CN113736084B - Transparent polyamide-imide resin and preparation method and application thereof - Google Patents
Transparent polyamide-imide resin and preparation method and application thereof Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 64
- 229920005989 resin Polymers 0.000 title claims abstract description 64
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 63
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims description 13
- 238000013086 organic photovoltaic Methods 0.000 claims abstract description 39
- 230000003287 optical effect Effects 0.000 claims abstract description 37
- 230000001681 protective effect Effects 0.000 claims description 23
- 239000011149 active material Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 7
- 230000005525 hole transport Effects 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 5
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 230000000865 phosphorylative effect Effects 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- XTEBLARUAVEBRF-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XTEBLARUAVEBRF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a transparent polyamide imide resin, which comprises the following repeated structural units:n is a repeating structural unit and is 800-3000. The polyamide-imide resin provided by the invention has high strength, high heat resistance and good optical transmittance and solubility by simultaneously introducing the rigid aromatic structure and the fluorine-containing group into the main chain of the polymer, and can be used for an optical protection film of an organic photovoltaic device.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a transparent polyamide-imide resin, a preparation method thereof and an organic photovoltaic device containing the transparent polyamide-imide resin.
Background
Solar energy is used as a green and environment-friendly renewable energy source, and attracts more and more scientists and enterprises to see. As a next generation photovoltaic technology, the organic solar cell has the advantages of light weight, good flexibility, solution processing and the like, and becomes a hot spot of current research. However, the currently commercialized photovoltaic devices are still based on inorganic silicon solar cells, and an important reason why organic photovoltaic devices are not commercialized on a large scale is that they are poor in stability. Therefore, how to improve the stability of the organic photovoltaic device plays a vital role in commercialization of the organic photovoltaic device.
The polyamide imide (PAI) main chain not only contains polar functional group amide bond, but also has rigid imide ring, so that the polyamide imide not only has good solubility but also has higher thermal stability through molecular optimization design, and can be expected to be used for an optical protection film of an organic photovoltaic device.
Disclosure of Invention
The invention aims to provide a transparent polyamide-imide resin which has good solubility and thermal stability and can meet the requirements of a protective film for an organic photovoltaic device.
A second object of the present invention is to provide a method for producing the transparent polyamideimide resin.
A third object of the present invention is to provide an application of the transparent polyamideimide resin in the preparation of organic photovoltaic devices.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the present invention provides a transparent polyamideimide resin having the following repeating structural units:
n is a repeating structural unit and is 800-3000.
The second aspect of the present invention provides a method for preparing the transparent polyamideimide resin, comprising the steps of:
trimellitic anhydride (TMA) and m-toluidine (DP) in a molar ratio of 1 (0.3-1.5) (preferably 1:0.4) are dissolved in acetic acid (CH) 3 COOH) is slowly heated to 70-130 ℃ (preferably 90 ℃) under the nitrogen atmosphere, reacted for 5-24 hours (preferably 12 hours), the reaction solution is cooled to room temperature, and the diacid monomer TMA-DP is obtained by centrifugation;
dissolving diacid monomer TMA-DP with the molar ratio of 1 (5-15): 1 (preferably 1:9:1), compatibilizer, 2-bis (4-aminophenyl) hexafluoropropane (DFP) and excessive phosphorylating agent in a solvent, slowly heating to 70-130 ℃ (preferably 105 ℃) under nitrogen atmosphere, reacting for 5-24 hours (preferably 11 hours), pouring into ethanol for precipitation, filtering and drying to obtain the polyamide imide resin TMA-DP-DFP.
The solvent is N-methyl pyrrolidone.
The phosphorylating agent is triphenyl phosphite (TPP).
The compatibilizer is a mixture of calcium chloride and lithium chloride, and the molar ratio of the calcium chloride to the lithium chloride is 2:3.
In a third aspect, the present invention provides an application of the transparent polyamideimide resin in preparing organic photovoltaic devices.
The organic photovoltaic device comprises an anode, a cathode and an optical protection film, wherein the anode and the cathode are oppositely arranged, the optical protection film is positioned on the outer surface of the cathode, a hole transmission layer, an active material layer and an electron transmission layer are sequentially arranged between the anode and the cathode from top to bottom, and the optical protection film is made of polyamide imide resin TMA-DP-DFP.
The thickness of the optical protective film was about 30 μm.
The thickness of the hole transport layer was 20nm.
The thickness of the active material layer was 200nm.
The thickness of the electron transport layer was 20nm.
