CN111205490B - Method for producing polyimide film - Google Patents
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- CN111205490B CN111205490B CN201811400525.9A CN201811400525A CN111205490B CN 111205490 B CN111205490 B CN 111205490B CN 201811400525 A CN201811400525 A CN 201811400525A CN 111205490 B CN111205490 B CN 111205490B
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- 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
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to a method for preparing a polyimide film, which comprises providing a polyamic acid copolymer, wherein the polyamic acid copolymer at least comprises semi-aromatic polyamic acid, and the semi-aromatic polyamic acid is obtained by reacting 1,2,3, 4-cyclobutyltetracarboxylic dianhydride (CBDA) with aromatic ring diamine; adding dehydrating agent and pyridine catalyst with ortho-position substituent group into the polyamic acid copolymer to make the polyamic acid copolymer implement imidization reaction by using chemical cyclization method so as to obtain the invented polyimide film.
Description
[ technical field ] A
The present invention relates to a method for manufacturing a polyimide film, and more particularly, to a method for manufacturing a polyimide film having excellent mechanical properties and being easy to manufacture.
[ background of the invention ]
The polyimide film is prepared by performing imidization reaction on polyamide acid which is a precursor of polyimide, wherein the imidization reaction mode is divided into chemical cyclization and thermal cyclization; the thermal cyclization is to imidize the polyamic acid precursor at high temperature, while the chemical cyclization is to use a dehydrating agent and a catalyst to make the polyamic acid precursor achieve partial imidization at lower temperature, and then put into high temperature for baking to make the imidization more complete. The thermal cyclization requires a long baking time in production, and also causes a decrease in mechanical properties and yellowing of the polyimide film after a long baking time. The chemical cyclization method is preferred for mass production because it takes a short time to produce and maintains good mechanical properties.
Polyimide films containing 1,2,3, 4-cyclobutyltetracarboxylic dianhydride (CBDA) have excellent optical properties and thermal stability, and are therefore used as a liquid crystal aligning agent for liquid crystal devices, semiconductor devices, or as a protective film, an insulating film, or an optical waveguide material for optical communications. U.S. Pat. No. 5,053,545 discloses that a polyimide film having excellent optical transparency and heat resistance can be produced by reacting CBDA with diamine to form polyamic acid and cyclizing the polyamic acid by a thermal ring closure method. In US6489431B1, a polyimide film having more excellent optical properties can be produced by cyclizing a constituent diamine having hexafluoropropylene in addition to CBDA by a thermal ring closure method. Although the above-mentioned articles use the thermal ring-closure method to form a film, the thermal ring-closure method takes a lot of baking time and the resulting polyimide film has mechanical properties inferior to those of the chemical ring-closure method, and thus many researchers have attempted to form a film by chemical ring-closure, but Hasegawa, journal of High performance, polymer.2001, 13, S93-S106, proposed that the polyamic acid having CBDA component causes precipitation due to solubility problem when chemically cyclized. So that no products using the dianhydride as a base are found in the technical field of chemical cyclization film preparation.
Therefore, the invention provides a method for preparing a polyimide film containing 1,2,3, 4-cyclobutyltetracarboxylic dianhydride (CBDA) by chemical cyclization, and the polyimide film prepared by the method has better mechanical properties.
[ summary of the invention ]
The invention provides a method for manufacturing a polyimide film, which is characterized by comprising the following steps: providing a polyamic acid copolymer which comprises semi-aromatic polyamic acid, wherein the semi-aromatic polyamic acid is obtained by reacting 1,2,3, 4-cyclobutyltetracarboxylic dianhydride (CBDA) with aromatic ring diamine; a dehydrating agent, a pyridine catalyst having an ortho-substituent, and an acid are added to the polyamic acid copolymer, and imidization is performed by a chemical cyclization method to produce a polyimide film.
<xnotran> , (PDA), 4,4' - (ODA), 2,2' - [4- (4- ) ] (BAPP), 2,2' - ( ) (TFMB), 3,5- (35 DABA), 4,4' - (44 DABA), 5 (6) - -1- (4- ) -1,3,3- (TMDA), 4,4' - (4- ) (BAPS), 4,4' - (4- ) (BAPB), 1,4- (4- ) (TPEQ), 2,2' - ( ) -4,4' - (6 FODA), 2,2- [4- (4- ) ] -1,1,1,3,3,3- (HFBAPP), 9,9- (4- ) (BAFL), 2- (4- ) -5- (5 BPOA), (mPDA), 4,4' - (44 DDS), 2,2- (4- ) (Bis-A-AF), 2,2- (3- -4- ) (</xnotran> 6 FAP), 4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ] (FAPB).
