CN114058049A - Transparent polyimide film with low thermal expansion coefficient - Google Patents
Transparent polyimide film with low thermal expansion coefficient Download PDFInfo
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- CN114058049A CN114058049A CN202111408659.7A CN202111408659A CN114058049A CN 114058049 A CN114058049 A CN 114058049A CN 202111408659 A CN202111408659 A CN 202111408659A CN 114058049 A CN114058049 A CN 114058049A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 45
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 128
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000011065 in-situ storage Methods 0.000 claims abstract description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 43
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 29
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 22
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 22
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 22
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 238000007792 addition Methods 0.000 claims description 56
- 238000006116 polymerization reaction Methods 0.000 claims description 44
- 108010025899 gelatin film Proteins 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- 230000002493 climbing effect Effects 0.000 claims description 13
- 239000004952 Polyamide Substances 0.000 claims description 11
- 229910000831 Steel Inorganic materials 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 11
- 230000009194 climbing Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 238000007493 shaping process Methods 0.000 claims description 11
- 239000010959 steel Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- 239000004642 Polyimide Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000012756 surface treatment agent Substances 0.000 abstract 1
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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Abstract
The invention discloses a transparent polyimide film with low thermal expansion coefficient, which is prepared from nano SiO2, a silane coupling agent, a dimethylformamide solution, biphenyl tetracarboxylic dianhydride, diaminodiphenyl ether, pyromellitic dianhydride and p-phenylenediamine. According to the invention, the nano SiO2 is added through the filler and is introduced into the polyimide film, the nano SiO2 is one of the materials with the lowest known thermal expansion coefficient, the thermal expansion coefficient of the hybrid material can be reduced, the thermal stability of the polyimide is improved, meanwhile, the nano SiO2 is subjected to surface activation treatment by taking a silane coupling agent as a surface treatment agent, so that the synthesized polyimide film has better mechanical property and lower thermal expansion coefficient, in the process of synthesizing the first polyamic acid solution and the second polyamic acid solution, an in-situ polycondensation reaction is adopted, the performance of the prepared product is more stable, and the problem that the traditional polyimide material at the present stage is difficult to have the requirements of high heat resistance and low expansion is solved.
Description
Technical Field
The invention relates to the technical field of films, in particular to a transparent polyimide film with a low thermal expansion coefficient.
Background
Polyimide is a highly regular polymer with a chemical structure containing imide rings on a high molecular main chain, and the special imide ring structure enables the polyimide to have excellent mechanical, thermal, dielectric, mechanical, radiation-resistant and solvent-resistant properties, so that the polyimide is widely used in the fields of aviation, aerospace, microelectronics, automobile industry and the like, and along with the rapid development of light weight and miniaturization of electronic products, the polyimide has higher and higher requirements on the mechanical property and dimensional stability of films when used as a base film on a flexible circuit board.
In industries such as photoelectric display and the like, the novel polyimide film is used for replacing a glass material, so that the characteristics of lightness, thinness, foldability and the like of a screen can be realized, the polyimide film is often combined with an inorganic material for use, but in the processing process, the material is subjected to a high-heat environment, and the traditional polyimide material at the present stage is difficult to have the requirements of high heat resistance and low expansion.
Disclosure of Invention
The invention aims to provide a transparent polyimide film with a low thermal expansion coefficient, which has the advantages of high heat resistance and low expansion, and solves the problem that the conventional polyimide material is difficult to meet the requirements of high heat resistance and low expansion because the polyimide film is often combined with an inorganic material for use, but the material is subjected to a high-heat environment in the processing process.
In order to achieve the purpose, the invention provides the following technical scheme: a transparent polyimide film with low thermal expansion coefficient is prepared from nano SiO2, silane coupling agent, dimethyl formamide solution, biphenyl tetracarboxylic dianhydride, diaminodiphenyl ether, pyromellitic dianhydride and p-phenylenediamine as raw materials, and its preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. and finally, drying and shaping the gel film to obtain the polyimide film.
Preferably, the temperature required for preparing the first solution in the step a is sixty to eighty degrees celsius.
Preferably, the time for ultrasonically dispersing the solution in the step A1 is twenty-five to eighty-five minutes.
