CN115716990B - Diamine, preparation method thereof, polyimide film and preparation method thereof - Google Patents
Diamine, preparation method thereof, polyimide film and preparation method thereof Download PDFInfo
- Publication number
- CN115716990B CN115716990B CN202211475433.3A CN202211475433A CN115716990B CN 115716990 B CN115716990 B CN 115716990B CN 202211475433 A CN202211475433 A CN 202211475433A CN 115716990 B CN115716990 B CN 115716990B
- Authority
- CN
- China
- Prior art keywords
- formula
- diamine
- polyimide film
- iii
- dianhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 56
- 150000004985 diamines Chemical class 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 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 29
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- 229920005575 poly(amic acid) Polymers 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 5
- 230000009878 intermolecular interaction Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 238000001035 drying Methods 0.000 description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 239000004952 Polyamide Substances 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 6
- KQEIJFWAXDQUPR-UHFFFAOYSA-N 2,4-diaminophenol;hydron;dichloride Chemical compound Cl.Cl.NC1=CC=C(O)C(N)=C1 KQEIJFWAXDQUPR-UHFFFAOYSA-N 0.000 description 5
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 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 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- BBTGUNMUUYNPLH-UHFFFAOYSA-N 5-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 BBTGUNMUUYNPLH-UHFFFAOYSA-N 0.000 description 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229920001646 UPILEX Polymers 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a polyimide film, which is prepared from specific diamine and aromatic dianhydride. The application also provides a preparation method of the polyimide film. Further, the application also provides a diamine monomer and a preparation method thereof. According to the polyimide film, due to the introduction of the nitrogen-containing aromatic heterocyclic structure in the diamine, the rigidity of a polyimide molecular chain and intermolecular interaction are improved, so that the performance of the polyimide film is improved, and the polyimide film has extremely low thermal expansion coefficient and excellent mechanical property.
Description
Technical Field
The invention relates to the technical field of organic thin films, in particular to diamine, a preparation method thereof, a polyimide thin film and a preparation method thereof.
Background
Polyimide is a high-performance polymer containing imide ring structure in molecular chain, and has various synthesis and processing modes, and material forms including fiber, film, resin, foam and the like. The polyimide film has excellent high and low temperature resistance, insulating property, irradiation resistance and mechanical property, and is widely applied to the fields of national defense and military industry, electrical insulation, aerospace, microelectronics and the like. Currently commercialized polyimide film marks mainly include Kapton, upilex, apical and the like.
In recent years, along with the progress of technology, miniaturization and portability are the development directions of small intelligent electronic devices in the future. Organic Light Emitting Diodes (OLEDs) have advantages of light and thin profile, fast response, wide color gamut, high contrast, and flexibility, compared to Liquid Crystal Displays (LCDs), and have been increasingly replacing liquid crystal displays as the mainstream displays. Flexible OLED displays have the advantage of being lightweight, foldable and wearable, while flexible substrate materials are key to achieving flexible OLED displays.
The substrate material needs to bear the high temperature of 350-450 ℃ in the processing process of the low temperature polysilicon thin film transistor (LTPS-TFT); it is also desirable that the Coefficient of Thermal Expansion (CTE) be between 0 and 5ppm/K, matching with the inorganic components of the device, to avoid curling and cracking during processing due to thermal cycling, polyimide being the preferred polymeric material for flexible substrates due to its excellent thermal properties. The heat resistance of the current commercial polyimide film can basically meet the processing requirement of LTPS-TFT, but the CTE is more than 10ppm/K. In order to further improve the performance and yield of the OLED device, it is necessary to reduce the thermal expansion coefficient of the polyimide film.
Disclosure of Invention
The technical problem solved by the invention is to provide a polyimide film which has extremely low thermal expansion coefficient and excellent mechanical property.
In view of this, the present application provides a polyimide film prepared from an aromatic dianhydride and a diamine selected from one or more of structures shown as formula (III-1), formula (III-2), formula (III-3) and formula (III-4);
preferably, the aromatic dianhydride is selected from one or more of structures shown in a formula (IV 1), a formula (IV 2), a formula (IV 3), a formula (IV 4), a formula (IV 5), a formula (IV 6) and a formula (IV 7);
preferably, the molar ratio of the dianhydride to the aromatic diamine is 0.9:1 to 1:0.9.