Furthermore, the polyamic acid copolymer also comprises aromatic polyamic acid which is obtained by reacting aromatic diamine and aromatic dianhydride.
Specifically, the aromatic dianhydride is selected from 1,2,4, 5-benzenetetracarboxylic anhydride (PMDA), 3',4' -biphenyltetracarboxylic dianhydride (BPDA), 4' -oxydiphthalic anhydride (ODPA), 3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3, 4-diphenylsulfone tetracarboxylic dianhydride (DSDA), 2, 3',4' -biphenyl tetracarboxylic dianhydride (α -BPDA), 4-hexafluoroisopropylphthalic anhydride (6 FDA), 4' - (4, 4' -isopropyldiphenoxy) diphthalic anhydride (BPADA); <xnotran> 2,2' - ( ) (TFMB), 2,2' - [4- (4- ) ] (BAPP), 2,2- [4- (4- ) ] -1,1,1,3,3,3- (HFBAPP), 5 (6) - -1- (4- ) -1,3,3- (TMDA), (PDA), 4,4' - (4- ) (BAPB), 2,2' - ( ) -4,4' - (6 FODA), 4,4' - (4- ) (BAPS), 9,9- (4- ) (BAFL), 4,4' - (44 DDS), 4,4' - (ODA), 4,4' - (44 DABA), 2,2- (4- ) (Bis-A-AF), (mPDA), 2,2- (3- -4- ) (6 FAP), 3,5- (35 DABA), 2- (4- ) -5- (5 BPOA), </xnotran> 1, 4-bis (4-aminophenoxy) benzene (TPEQ), 4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ] (FAPB).
Further, the pyridine catalyst structure with ortho-substituent is selected from
Wherein at least one of R1 and R2 is a substituent other than hydrogen.
Preferably, the pyridine catalyst with an ortho-substituent is 2-methylpyridine.
Preferably, the pyridine catalyst with ortho-substituent is added in a molar number which is greater than or equal to that of the polyamic acid copolymer; the mole number of the semi-aromatic polyamic acid dianhydride may be 30 to 50 percent of the total mole number of the acid anhydride of the copolymerized polyamic acid.
The invention provides a specific implementation method which comprises the steps of adding 0.1342 mole of 2,2 '-bis (trifluoromethyl) diaminobiphenyl into 0.1074mole of N, N-dimethylacetamide, adding 21.053 grams of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride after the 2,2' -bis (trifluoromethyl) diaminobiphenyl is completely dissolved, stirring for reacting for six hours, adding 0.0805 mole of 2,2 '-bis (trifluoromethyl) diaminobiphenyl, stirring until the 2,2' -bis (trifluoromethyl) diaminobiphenyl is completely dissolved, adding 0.1074mole of 4, 4-hexafluoroisopropyl phthalic anhydride, stirring for dissolving and reacting to obtain a polyamic acid copolymer with the solid content of 25%; taking out 57 g of polyamic acid copolymer, diluting the solid content to 17.8% by using N, N-dimethylacetamide, then respectively adding 12.6 ml of acetic anhydride and 19.5 ml of 2-methylpyridine, stirring, coating and drying to obtain the polyamic acid copolymer.
The invention also provides a polyimide film prepared by any one of the methods, which is characterized in that when the thickness of the polyimide film is 50um, the elongation is more than 12%.
The invention also provides a polyimide film prepared from the copolymer polyamic acid, which is characterized in that the copolymer polyamic acid comprises semi-aromatic polyamic acid, and the semi-aromatic polyamic acid is obtained by reacting 1,2,3, 4-cyclobutyltetracarboxylic dianhydride (CBDA) with aromatic diamine; when the thickness of the polyimide film is 50um, the elongation is 12-26%
[ description of the drawings ]
FIG. 1 is a flow chart of a method for producing a polyimide film according to the present invention.
Wherein, each symbol is described as follows:
providing a polyamic acid copolymer (S1)
Adding dehydrating agent, pyridine catalyst without substituent at ortho-position and acid (S2)
The imidization reaction (S3) is carried out by a chemical cyclization method.
