CN110283313B - Transparent polyimide with high glass transition temperature and preparation method thereof - Google Patents
Transparent polyimide with high glass transition temperature and preparation method thereof Download PDFInfo
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- CN110283313B CN110283313B CN201910556814.6A CN201910556814A CN110283313B CN 110283313 B CN110283313 B CN 110283313B CN 201910556814 A CN201910556814 A CN 201910556814A CN 110283313 B CN110283313 B CN 110283313B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 54
- 239000004642 Polyimide Substances 0.000 title claims abstract description 34
- 230000009477 glass transition Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 115
- 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 54
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- 229920001621 AMOLED Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
Classifications
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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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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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
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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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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses transparent polyimide with high glass transition temperature and a preparation method thereof. The method comprises the steps of firstly carrying out solution polymerization on monomers A and B and other dianhydride monomers to generate a polyamic acid copolymer, then adjusting the solid content of the polyamic acid copolymer solution to 10-25%, coating, removing a solvent at a high temperature and imidizing to obtain the transparent polyimide with a high glass transition temperature. The polyimide film of the invention has high tensile strength and glass transition temperature while maintaining colorless transparency, and is suitable for flexible display devices.
Description
Technical Field
The invention belongs to the technical field of polyimide materials, and relates to transparent polyimide with high glass transition temperature and a preparation method thereof.
Background
Polyimide (PI) is a polymer containing imide ring units on a main chain, has the characteristics of outstanding heat resistance, chemical stability, excellent mechanical property, good dielectric property and the like, and is widely applied to the fields of semiconductor packaging, solar cells, liquid crystal displays, aerospace military industry, machinery, automobiles and the like.
In recent years, flexible electronics and flexible display technologies have received much attention. The flexible AMOLED adopts the flexible substrate to replace the traditional glass substrate, and due to the adoption of the ultrathin film which has strong impact resistance, good toughness and can be folded and bent, the flexible display development is smoothly carried out. In the manufacturing process of the photoelectric device, in order to realize better product performance, the substrate material needs to be subjected to high-temperature heat treatment at the temperature of 300-500 ℃. At present, the colored PI substrate has begun to be widely applied to flexible display devices due to its excellent high-temperature stability and good mechanical properties. However, the application of the colorless and transparent PI substrate with high glass transition temperature in the flexible display field has more development potential.
In the traditional high-temperature-resistant wholly aromatic PI material, due to the existence of a Charge Transfer Complex (CTC) formed by intramolecular and intermolecular charge transfer complexation, a PI film generally presents light yellow to dark brown, and the visible light transmittance is low. Semi-aromatic PI and full aliphatic PI are light in color or nearly colorless, but the PI is generally poor in heat resistance. That is, the PI material is difficult to be used in the electronic field because of the mutual constraints among heat resistance, optical transparency, and other properties (such as mechanical properties).
In order to obtain the transparent polyimide material with high glass transition temperature, the formation of charge transfer complex in the polymerized polyimide molecules can be reduced by controlling the structure of the monomer, so that the effect of transparent film is achieved, and the transparent polyimide material has high glass transition temperature. The prior art discloses a number of processes for the preparation of colorless transparent polyimide materials. For example, according to the Chinese patent application 201811476033.8, on the basis of the formula of the traditional colorless polyimide, through the design of the overall structure of a polymer, aromatic regulating dianhydride with a mirror symmetry structure is introduced, and the obtained high-heat-resistant colorless transparent polyimide has the light transmittance of more than 88%, the glass transition temperature of more than 336 ℃, the tensile strength of 109-120 MPa and the elongation at break of 20-26%. The Chinese patent application 201710583631.4 introduces fluorine element, sulfuryl or ether bond, etc. into the main chain of polyimide molecule through molecular design, which destroys the coplanarity of the molecular structure, inhibits the charge transfer in or between molecules, and obviously improves the optical performance of the polyimide film. The glass transition temperature of the prepared polyimide film is 280-300 ℃, and the light transmittance at 450nm is more than 80%. The transparent polyimide film disclosed in chinese patent application 201710726433.9 has a relatively flexible structure unit of triphenyldiethanetetracarboxylic dianhydride introduced into a structure unit with relatively high rigidity, so that the flexing resistance of the film is greatly improved, and the film has the characteristics of high light transmittance, good mechanical properties, high heat resistance, good flexing resistance and the like. Chinese patent application 201210103579.5 discloses a polyimide film and a preparation method thereof, wherein 2,3',3,4' -biphenyl tetracarboxylic dianhydride is used as a dianhydride monomer, 4,4 '-diamino-2, 2' -bis-trifluoromethyl biphenyl is used as a diamine monomer, and the polyimide film is obtained by polycondensation, wherein the ultraviolet light transmission cut-off wavelength of the polyimide film is 390 nm-400 nm, and the glass transition temperature is 306-324 ℃. However, the above colorless transparent PI materials have significant defects in both heat resistance and high temperature transparency, and the transparent polyimide materials with high glass transition temperature cannot simultaneously satisfy the requirements that the ultraviolet transmittance (450 nm) is greater than 90% and the glass transition temperature is higher than 355 ℃.