The application also provides a preparation method of the polyimide film, which comprises the following steps:
mixing aromatic dianhydride and diamine in a solvent and then polymerizing to obtain polyamic acid solution;
the polyamic acid solution is cast into a film, and then is dried and thermally imidized in sequence to obtain a polyimide film;
the diamine is selected from one or more of structures shown as a formula (III-1), a formula (III-2), a formula (III-3) and a formula (III-4);
preferably, the molar ratio of the aromatic dianhydride to the diamine is 0.9:1 to 1:0.9.
Preferably, the polymerization temperature is-5-50 ℃ and the polymerization time is 5-108 h.
Preferably, the aromatic diamine is further selected from one or more of structures shown in formula (v 1), formula (v 2), formula (v 3) and formula (v 4);
wherein X is selected from O, S, sulfone, carbonyl or C (CF) 3 ) 2 ；
Y is selected from O, N or S.
The application also provides diamine which has a structure shown in a formula (III-1), a formula (III-2), a formula (III-3) or a formula (III-4);
the application also provides a preparation method of the diamine, which comprises the following steps:
mixing a compound shown in a formula (I) and a compound shown in a formula (II) in a solvent, and reacting after heating to obtain diamine;
wherein R is 1 And R is 2 Independently selected from carboxylic acids or acid chlorides.
Preferably, the solvent is selected from one or more of boric acid, polyphosphoric acid and concentrated sulfuric acid, and the reaction is performed in a reduction system; the molar ratio of the compound shown in the formula (I) to the compound shown in the formula (II) is 1:2.0 to 1.0:0.5.
the application provides a polyimide film, which is prepared from specific diamine and aromatic dianhydride, wherein the diamine contains nitrogen aromatic heterocyclic ring structure, so that the rigidity of a polyimide molecular chain and intermolecular interaction are improved, the performance of the polyimide film is improved, and the polyimide film has extremely low thermal expansion coefficient and excellent mechanical property.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a diamine monomer prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of a diamine monomer prepared in example 2 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of a diamine monomer prepared in example 3 of the present invention;
FIG. 4 is a DMA graph of the polyimide film prepared in example 4 of the present invention;
FIG. 5 is a TMA graph of a polyimide film prepared in example 4 of the present invention;
FIG. 6 is a graph showing the tensile-strain curves of the polyimide film prepared in example 4 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
In order to widen the application field of the polyimide film and improve the thermal expansion coefficient of the polyimide film, the application provides the polyimide film, which is prepared by introducing diamine with a specific structure, namely a nitrogen-containing heteroaromatic ring structure into a polyimide molecular main chain, so that the rigidity of molecular weight is improved, the intermolecular acting force is increased, and the polyimide has excellent heat resistance, dimensional stability and mechanical property. Specifically, the embodiment of the invention discloses a polyimide film, which is prepared from aromatic dianhydride and diamine, wherein the diamine is selected from one or more of structures shown in a formula (III-1), a formula (III-2), a formula (III-3) and a formula (III-4);
the diamine provided by the application has a nitrogen-containing heteroaromatic ring structure, which is beneficial to improving the rigidity of a molecular chain and intermolecular interaction force.
In the polyimide film provided by the application, the aromatic dianhydride is selected from one or more of structures shown in a formula (IV 1), a formula (IV 2), a formula (IV 3), a formula (IV 4), a formula (IV 5), a formula (IV 6) and a formula (IV 7);
wherein, the dianhydride of the structure of formula (IV 1) is called PMDA for short, the dianhydride of the structure of formula (IV 2) is called BPDA for short, the dianhydride of the structure of formula (IV 3) is called ODPA for short, the dianhydride of the structure of formula (IV 4) is called 6FDA for short, the dianhydride of the structure of formula (IV 5) is called BTDA for short, the dianhydride of the structure of formula (IV 6) is called HQDA for short, the dianhydride of the structure of formula (IV 7) is called BPADA for short, and the dianhydride monomer can be a commercial product or can be prepared according to the prior method.
In the present application, the diamine further includes one or more of structures shown as formula (v 1), shown as formula (v 2), shown as formula (v 3), and shown as formula (v 4);
wherein X is selected from O, S, sulfone, carbonyl or C (CF) 3 ) 2 ；
Y is selected from O, N or S.
The diamines mentioned above are well known to the person skilled in the art and can be added selectively, and can be prepared according to existing methods or can be commercially available products.