[ embodiments ] A method for producing a semiconductor device
Referring to fig. 1, the present invention is a flow chart of a method for manufacturing a polyimide film, which includes; providing a polyamic acid copolymer (S1) which at least comprises semi-aromatic polyamic acid, wherein the semi-aromatic polyamic acid is obtained by the reaction of 1,2,3, 4-cyclobutyltetracarboxyl dianhydride (CBDA) and aromatic diamine; a dehydrating agent and a pyridine catalyst having an ortho-substituent are added to the polyamic acid copolymer (S2) to perform imidization of the polyamic acid copolymer by a chemical cyclization method (S3), thereby producing a polyimide film.
<xnotran> (PDA), 4,4' - (ODA), 2,2' - [4- (4- ) ] (BAPP), 2,2' - ( ) (TFMB), 3,5- (35 DABA), 4,4' - (44 DABA), 5 (6) - -1- (4- ) -1,3,3- (TMDA), 4,4' - (4- ) (BAPS), 4,4' - (4- ) (BAPB), 1,4- (4- ) (TPEQ), 2,2' - ( ) -4,4' - (6 FODA), 2,2- [4- (4- ) ] -1,1,1,3,3,3- (HFBAPP), 9,9- (4- ) (BAFL), 2- (4- ) -5- (5 BPOA), (mPDA), 4,4' - (44 DDS), 2,2- (4- ) (Bis-A-AF), </xnotran> 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), 4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ] (FAPB).
The polyamic acid copolymer may include aromatic polyamic acid obtained by reacting aromatic diamine and aromatic anhydride. <xnotran> 2,2' - ( ) (TFMB), 2,2' - [4- (4- ) ] (BAPP), 2,2- [4- (4- ) ] -1,1,1,3,3,3- (HFBAPP), 5 (6) - -1- (4- ) -1,3,3- (TMDA), (PDA), 4,4' - (4- ) (BAPB), 2,2' - ( ) -4,4' - (6 FODA), 4,4' - (4- ) (BAPS), 9,9- (4- ) (BAFL), 4,4' - (44 DDS), 4,4' - (ODA), 4,4' - (44 DABA), 2,2- (4- ) (Bis-A-AF), (mPDA), 2,2- (3- -4- ) (6 FAP), 3,5- (35 DABA), 2- (4- ) -5- (5 BPOA), </xnotran> 1, 4-bis (4-aminophenoxy) benzene (TPEQ), 4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ] (FAPB). Wherein the aromatic dianhydride comprises 1,2,4, 5-benzenetetracarboxylic anhydride (PMDA), 3',4' -biphenyltetracarboxylic dianhydride (BPDA), 4' -oxydiphthalic anhydride (ODPA), 3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3, 4-diphenylsulfone tetracarboxylic dianhydride (DSDA), 2, 3',4' -biphenyltetracarboxylic dianhydride (alpha-BPDA), 4-hexafluoroisopropylphthalic anhydride (6 FDA), 4' - (4, 4' -isopropyldiphenoxy) diphthalic anhydride (BPADA).
The polyamic acid copolymer is subjected to imidization reaction by using a chemical cyclization method, and a dehydrating agent and a pyridine catalyst with an ortho-position substituent are added, wherein the pyridine catalyst with the ortho-position substituent can have the following structure:
wherein at least one of R1 and R2 is a substituent group other than hydrogen, and the addition amount of the pyridine catalyst with an ortho-substituent is preferably greater than or equal to the mole number of the polyamic acid copolymer.
Examples
< detection method >
Elongation was measured according to ASTM D882 Standard Specification using a Hounsfield H10K-S tensile machine.
< example 1>
Production of Polyamic acid copolymer
42.972 g of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFMB, 0.1342)
mole, 0.625 mole percent of total diamine), 412.5 grams of N, N-dimethylacetamide (DMAc) was added, 21.053 grams of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA, 0.1074mole, 50 mole percent of total anhydride) was added after all dissolved, the temperature was controlled at 25 ℃ with stirring for six hours and the temperature was maintained at 25 ℃ continuously. After six hours, 25.783 g of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFMB, 0.0805 mol) was added and stirred until completely dissolved, 47.691 g of 4, 4-hexafluoroisopropylphthalic anhydride (6 FDA,0.1074 mol) was further added and stirred for a certain period of time to dissolve and react, and the temperature of the solution was maintained at 25 ℃ to finally obtain a polyamic acid copolymer having a solid content of 25%.
Polyimide film fabrication
57 g of the polyamic acid copolymer was taken out, and the solid content was diluted to 17.8% with N, N-dimethylacetamide (DMAc), and then 12.6 ml of acetic anhydride and 19.5 ml of 2-methylpyridine were added, respectively, and after uniform stirring, the solution was applied to a glass plate and then applied using a 900 μm-gap doctor blade. And (3) placing the coated sample in a 50 ℃ oven for baking for 20 minutes, slowly heating to 170 ℃ for baking for 20 minutes, and heating the oven to 260 ℃ for baking for 20 minutes as final treatment to prepare the polyimide film.