Disclosure of Invention
The invention aims to provide a transparent polyimide film with high glass transition temperature and a preparation method thereof. The film has high tensile strength and glass transition temperature while maintaining colorless transparency and transmittance of over 90%.
The technical scheme for realizing the purpose of the invention is as follows:
polyamic acid having the structural formula:
the transparent polyimide with high glass transition temperature has the following structural formula:
the synthetic route of the polyamic acid and the transparent polyimide with high glass transition temperature is as follows:
the preparation method of the polyamic acid is prepared by solution polymerization of a diamine monomer A monomer, a dianhydride monomer B monomer and other dianhydride monomers, and comprises the following specific steps:
dissolving the monomer A in an organic solvent according to the ratio of the molar amount of the monomer A to the total molar amount of the monomer B and the dianhydride monomer of 1.06: 1-1: 1.06, adding the monomer B and the dianhydride monomer at 0-20 ℃, and reacting at constant temperature to obtain a polyamic acid copolymer; the structural formula of the monomer A is as follows:
the structural formula of the B monomer is as follows:
the preparation method of the transparent polyimide with high glass transition temperature comprises the following specific steps:
step 1, according to the molar amount of the monomer A and the monomer BDissolving a monomer A in an organic solvent, adding a monomer B and a dianhydride monomer at 0-20 ℃, and reacting at constant temperature to obtain a polyamide acid copolymer solution, wherein the total molar weight ratio of the monomer A to the dianhydride monomer is 1.06: 1-1: 1.06; the structural formula of the monomer A is as follows:
the structural formula of the B monomer is as follows:
and 2, adjusting the solid content of the polyamic acid copolymer solution to 10-25%, coating, drying at 80-150 ℃ to remove the organic solvent, and imidizing at 150-400 ℃ to obtain the transparent polyimide film with high glass transition temperature.
Preferably, in the step 1, the molar ratio of the monomer A to the total molar amount of the monomer B and the dianhydride monomer is 1.06: 1-1: 1.06, and more preferably 1: 1-1: 1.02.
Preferably, in step 1, the amount of the B monomer is not less than 30% of the total molar amount of the B monomer and the dianhydride monomer.
Preferably, in step 1, the dianhydride monomer may be one or more selected from pyromellitic dianhydride, 3-diphenyl sulfide-4, 4', 5, 5' -biphenyl tetracarboxylic dianhydride, 3', 4,4' -benzophenone tetracarboxylic dianhydride, 3', 4,4' -diphenyl ether tetracarboxylic dianhydride, 3', 4,4' -triphenyl diether tetracarboxylic dianhydride, or 4, 4-hexafluoroisopropyl phthalic anhydride.
Preferably, in step 1, the organic solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetone, butanone and N-methylpyrrolidone.
Preferably, in step 1, the B monomer and the dianhydride monomer are added in batches.
Preferably, in the step 1, the monomer A is dissolved in an organic solvent under constant temperature stirring at 45-70 ℃.
Preferably, in the step 1, the constant-temperature reaction time is 3-24 hours.
Preferably, in step 2, the substrate of the coating film is selected from a glass plate, a metal plate, a ceramic plate or a plastic plate.
Compared with the prior art, the invention has the following advantages:
according to the invention, the monomers A and B are used as raw materials, the molecular chain of the prepared polyimide can form a halogen bond, and the halogen bond is used as a non-covalent bond acting force, so that the acting force between molecular chain segments can be increased, the glass transition temperature of the film is greatly increased and is higher than 355 ℃, and the heat resistance of the material is improved; meanwhile, due to the existence of halogen bonds, the formation of intramolecular and intermolecular charge transfer complexes can be effectively prevented, so that the film has very excellent light transmittance, and the transmittance reaches over 90 percent.
Detailed Description
The present invention will be described in more detail with reference to specific examples.
Example 1
0.10mol of monomer A is dissolved in N-methyl pyrrolidone in a reactor with reflux and nitrogen filling, the mixture is stirred at a constant temperature of 60 ℃, after the monomer A is completely dissolved, the reaction temperature is reduced to 10 ℃, and then 0.03mol of monomer B and 0.07mol of 3, 3', 4,4' -triphendiether tetracid dianhydride are added in 6 times in 1 hour. After the dianhydride monomer is added, the reaction is carried out for 10 hours at constant temperature, and a polyamic acid copolymer solution is obtained. (the amount of the B monomer accounts for 30.00 percent of the total dianhydride monomer amount; and the molar ratio of the diamine monomer (A monomer) to the total dianhydride monomer (B monomer and other dianhydride monomers) is 1: 1).