The thickness of the cathode is 100nm.
The thickness of the anode was 7 μm.
The hole transport layer is made of PEDOT and PSS, and the structures of the PEDOT and the PSS are as follows:
the active material layer is made of a donor material and an acceptor material, wherein the donor material is P3HT, PSBTBT, PBDB-T, the acceptor material is PCBM and IT-M, and the structural formula of the P3HT, PCBM, PSBTBT is shown as follows:
the electron transport layer is made of Ca and PFN-Br, and the PFN-Br has the following structure:
the cathode material is Al.
The anode material is ITO.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
according to the polyamide-imide resin provided by the invention, the fluorine-containing groups are introduced into the polymer main chain, so that the solubility of polyamide-imide can be improved, the charge transfer complex between molecules and in molecules can be weakened, and the optical transmittance of the resin can be improved. According to the polyamide-imide resin provided by the invention, a large number of rigid aromatic groups are introduced into the main chain of the polymer, so that the mechanical property of the resin can be improved, and the thermal stability of the resin can be improved.
The polyamide-imide resin provided by the invention has high strength, high heat resistance and good optical transmittance and solubility by simultaneously introducing the rigid aromatic structure and the fluorine-containing group into the main chain of the polymer, and can be used for an optical protection film of an organic photovoltaic device.
The polyamide imide resin provided by the invention is used for the protective film of the organic photovoltaic device, and has high strength, high heat resistance, good solubility and good optical transmittance by introducing the rigid aromatic structure and the fluorine-containing group into the polymer main chain at the same time, and can be used for the optical protective film of the organic photovoltaic device.
The transparent polyamide imide resin TMA-DP-DFP provided by the invention has the optical transmittance of 86% at 450nm, the tensile strength of 100MPa, the Young modulus of 1.84GPa, the initial decomposition temperature of 505 ℃ and can be dissolved in N, N-dimethylacetamide. Therefore, TMA-DP-DFP has both high strength and high heat resistance of polyimide resin and good solution processability of traditional optical protective film polyethylene terephthalate resin, and has excellent comprehensive performance. Further, the energy conversion efficiency of the organic photovoltaic device using TMA-DP-DFP as the optical protective film after acid-base treatment is more than 90% of that before acid-base treatment.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a polyamideimide resin TMA-DP-DFP synthesized in example 1;
FIG. 2 is an infrared spectrum of a polyamideimide resin TMA-DP-DFP synthesized in example 1;
FIG. 3 is a graph showing the light transmittance of the polyamideimide resin TMA-DP-DFP synthesized in example 1;
FIG. 4 is a schematic diagram showing stress-strain curves of the polyamideimide resin TMA-DP-DFP synthesized in example 1;
FIG. 5 is a thermogravimetric analysis spectrum of the polyamideimide resin TMA-DP-DFP synthesized in example 1;
FIG. 6 is a graph showing the thermal expansion coefficient of the polyamideimide resin TMA-DP-DFP synthesized in example 1.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental materials, reagents and the like used in the following experimental examples can be obtained by commercial methods or known experimental methods.
Example 1
A transparent polyamideimide resin having the following repeating structural units, which is designated as TMA-DP-DFP.
n is a repeating structural unit and is 800-3000.
A preparation method of transparent polyamide imide resin TMA-DP-DFP comprises the following steps:
(1) Synthesis of diacid monomer TMA-DP, the reaction can be represented by the following reaction formula:
to a 250ml three-necked flask, trimellitic anhydride TMA (9.6 g,0.05 mol), m-tolidine (DP) (4.24 g,0.02 mol) and 100ml acetic acid were charged, and the temperature was slowly raised to 90℃under a nitrogen atmosphere to react for 12 hours. The reaction solution was cooled to room temperature and centrifuged to give a white diacid monomer (TMA-DP) (25.26 g,0.045 mol), yield: 90.2%.