The polyimide film obtained above had an elongation of 26%.
< example 2>
Production of Polyamic acid copolymer
20.100 g of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFMB, 0.0627mole, 0.315 mole percent of total diamine) was added to 412.5 g of N, N-dimethylacetamide (DMAc), 11.723 g of 1,2,3, 4-cyclobutyltetracarboxydianhydride (CBDA, 0.0598mole, 30 mole percent of total acid anhydride) was added after all had dissolved, and the reaction was stirred for six hours with the temperature maintained continuously at 25 ℃. 43.711 g of 2,2' -bis (trifluoromethyl) benzidine (TFMB, 0.1365 mole) was added to the polyamic acid solution, and stirred until completely dissolved, and 61.965 g of 4, 4-hexafluoroisopropylphthalic anhydride (6 FDA,0.1395 mole) was added thereto, and stirred for a certain period of time to dissolve and react, and the temperature of the solution was maintained at 25 ℃ to finally obtain a polyamic acid copolymer having a solid content of 25%.
Production of polyimide film
57 g of the polyamic acid copolymer was taken out, and the solid content was diluted to 17.8% with N, N-dimethylacetamide (DMAc), and then 11.7 ml of acetic anhydride and 4 ml of 2-methylpyridine were added, respectively, and after uniform stirring, the solution was applied to a glass plate and then applied using a doctor blade with a gap of 900. Mu.m. And (3) placing the coated sample in a 50 ℃ oven to be baked for 20 minutes, slowly heating to 170 ℃ to be baked for 20 minutes, and heating the oven to 260 ℃ to be baked for 20 minutes as final treatment to prepare the polyimide film.
The polyimide film obtained above had an elongation of 12%.
< comparative example 1>
Preparation of Polyamic acid copolymer
The manufacturing method is the same as that of example 1.
Production of polyimide film
57 g of the polyamic acid copolymer was taken out, and the solid content was diluted to 17.8% with N, N-dimethylacetamide (DMAc), and then 12.6 ml of acetic anhydride and 4.3 ml of 3-methylpyridine were added, respectively, and after stirring, gelation occurred rapidly, and thus a film could not be formed.
< comparative example 2>
Preparation of Polyamic acid copolymer
The manufacturing method is the same as in example 1.
Production of polyimide film
57 g of the polyamic acid copolymer was taken out, and the solid content was diluted to 17.8% with N, N-dimethylacetamide (DMAc), and the solution was applied to a glass plate and then applied using a doctor blade with a gap of 900. Mu.m. And (3) placing the coated sample in an oven at 50 ℃ for baking for 20 minutes, slowly heating to 170 ℃ for baking for 20 minutes, and heating the oven to 260 ℃ for baking for 20 minutes to obtain the final treatment.
The physical properties of the polyimide film obtained above are fragile, and therefore, the elongation thereof cannot be measured.
< comparative example 3>
Preparation of Polyamic acid copolymer
The manufacturing method is the same as in example 2.
Production of polyimide film
57 g of the polyamic acid copolymer was taken out, and the solid content was diluted to 17.8% with N, N-dimethylacetamide (DMAc), and the solution was applied to a glass plate and then applied using a doctor blade with a gap of 900. Mu.m. And (3) placing the coated sample in a 50 ℃ oven for baking for 20 minutes, slowly heating to 170 ℃ for baking for 20 minutes, and heating the oven to 260 ℃ for baking for 20 minutes to obtain the final treatment.
The elongation of the polyimide film obtained above was 2%.
Experimental comparison table
X is unable to form film; o can form a film
Pyridine catalyst with ortho-substituent 2-methylpyridine
Pyridine catalyst without ortho-substituent 3-methyl pyridine
The foregoing description of the specific embodiments is provided for the purpose of illustrating the invention in detail, however, the embodiments are for the purpose of illustration only and are not intended to limit the invention. It will be appreciated by those skilled in the art that the present invention may be practiced without departing from the scope of the appended claims. Various changes or modifications may be made to the invention as described herein.