The solid content of the polyamic acid copolymer solution was adjusted to 15% by the solvent used in the polymerization, the solution was then coated on a clean and dry stainless steel plate, and the coated plate was dried in a vacuum oven at 80 ℃, 120 ℃, 150 ℃ for 1 hour each, and then heat-treated in a muffle furnace according to the following temperature rising procedure: drying at 200 deg.C, 240 deg.C, 270 deg.C, 300 deg.C, 330 deg.C, 350 deg.C, 370 deg.C and 400 deg.C for 0.5 hr to obtain transparent polyimide film with high glass transition temperature. The polyimide film had a tensile strength of 321MPa, an ultraviolet transmittance at 450nm of 93%, and a glass transition temperature of 364 ℃ by DSC method.
Example 2
In a reactor with reflux and nitrogen gas filling, 0.50mol of A monomer is dissolved in N, N-dimethylacetamide, stirred at a constant temperature of 45 ℃, after complete dissolution, the reaction temperature is reduced to 5 ℃, and then 0.30mol of B monomer and 0.21mol of pyromellitic dianhydride are added in 6 times within 1 hour. After the dianhydride monomer is added, the reaction is carried out for 5 hours at constant temperature, and a polyamic acid copolymer solution is obtained. (the amount of the B monomer accounts for 58.82 percent of the total dianhydride monomer amount; and the molar ratio of the diamine monomer (A monomer) to the total dianhydride monomer (B monomer and other dianhydride monomers) is 1: 1.02).
The solid content of the polyamic acid copolymer solution was adjusted to 20% by the solvent used in the polymerization, the solution was uniformly applied to a clean and dry stainless steel plate, and the coated plate was dried in a vacuum oven at 80 ℃, 120 ℃, and 150 ℃ for 1 hour, respectively, and then heat-treated in a muffle furnace according to the following temperature-raising procedure: drying at 150 deg.C, 200 deg.C, 250 deg.C, 300 deg.C, 350 deg.C and 400 deg.C for 1 hr to obtain transparent polyimide film with high glass transition temperature. The tensile strength of the polyimide film was 336MPa, the ultraviolet transmittance at 450nm was 90%, and the glass transition temperature was 370 ℃ (DSC method).
Example 3
In a reactor with reflux and nitrogen filling, 0.50mol of A monomer is firstly dissolved in N, N-dimethylformamide, stirred at a constant temperature of 50 ℃, after complete dissolution, the reaction temperature is reduced to 10 ℃, and then 0.25mol of B monomer and 0.25mol of 3, 3', 4,4' -biphenyltetracarboxylic dianhydride are added in 6 times in 1 hour. After the dianhydride monomer is added, the constant temperature reaction is carried out for 15 hours to obtain polyamic acid copolymer solution. (the amount of the B monomer accounts for 50.00 percent of the total dianhydride monomer amount; and the molar ratio of the diamine monomer (A monomer) to the total dianhydride monomer (B monomer and other dianhydride monomers) is 1: 1).
The polyamic acid copolymer solution was adjusted to a solid content of 10% with N, N-dimethylformamide, then coated on a clean and dried stainless steel plate, and the coated plate was dried in a vacuum oven at 80 ℃, 120 ℃, 150 ℃ for 1 hour each, followed by heat treatment in a muffle furnace according to the following temperature rising procedure: drying at 150 deg.C, 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C, 300 deg.C, 330 deg.C, 360 deg.C, 390 deg.C for 0.5 hr respectively to obtain transparent polyimide film with high glass transition temperature. The tensile strength of the polyimide film is 317MPa, the ultraviolet transmittance at 450nm is 91%, and the glass transition temperature is 367 ℃ (DSC method).
Example 4
In a reactor with reflux and nitrogen filling, 1.00mol of monomer A is dissolved in dimethyl sulfoxide, stirred at a constant temperature of 70 ℃, the reaction temperature is reduced to 15 ℃ after complete dissolution, and then 0.40mol of monomer B and 0.61mol of 4, 4-hexafluoroisopropyl phthalic anhydride are added in 6 times within 1 hour. After the dianhydride monomer is added, the reaction is carried out for 24 hours at constant temperature, and a polyamic acid copolymer solution is obtained. (the amount of the B monomer accounts for 39.60% of the total dianhydride monomer amount; and the molar ratio of the diamine monomer (A monomer) to the total dianhydride monomer (B monomer and other dianhydride monomers) is 1: 1.01).