Nuclear magnetic and infrared data: 1 H NMR(Trifluoroacetic acid-d,500MHz,δ/ppm)：11.75(broad,COOH),8.82(d,2H),8.75-8.78(m,2H),8.31(d,2H),8.26(d,2H),7.43(d,2H),7.36-7.38(dd,2H),2.26(s,6H)。FTIR(KBr,ν,cm -1 )：3424，1780，1719，1686,1624，1610，1406，1376。
(2) Synthesis of transparent polyamideimide resin TMA-DP-DFP, the reaction can be represented by the following reaction formula:
a white diacid monomer TMA-DP (2.8 g,0.005 mol) was added to a 250mL three-necked flask equipped with a nitrogen inlet and outlet and a mechanical stirring device, and then 10mL N-methylpyrrolidone (NMP) was measured and added to the flask, followed by stirring at room temperature to dissolve. Adding CaCl 2 (2 g,0.018 mol), liCl (1.12 g,0.027 mol), 7mL of triphenyl phosphite (TPP) were added to the flask, followed by the final addition of 2, 2-bis (4-aminophenyl) hexafluoropropane (DFP) (0.835 g,0.005 mol) and 12mL of NMP. After the addition, slowly heating to 105 ℃ under the nitrogen atmosphere, reacting for 11 hours, pouring into ethanol for precipitation, filtering and drying to obtain the polyamide imide resin TMA-DP-DFP.
Nuclear magnetic and infrared data for transparent polyamideimide resin TMA-DP-DFP: as shown in FIGS. 1 and 2, FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of the polyamideimide resin TMA-DP-DFP synthesized in example 1. FIG. 2 is an infrared spectrum of a polyamideimide resin TMA-DP-DFP synthesized in example 1. 1 H NMR(Trifluoroacetic acid-d,500MHz,δ/ppm)：11.66(s,2H),8.77(s,2H),8.56-8.61(d,2H),8.42(d,2H),8.31(s,2H),8.25(d,2H),7.57-7.60(d,2H),7.39-7.44(dd,4H),7.31(d,4H),2.17-2.26(t,6H)。FTIR(KBr,ν,cm -1 ):3323,2929，2852，1781，1724，1671，1602，1372，1257，1207，1173。
The polyamide-imide resin TMA-DP-DFP prepared above was subjected to the following performance test, and the test results are shown in Table 1:
optical transmittance: the optical transmittance of TMA-DP-DFP is tested by an UltraScan PRO full-automatic color difference meter, the wavelength is selected to be 375-1000 nm, and the thickness of the film is 50 mu m.
Mechanical properties: the mechanical properties of TMA-DP-DFP were tested by WDT-10 electronic universal tester according to national standard GB/T1040.3-2006.
Thermal stability test: thermal stability testing of TMA-DP-DFP was performed on a TGA 4000 thermogravimetric analyzer from Perkinelmer, inc., U.S.A.. Specific parameter setting: sample mass: 40.2mg; test temperature: 30-800 ℃; rate of temperature rise: 10 ℃/min; test environment: and (3) nitrogen atmosphere.
Coefficient of thermal expansion test: coefficient of thermal expansion test of TMA-DP-DFP static stretching was performed on a DMA 8000-type thermo-mechanical analyzer from Perkinelmer, inc. of America. The heating rate is 5 ℃/min, the pre-load is 0.005N, the frequency is 1Hz, and the temperature is 30-300 ℃.
Specifically, as shown in FIG. 3, FIG. 4, FIG. 5, and FIG. 6, FIG. 3 is a schematic diagram showing the light transmittance curve of the polyamideimide resin TMA-DP-DFP synthesized in example 1. As can be seen from the figure, the polyamide imide resin TMA-DP-DFP prepared by the invention has good optical transmittance. FIG. 4 is a schematic diagram showing stress-strain curves of the polyamideimide resin TMA-DP-DFP synthesized in example 1. As can be seen from the figure, the polyamide imide resin TMA-DP-DFP prepared by the invention has higher mechanical strength. FIG. 5 is a thermogravimetric analysis of the polyamideimide resin TMA-DP-DFP synthesized in example 1. As can be seen from the figure, the polyamide imide resin TMA-DP-DFP prepared by the invention has higher thermal stability. FIG. 6 is a graph showing the thermal expansion coefficient of the polyamideimide resin TMA-DP-DFP synthesized in example 1. As can be seen from the figure, the polyamideimide resin TMA-DP-DFP prepared by the present invention has excellent thermo-mechanical properties.
TABLE 1
The transparent polyamideimide resin TMA-DP-DFP prepared as described above was subjected to a solubility test, and the test results are shown in Table 2:
solubility test conditions: 200 mg of the polyamideimide resin TMA-DP-DFP was put into 5 ml of a different solvent, which was designated "+", which was completely dissolved at room temperature, and "-", which was completely dissolved at 60 ℃. N, N-dimethylformamide is abbreviated as DMF and N, N-dimethylacetamide is abbreviated as DMAc.