Claims (6)
1. A method for producing a polyimide film, comprising:
providing a polyamic acid copolymer which comprises semi-aromatic polyamic acid, wherein the semi-aromatic polyamic acid is obtained by reacting 1,2,3, 4-cyclobutyltetracarboxyl dianhydride (CBDA) with aromatic diamine;
adding a dehydrating agent and a pyridine catalyst with an ortho-position substituent group into the polyamic acid copolymer, and carrying out imidization reaction by a chemical cyclization method to prepare a polyimide film;
the polyamic acid copolymer also comprises aromatic polyamic acid, and the aromatic polyamic acid is obtained by reacting aromatic diamine and aromatic dianhydride;
the pyridine catalyst with ortho-substituent is added in a molar number which is more than or equal to that of the polyamic acid copolymer; the mole number of the semi-aromatic polyamic acid dianhydride accounts for 30-50% of the total mole number of the acid anhydride of the copolymerized polyamic acid;
the pyridine catalyst with ortho-substituent is 2-methylpyridine.
2. <xnotran> 1 , , (PDA), 4,4' - (ODA), 2,2' - [4- (4- ) ] (BAPP), 2,2' - ( ) (TFMB), 3,5- (35 DABA), 4,4' - (44 DABA), 5 (6) - -1- (4- ) -1,3,3- (TMDA), 4,4' - (4- ) (BAPS), 4,4' - (4- ) (BAPB), 1,4- (4- ) (TPEQ), 2,2' - ( ) -4,4' - (6 FODA), 2,2- [4- (4- ) ] -1,1,1,3,3,3- (HFBAPP), 9,9- (4- ) (BAFL), 2- (4- ) -5- (5 BPOA), (mPDA), 4,4' - (44 DDS), 2,2- (4- ) (Bis-A-AF), </xnotran> 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), 4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ] (FAPB).
3. The method according to claim 1, wherein the aromatic dianhydride is selected from 1,2,4, 5-benzenetetracarboxylic dianhydride (PMDA), 3',4' -biphenyltetracarboxylic dianhydride (BPDA), 4' -oxydiphthalic anhydride (ODPA), 3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3, 4-diphenylsulfone tetracarboxylic dianhydride (DSDA), 2, 3',4' -biphenyl tetracarboxylic dianhydride (. Alpha. -BPDA), 4-hexafluoroisopropylphthalic anhydride (6 FDA), 4' - (4, 4' -isopropyldiphenoxy) diphthalic anhydride (BPADA).
4. The method of claim 1,
adding 0.1342 mol of 2,2 '-bis (trifluoromethyl) diaminobiphenyl into 0.1074mol of N, N-dimethylacetamide, adding 21.053 g of 1,2,3, 4-cyclobutane tetracarboxyl dianhydride after completely dissolving, stirring for reacting for six hours, adding 0.0805 mol of 2,2' -bis (trifluoromethyl) diaminobiphenyl, stirring until completely dissolving, adding 0.1074mol of 4, 4-hexafluoroisopropyl phthalic anhydride, stirring for dissolving and reacting to obtain a polyamic acid copolymer with the solid content of 25%;
taking out 57 g of polyamic acid copolymer, diluting the solid content to 17.8% by using N, N-dimethylacetamide, then respectively adding 12.6 ml of acetic anhydride and 19.5 ml of 2-methylpyridine, stirring, coating and drying to obtain the polyamic acid copolymer.
5. The polyimide film obtained by the method according to any one of claims 1 to 4, wherein the polyimide film has an elongation of more than 12% at a film thickness of 50 μm.
6. The polyimide film according to claim 5, which is prepared from a copolymerized polyamic acid,
the copolymerized polyamic acid comprises semi-aromatic polyamic acid, wherein the semi-aromatic polyamic acid is obtained by reacting 1,2,3, 4-cyclotetramethylene tetracarboxylic dianhydride (CBDA) with aromatic ring diamine; when the thickness of the polyimide film is 50 mu m, the elongation is 12-26%.
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| US11603440B2 (en) | 2019-09-12 | 2023-03-14 | Dupont Electronics, Inc. | Polyimide films and electronic devices |
| CN113621234B (en) * | 2021-08-04 | 2022-08-30 | 深圳瑞华泰薄膜科技股份有限公司 | Ultrahigh-modulus high-transmittance polyimide film and preparation method and application thereof |
| CN117285709B (en) * | 2022-06-16 | 2024-09-10 | 比亚迪股份有限公司 | Catalyst for synthesizing polyimide and preparation method and application thereof |
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| CN104583273A (en) * | 2012-05-14 | 2015-04-29 | 国立大学法人岩手大学 | Polyimide precursor, polyimide, polyimide film, polyimide metal laminate, and polyimide solution |
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