripping the film, and drying in an oven.
(3) Flatly paving the dried film obtained in the step (2) on a substrate, fixing the film by adopting a metal support frame, placing the film in a high-temperature oven, and gradually heating to 260 ℃/1 hour and 380 ℃/30 minutes to finish film annealing treatment; then cooling to room temperature to prepare the final polyimide film.
The main properties of the polyimide films prepared in the respective examples are shown in table 1.
TABLE 1 Main Properties of polyimide films
Figure BDA0001693206860000141
Note: a negative coefficient of thermal expansion indicates shrinkage of the polyimide film during the test.
a apparent viscosity of Polyamic acid measured with a Brookfield rotational viscometer at a test temperature of 25 ℃.
b thermal dimensional stability of the film was measured using a static mechanical analyzer (TMA) in a nitrogen atmosphere.
And c, measuring the heat resistance of the film by using a dynamic analyzer (DMA) in a nitrogen atmosphere.
d thermal decomposition temperature of the film was measured by thermogravimetric analysis (TGA) under nitrogen atmosphere, T5％Is the temperature at 5% weight loss.
Table 1 shows the main heat resistance and the like of the homopolymeric and copolymeric polyimide films prepared in the above examples 1 to 8, which specifically include: coefficient of linear thermal expansion (CTE) and glass transition temperature (T) of the film in a normal temperature range (50-200 ℃) and a wide temperature range (30-350 ℃), andg) 5% weight loss thermal decomposition temperature (T)5％) And the like. As can be seen from Table 1, in examples 1 to 8, by using the method of the present invention, the prepared polyimide film had a coefficient of linear thermal expansion of-0.58 to 3.77 ppm/deg.C in the normal temperature range (50 to 200 deg.C), a coefficient of linear thermal expansion of-2.60 to 4.41 ppm/deg.C in the wide temperature range (30 to 350 deg.C), and absolute values of the coefficients of thermal expansion were all less than 5, indicating that the polyimide film of the present invention has an ultra-low coefficient of thermal expansion, excellent heat resistance, a glass transition temperature of 436 deg.C or higher, and a thermal decomposition temperature of 489 deg.C or higher. Therefore, the polyimide film containing the rigid structure and the amide group in the molecular main chain has excellent heat resistance and ultralow thermal expansion coefficient in a wide temperature range, and can be applied to the fields of flexible photoelectricity and the like.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (9)

1. A high heat-resistant ultralow-expansion polyimide film is characterized in that a molecular main chain structure of polyimide contains a linear rigid unit and a polar amide group; the polyimide film is prepared from raw materials including aromatic dianhydride and diamine with an amide structure; the polyimide film is obtained by fixing and annealing treatment, wherein the annealing treatment comprises the following steps: treating at 250-300 deg.c for 0.5-1 hr and treating at 350-400 deg.c for 10-30 min;
the heat-resistant temperature of the polyimide film is above 400 ℃, and the absolute value of the thermal expansion coefficient within the range of 30-350 ℃ is less than 5 ppm/DEG C;
the polyimide has the general formula I shown below:
Figure FDA0002375242570000011
in the general formula I, n is the number of polymer structural units, Ar is one of the following aromatic structures:
Figure FDA0002375242570000012
r is one of a general formula II or a general formula III shown as follows:
Figure FDA0002375242570000013
in the general formula II, X is H, CH3Or OCH3Y is H, CH3Or OCH3And at least one of X and Y is H;
in the general formula III, the structure of M is selected from any one of the following structures:
Figure FDA0002375242570000021
2. the highly heat-resistant ultralow expansion polyimide film according to claim 1, wherein said diamine having an amide structure is an aromatic diamine, and said aromatic diamine is N, N '-bis (4-aminophenyl) -terephthalamide, N' -bis (4-amino-2-methylphenyl) -terephthalamide, N '-bis (4-amino-2-methoxyphenyl) -terephthalamide, N' -bis (4-amino-3-methylphenyl) -terephthalamide, N '-bis (4-amino-3-methoxyphenyl) -terephthalamide, N' - (1, 4-phenylene) -bis (4-aminobenzamide); or a salt thereof, One or more of N, N '- (1, 1' -biphenyl) -4,4 '-diaminobenzamide, N' -3,3 '-dimethyl- (1, 1' -biphenyl) -4,4 '-diaminobenzamide, N' -3,3 '-dimethoxy- (1, 1' -biphenyl) -4,4 '-diaminobenzamide, N' -2,2 '-dimethyl- (1, 1-biphenyl) -4, 4' -diaminobenzamide, and N, N '-2, 2' -dimethoxy- (1,1 '-biphenyl) -4, 4' -disubstituted aminobenzamide.
3. The highly heat-resistant ultralow expansion polyimide film according to claim 1, wherein said aromatic dianhydride is one or more of 1,2,4, 5-pyromellitic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, 3 ', 4, 4' -benzophenone tetracarboxylic dianhydride and 3,3 ', 4, 4' -diphenylsulfone tetracarboxylic dianhydride.
4. A method for preparing a high heat-resistant ultralow-expansion polyimide film according to any one of claims 1 to 3, comprising the steps of:
step 1: under the protection of inert gas, dissolving aromatic diamine in an organic solvent, and adding aromatic dianhydride at the low temperature of-10-15 ℃ to obtain polyamide acid homogeneous phase solution;
step 2: coating the polyamide acid homogeneous phase solution on a substrate, curing, stripping and drying to obtain a polyimide film to be treated;
and step 3: the polyimide film to be treated is laid on a substrate, fixed and annealed to obtain the polyimide film;
the curing comprises the following steps: curing at 60-100 ℃ for 1-2 hours, curing at 180-250 ℃ for 1-2 hours, and curing at 300-350 ℃ for 0.5-1 hour.
5. The method for preparing a high heat resistance ultra-low expansion polyimide film according to claim 4, wherein the annealing treatment comprises the following steps: at the temperature of 250 ℃ and 300 ℃ for 0.5-1 hour, and at the temperature of 350 ℃ and 400 ℃ for 10-30 minutes.
6. The method for preparing a high heat resistance ultra-low expansion polyimide film according to claim 4, wherein the solid content of the polyamic acid homogeneous solution is 10 wt.% to 30 wt.%; the molar ratio of the aromatic diamine to the aromatic dianhydride is (0.95-1.05): 1.
7. The method as claimed in claim 4, wherein the means for fixing the polyimide film to be treated on the substrate in step 3 is a means capable of applying a tensile stress to the film.
8. The method for preparing a highly heat-resistant ultralow expansion polyimide film according to any one of claims 4 to 7, wherein said organic solvent is one or more of N-methylpyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethyl sulfoxide, cyclopentanone and γ -butyrolactone.
9. The highly heat-resistant ultralow-expansion polyimide film as defined in any one of claims 1 to 3 as a substrate material for use in the fields of electronics, microelectronics, optical displays or optical communications.
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