CN114058049A - Transparent polyimide film with low thermal expansion coefficient - Google Patents
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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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