The solid content of the polyamic acid copolymer solution was adjusted to 25% by the solvent used in the polymerization, the solution was then coated on a clean and dry stainless steel plate, and the coated plate was dried in a vacuum oven at 80 ℃, 100 ℃, 120 ℃, 140 ℃ for 0.5 hour each, followed by heat treatment in a muffle furnace according to the following temperature rise program: drying at 200 deg.C, 240 deg.C, 270 deg.C, 300 deg.C, 330 deg.C, 350 deg.C, 370 deg.C and 400 deg.C for 0.5 hr to obtain transparent polyimide film with high glass transition temperature. The polyimide film had a tensile strength of 291MPa, a UV transmittance at 450nm of 94% and a glass transition temperature of 359 ℃ (DSC method).
Comparative example 1
Comparative example 1 the procedure of example 1 was followed except that the B monomer was used in an amount of 0.02mol and the 3, 3', 4,4' -triphendiether tetracarboxylic dianhydride was used in an amount of 0.08 mol. (the amount of B monomer is 20.00% of the total dianhydride monomer).
The polyimide film had a tensile strength of 321MPa, an ultraviolet transmittance at 450nm of 89%, and a glass transition temperature of 335 ℃ (DSC method).
Comparative example 2
Comparative example 2 the procedure of example 3 was followed except that the B monomer was used in an amount of 0.27mol and 3, 3', 4,4' -biphenyltetracarboxylic dianhydride was used in an amount of 0.27 mol. (the amount of B monomer is 50.00% of the total dianhydride monomer).
The tensile strength of the polyimide film is 320MPa, the ultraviolet transmittance at 450nm is 87%, and the glass transition temperature is 360 ℃ (DSC method).
Claims (6)
1. A polyamic acid characterized by a structural formula as shown below:
is prepared by the following steps:
dissolving the monomer A in an organic solvent according to the ratio of the molar amount of the monomer A to the total molar amount of the monomer B and the dianhydride monomer of 1.06: 1-1: 1.06, adding the monomer B and the dianhydride monomer at 0-20 ℃, and reacting at constant temperature to obtain a polyamic acid copolymer; the structural formula of the monomer A is as follows:
the structural formula of the B monomer is as follows:
(ii) a In the total molar weight of the monomer B and the dianhydride monomer, the using amount of the monomer B is not less than 30 percent; the dianhydride monomer is one or more of pyromellitic dianhydride, 3-diphenyl sulfide-4, 4', 5, 5' -biphenyl tetracarboxylic dianhydride, 3', 4,4' -benzophenone tetracarboxylic dianhydride, 3', 4,4' -diphenyl methyl ether tetracarboxylic dianhydride, 3', 4,4' -triphenyl diether tetracarboxylic dianhydride or 4, 4-hexafluoroisopropyl phthalic anhydride.
2. The transparent polyimide with high glass transition temperature is characterized in that the structural formula is as follows:
is prepared by the following steps: step 1, dissolving a monomer A in an organic solvent according to the ratio of the molar amount of the monomer A to the total molar amount of the monomer B and a dianhydride monomer of 1.06: 1-1: 1.06, adding the monomer B and the dianhydride monomer at 0-20 ℃, and reacting at constant temperature to obtain a polyamic acid copolymer solution; the structural formula of the monomer A is as follows:
the structural formula of the B monomer is as follows:
(ii) a In the total molar weight of the monomer B and the dianhydride monomer, the using amount of the monomer B is not less than 30 percent; the dianhydride monomer is one or more of pyromellitic dianhydride, 3-diphenyl sulfide-4, 4', 5, 5' -biphenyl tetracarboxylic dianhydride, 3', 4,4' -benzophenone tetracarboxylic dianhydride, 3', 4,4' -diphenyl methyl ether tetracarboxylic dianhydride, 3', 4,4' -triphenyl diether tetracarboxylic dianhydride or 4, 4-hexafluoroisopropyl phthalic anhydride;
step 2, adjusting the solid content of the polyamic acid copolymer solution to 10-25%, coating, drying at 80-150 ℃ to remove the organic solvent, and imidizing at 150-400 ℃ to obtain a transparent polyimide film with high glass transition temperature;
the synthetic route is as follows:
3. the polyamic acid according to claim 1 or the transparent polyimide according to claim 2, wherein the molar ratio of the total molar amount of the monomer A, the monomer B and the dianhydride monomer is 1:1 to 1: 1.02.
4. The polyamic acid according to claim 1 or the transparent polyimide according to claim 2, wherein the organic solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetone, methyl ethyl ketone and N-methylpyrrolidone.
5. The polyamic acid according to claim 1 or the transparent polyimide according to claim 2, wherein the B monomer and the dianhydride monomer are added in a batch manner; the monomer A is dissolved in an organic solvent under constant-temperature stirring at the temperature of 45-70 ℃; the constant temperature reaction time is 3-24 hours.
6. The transparent polyimide according to claim 2, wherein in step 2, the substrate of the coating film is selected from a glass plate, a metal plate, a ceramic plate or a plastic plate.
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