Preferably, the molar ratio of the biphenyl tetracarboxylic dianhydride to the diaminodiphenyl ether in the step B1 is 0.993:1-0.997: 1.
Preferably, in the step B2, the two adjacent additions are separated by thirty to sixty minutes during the addition of the biphenyltetracarboxylic dianhydride.
Preferably, the molar ratio of the pyromellitic dianhydride to the p-phenylenediamine in the step C1 is 0.993:1-0.997: 1.
Preferably, the time interval between two adjacent additions in the step C2 during the addition of pyromellitic dianhydride is thirty to sixty minutes.
Preferably, the temperature required for high-speed stirring in the step D1 is thirty-five to forty degrees celsius, and the high-speed stirring time is thirty to sixty minutes.
Preferably, the step E1 requires that pyromellitic dianhydride be added to the third polyamic acid solution at twenty to thirty-five degrees celsius to generate a pole-climbing effect.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adds nano SiO2 through the filler, the nano SiO2 is one of the materials with the minimum thermal expansion coefficient at present, the nano SiO2 is introduced into the polyimide film, can reduce the thermal expansion coefficient of the hybrid material, improve the thermal stability of the polyimide, simultaneously, by using the silane coupling agent as the surface treating agent, the surface activation treatment is carried out on the nano SiO2, so that the synthesized polyimide film has better mechanical property and lower thermal expansion coefficient, in the process of synthesizing the first polyamic acid solution and the second polyamic acid solution, in-situ polycondensation is adopted, so that the performance of the prepared product is more stable, thereby solving the problems that the polyimide film is often combined with inorganic materials for use, but in the processing process, the material is subjected to a high-heat environment, and the traditional polyimide material at the present stage is difficult to have the problems of high heat resistance and low expansion requirement.
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. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that:
a transparent polyimide film with low thermal expansion coefficient is prepared from nano SiO2, silane coupling agent, dimethyl formamide solution, biphenyl tetracarboxylic dianhydride, diaminodiphenyl ether, pyromellitic dianhydride and p-phenylenediamine as raw materials, and its preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. finally drying and shaping the gel film to obtain the polyimide film
Example two:
in the first embodiment, the following steps are added:
the temperature required for making the first solution in step a is sixty to eighty degrees celsius.
The preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. finally drying and shaping the gel film to obtain the polyimide film
Example three:
in the second embodiment, the following steps are added:
the time for ultrasonically dispersing the solution in step a1 was twenty-five to eighty-five minutes.
The preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. and finally, drying and shaping the gel film to obtain the polyimide film.
Example four:
in the third embodiment, the following steps are added:
in the step B1, the molar ratio of the biphenyl tetracarboxylic dianhydride to the diaminodiphenyl ether is 0.993:1-0.997: 1.
The preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. and finally, drying and shaping the gel film to obtain the polyimide film.
Example five:
in the fourth example, the following steps were added:
in the step B2, the time interval between two adjacent additions is thirty to sixty minutes during the addition of the biphenyl tetracarboxylic dianhydride.
The preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. and finally, drying and shaping the gel film to obtain the polyimide film.
Example six:
in the fifth example, the following steps were added:
in the step C1, the molar ratio of the pyromellitic dianhydride to the p-phenylenediamine is 0.993:1-0.997: 1.
The preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. and finally, drying and shaping the gel film to obtain the polyimide film.
Example seven:
in example six, the following steps were added:
in the step C2, the time interval between two adjacent additions is thirty to sixty minutes during the addition of the pyromellitic dianhydride.
The preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. and finally, drying and shaping the gel film to obtain the polyimide film.
Example eight:
in example seven, the following steps were added:
the temperature required for high-speed stirring in step D1 is thirty-five to forty degrees celsius, and the high-speed stirring time is thirty to sixty minutes.
The preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. and finally, drying and shaping the gel film to obtain the polyimide film.
Example nine:
in example eight, the following steps were added:
in step E1, pyromellitic dianhydride needs to be added into the third polyamic acid solution under the condition of twenty to thirty-five degrees centigrade to generate the pole climbing effect.
The preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. and finally, drying and shaping the gel film to obtain the polyimide film.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A transparent polyimide film with low thermal expansion coefficient is prepared from nano SiO2, silane coupling agent, dimethyl formamide solution, biphenyl tetracarboxylic dianhydride, diaminodiphenyl ether, pyromellitic dianhydride and p-phenylenediamine as raw materials, and is characterized in that: the preparation method comprises the following steps:
A. preparing a first solution:
a1, adding nano SiO2 and a silane coupling agent into a dimethylformamide solution, and preparing a uniform first solution after ultrasonic dispersion;
B. preparation of a first polyamic acid solution:
b1, putting biphenyl tetracarboxylic dianhydride and diaminodiphenyl ether into the first solution for in-situ polymerization:
b2, during the in-situ polymerization reaction, firstly dissolving diaminodiphenyl ether in the first solution, then adding the biphenyl tetracarboxylic dianhydride for four times, wherein the addition amount of each time accounts for 45-60% of the balance during the previous three times of addition, and after the addition of the biphenyl tetracarboxylic dianhydride is finished, reacting for fifty-eighty minutes to obtain a first polyamide acid solution with the solid content of 20-30 wt%;
C. making a second polyamic acid solution:
c1, putting pyromellitic dianhydride and p-phenylenediamine into the first solution for in-situ polymerization:
c2, during the in-situ polymerization reaction, firstly dissolving p-phenylenediamine in the first solution, then adding pyromellitic dianhydride in four times, wherein the adding amount of each time accounts for 45-60% of the balance during the first three times of addition, and reacting for fifty-eighty minutes after the pyromellitic dianhydride is added, thus obtaining a second polyamic acid solution with the solid content of 20-30 wt%;
D. preparation of a third polyamic acid solution:
d1, mixing the first polyamic acid solution and the second polyamic acid solution together according to the weight ratio of 1:1.5-1:2.0, and then stirring and mixing at a high speed to obtain a third polyamic acid solution;
E. causing the third polyamic acid solution to undergo a rod climbing reaction:
e1, adding pyromellitic dianhydride into the third polyamic acid solution to generate a rod climbing effect, and controlling the rotational viscosity of the third polyamic acid solution to 2200-4200P;
F. defoaming the reacted polyamic acid solution;
G. casting the defoamed solution on a steel plate support, and heating to 110-140 ℃ to obtain a gel film;
H. then the gel film is sent into an imidization furnace for biaxial stretching and imidization reaction;
I. and finally, drying and shaping the gel film to obtain the polyimide film.
2. A transparent polyimide film having a low coefficient of thermal expansion according to claim 1, wherein: the temperature required for making the first solution in step a is sixty to eighty degrees celsius.
3. A transparent polyimide film having a low coefficient of thermal expansion according to claim 1, wherein: the time for ultrasonically dispersing the solution in the step A1 is twenty-five to eighty-five minutes.
4. A transparent polyimide film having a low coefficient of thermal expansion according to claim 1, wherein: in the step B1, the molar ratio of the biphenyl tetracarboxylic dianhydride to the diaminodiphenyl ether is 0.993:1-0.997: 1.
5. A transparent polyimide film having a low coefficient of thermal expansion according to claim 1, wherein: in the step B2, the time interval between two adjacent additions is thirty to sixty minutes during the addition of the biphenyl tetracarboxylic dianhydride.
6. A transparent polyimide film having a low coefficient of thermal expansion according to claim 1, wherein: in the step C1, the molar ratio of the pyromellitic dianhydride to the p-phenylenediamine is 0.993:1-0.997: 1.
7. A transparent polyimide film having a low coefficient of thermal expansion according to claim 1, wherein: in the step C2, the time interval between two adjacent additions is thirty to sixty minutes during the addition of the pyromellitic dianhydride.
8. A transparent polyimide film having a low coefficient of thermal expansion according to claim 1, wherein: the required temperature for high-speed stirring in the step D1 is thirty-five to forty ℃, and the high-speed stirring time is thirty to sixty minutes.
9. A transparent polyimide film having a low coefficient of thermal expansion according to claim 1, wherein: in the step E1, pyromellitic dianhydride needs to be added into the third polyamic acid solution under the condition of twenty to thirty-five degrees centigrade to generate the pole climbing effect.
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