TABLE 2
| Sample of | M-cresol | N-methylpyrrolidone | Tetrahydrofuran (THF) | DMAc | DMF |
| TMA-DP-DFP | + | + | + | + | — |
As can be seen from tables 1 and 2, TMA-DP-DFP synthesized by the method of the present invention has high mechanical strength and thermal stability, and good solubility and excellent comprehensive properties.
Application example 1
An organic photovoltaic device taking the polyamide-imide resin as a protective film comprises an anode, a cathode and an optical protective film, wherein the anode and the cathode are oppositely arranged, the optical protective film is positioned on the outer surface of the cathode, a hole transmission layer, an active material layer and an electron transmission layer are sequentially arranged between the anode and the cathode from top to bottom, the optical protective film is made of the polyamide-imide resin TMA-DP-DFP, and the thickness of the optical protective film is about 30 mu m; the thickness of the hole transport layer is 20nm; the thickness of the active material layer is 200nm; the thickness of the electron transport layer is 20nm; the thickness of the cathode was 100nm and the thickness of the anode was 7. Mu.m.
The preparation method of the organic photovoltaic device comprises the following steps:
in the first step, a PEDOT/PSS solution (mass ratio of PEDOT to PSS: 1:6) was spin-coated on a cleaned anode (ITO), and heated at 140℃for 10 minutes to form a PEDOT/PSS film as a hole transport layer having a thickness of 20nm.
The structures of PEDOT and PSS are as follows:
in a second step, donor material (P3 HT) and acceptor material (PCBM) in a mass ratio of 1:1 are dissolved in an o-dichlorobenzene solution at a total concentration of 40mg ml -1 The solution was spin-coated on a PEDOT: PSS film, and dried to form an active material layer having a thickness of 200nm. Wherein the structural formulas of P3HT and PCBM are as follows:
and thirdly, evaporating an electron transport layer (Ca) on the active material layer, wherein the thickness of the electron transport layer (Ca) is 20nm.
And fourthly, evaporating Al on the surface of the electron transport layer to form a cathode, wherein the thickness of the cathode is 100nm.
And fifthly, spin-coating a polyamide imide resin TMA-DP-DFP solution on the cathode to form an optical protection film with the thickness of 30 mu m, thereby obtaining the organic photovoltaic device.
Application example 2
The organic photovoltaic device is different from application example 1 in that the donor material in the active material layer is PSBTBT, and the rest conditions and the preparation method are the same as application example 1, wherein the structural formula of PSBTBT is as follows:
application example 3
An organic photovoltaic device differs from application example 1 in that the donor material in the active material layer is PBDB-T, the acceptor material is IT-M, the electron transport layer material is PFN-Br, and the electron transport layer is coated on the active material layer by spin coating, and the remaining conditions and preparation methods are the same as application example 1. Wherein the structural formulas of PBDB-T, IT-M and PFN-Br are as follows:
comparative example 1 was used
The difference from application example 1 is that application comparative example 1 has no optical protective film.
Comparative example 2 was used
The difference from application example 2 is that application comparative example 2 has no optical protective film.
Comparative example 3 was used
The difference from application example 3 is that application comparative example 3 has no optical protective film.
Comparative example 4 was used
The difference from application example 1 is that the optical protective film of application comparative example 4 is polyethylene terephthalate.
Comparative example 5 was used
The difference from application example 2 is that the optical protective film of application comparative example 5 is polyethylene terephthalate.
Comparative example 6 was used
The difference from application example 3 is that the optical protective film of application comparative example 6 is polyethylene terephthalate.
The following performance tests were conducted on the organic photovoltaic devices prepared in application examples 1 to 3 and application comparative examples 1 to 6, and the test results are shown in table 3:
under standard test conditions (AM 1.5G,100mW/cm 2 ) The organic photovoltaic devices provided in application examples 1 to 3 and application comparative examples 1 to 6 were subjected to current-voltage curve test, and the test results are shown in table 3. Wherein J SC Is short-circuit current, V OC Open circuit voltage, FF as a fill factor, PCE as energy conversion efficiency.
Acid resistance test: and (3) spin-coating an acid solution with the pH of 3 prepared by hydrochloric acid on the prepared organic photovoltaic device, taking out and drying, and testing the change of the photovoltaic performance of the organic photovoltaic device before and after the acid solution is spin-coated.
Alkali resistance test: and (3) spin-coating an alkaline solution with the pH of 12 prepared by sodium hydroxide on the prepared organic photovoltaic device, taking out and drying, and testing the change of the photovoltaic performance of the organic photovoltaic device before and after the spin-coating of the alkaline solution.
TABLE 3 Table 3
As can be seen from table 3, the performance parameters of the organic photovoltaic devices with optical protective films prepared in application examples 1 to 3 were comparable to those of the conventional organic photovoltaic devices without optical protective films prepared in application comparative examples 1 to 6. However, after acid-base treatment, the organic photovoltaic devices without the optical protective film prepared in comparative examples 1 to 3 were used to lose photovoltaic properties, the organic photovoltaic devices with polyethylene terephthalate as a protective film prepared in comparative examples 4 to 6 were used to lose photovoltaic properties, and the photovoltaic properties of the organic photovoltaic devices with polyamideimide resin TMA-DP-DFP as an optical protective film prepared in the invention were kept unchanged.
In conclusion, the polyamide-imide resin TMA-DP-DFP prepared by the invention has higher mechanical strength and thermal stability, has better solubility, namely excellent comprehensive performance, and can be used as an optical protection film of an organic photovoltaic device.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (10)
1. A transparent polyamideimide resin characterized by having the following repeating structural unit:
n is a repeating structural unit and is 800-3000.
2. A method for producing the transparent polyamideimide resin according to claim 1, comprising the steps of:
dissolving trimellitic anhydride and m-toluidine with the molar ratio of 1 (0.3-0.4) in acetic acid, slowly heating to 70-130 ℃ under the nitrogen atmosphere, reacting for 5-24 h, cooling the reaction solution to room temperature, and centrifuging to obtain diacid monomer TMA-DP;
dissolving diacid monomer TMA-DP with the molar ratio of 1 (5-15) to 1, compatibilizer, 2-bis (4-aminophenyl) hexafluoropropane and excessive phosphorylating agent in solvent, slowly heating to 70-130 ℃ under nitrogen atmosphere, reacting for 5-24 h, pouring into ethanol for precipitation, filtering and drying to obtain the polyamide-imide resin TMA-DP-DFP.
3. The method for producing a transparent polyamideimide resin according to claim 2, wherein the solvent is N-methylpyrrolidone;
the phosphorylating reagent is triphenyl phosphite;
the compatibilizer is a mixture of calcium chloride and lithium chloride, and the molar ratio of the calcium chloride to the lithium chloride is 2:3.
4. Use of the transparent polyamideimide resin of claim 1 in the preparation of organic photovoltaic devices.
5. The use of the transparent polyamideimide resin according to claim 4 for preparing an organic photovoltaic device, wherein the organic photovoltaic device comprises an anode, a cathode and an optical protection film positioned on the outer surface of the cathode, a hole transport layer, an active material layer and an electron transport layer are sequentially arranged between the anode and the cathode from top to bottom, and the optical protection film is made of polyamideimide resin TMA-DP-DFP.
6. The use of the transparent polyamideimide resin according to claim 5 for the preparation of an organic photovoltaic device, wherein the thickness of the optical protective film is 30 μm;
the thickness of the hole transport layer is 20nm;
the thickness of the active material layer is 200nm;
the thickness of the electron transport layer is 20nm;
the thickness of the cathode is 100nm;
the thickness of the anode was 7 μm.
7. The use of the transparent polyamideimide resin according to claim 5 for the preparation of organic photovoltaic devices, wherein the hole transport layer is made of PEDOT and PSS having the following structure:
8. the use of a transparent polyamideimide resin according to claim 5 for the preparation of organic photovoltaic devices, wherein the active material layer is made of a donor material, P3HT, PSBTBT, PBDB-T, and a acceptor material, PCBM, IT-M, the structural formula of P3HT, PSBTBT, PBDB-T, PCBM, IT-M being as follows:
9. the use of the transparent polyamideimide resin according to claim 5 for preparing organic photovoltaic devices, wherein the electron transport layer is made of Ca, PFN-Br, and the structure of PFN-Br is as follows:
10. the use of the transparent polyamideimide resin according to claim 5 for the preparation of organic photovoltaic devices, wherein the cathode material is Al; the anode material is ITO.
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| JP2012229402A (en) * | 2011-04-12 | 2012-11-22 | Toyobo Co Ltd | Method for producing polyamide-imide film |
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| CN102666659A (en) * | 2009-11-26 | 2012-09-12 | 株式会社钟化 | Optical film, optical film manufacturing method, transparent substrate, image display device, and solar cell |
| JP2012229402A (en) * | 2011-04-12 | 2012-11-22 | Toyobo Co Ltd | Method for producing polyamide-imide film |
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