The molar ratio of the dianhydride to the aromatic diamine is 0.9: 1-1:0.9, specifically 1:1.
The application also provides a preparation method of the polyimide film, which comprises the following steps:
mixing aromatic dianhydride and diamine in a solvent and then polymerizing to obtain polyamic acid solution;
the polyamide acid solution is cast into a film, and then is dried, pressed by hot pressing and solidified in sequence to obtain a polyimide film;
the diamine is selected from one or more of structures shown as a formula (III-1), a formula (III-2), a formula (III-3) and a formula (III-4);
in the process of preparing the polyimide film, firstly, mixing aromatic dianhydride and diamine in a solvent and then polymerizing to obtain a polyamic acid solution; the solvent is selected from organic solvents well known to those skilled in the art for dissolving the raw materials, and specifically may be selected from aprotic solvents such as N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Dimethylsulfoxide (DMSO), and the like. The polymerization temperature is-5 to 50 ℃, more specifically, the polymerization time is 0 to 40 ℃; the polymerization time is 5 to 108 hours, more specifically, the polymerization time is 24 to 72 hours. The raw materials in the polymerization process are described in detail above, and will not be described in detail here.
The application then carries out curtain coating film forming and then sequentially drying and thermal imidization on the polyamic acid solution to obtain the polyimide film. The above-mentioned steps of casting into a film are well known to those skilled in the art, and the present application is not particularly limited, and the drying may be specifically performed in an oven, and the thermal imidization is performed at different temperatures and for different times, specifically 100 to 120 ℃/1h,150 to 200 ℃/1h,250 to 300 ℃/1h,350 to 380 ℃/1h,400 to 420 ℃/1h.
The present invention further provides a diamine having a structure represented by formula (III-1), formula (III-2), formula (III-3) or formula (III-4);
on the basis of the diamine, the application also provides a preparation method of the diamine, which comprises the following steps:
mixing a compound shown in a formula (I) and a compound shown in a formula (II) in a solvent, and reacting after heating to obtain diamine;
wherein R is 1 And R is 2 Independently selected from carboxylic acids or acid chlorides.
In the process of preparing diamine, the compound shown in the formula (I) and the compound shown in the formula (II) are mixed in a solvent, heated and reacted to obtain the diamine. In this process, the molar ratio of the compound represented by formula (I) to the compound represented by formula (II) is 1:2.0 to 1.0:0.5; the solvent is selected from one or more of boric acid, polyphosphoric acid and concentrated sulfuric acid, and the mass ratio of the solvent to the compound shown as the formula (II) is (5-15): 1, specifically, the mass ratio of the solvent to the compound shown as the formula (II) is (8-13): 1. the reaction is carried out in a reducing system, wherein the reducing system is selected from tin powder and/or stannous chloride, the molar amount of the reducing system is 5-30wt% of the compound shown as the formula (II), and specifically, the molar amount of the reducing system is 10-20wt% of the compound shown as the formula (II). After the reaction, phosphorus pentoxide is used as an absorbent in a molar amount of 0.5 to 2 times that of the compound represented by the formula (I), specifically in a molar amount of 1 to 1.5 times that of the compound represented by the formula (I). The reaction is carried out in an inert atmosphere, in particular under nitrogen or argon.
In order to further understand the present invention, the polyimide film and the preparation method thereof, the diamine and the preparation method thereof provided by the present invention are described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
Polyphosphoric acid (1000 g), 2, 6-pyridinedicarboxylic acid (33.424 g,0.2 mol), stannous chloride dihydrate (4.513 g,0.02 mol) and 2, 4-diaminophenol dihydrochloride (78.284 g,0.4 mol) were added in portions to a 2L three-necked flask, respectively, under nitrogen protection; after the charging is finished, stirring for 3 hours until HCl gas is not volatilized any more; after that, phosphorus pentoxide (P) is added 2 O 5 ) (28.3838 g,0.2 mol) for 0.5h; slowly heating to 150 ℃, stirring for 3 hours, heating to 200 ℃ and reacting for 10 hours; after the reaction is completed, cooling the solution to room temperature; then, the pH value of the solution is regulated to about 8-9 by using saturated sodium carbonate solution, the solution is respectively washed for three times by using water and ethanol, the crude product of diamine is obtained by filtering and drying, and the light yellow solid is obtained after purification, and the yield is 75%.
The nuclear magnetic hydrogen spectrum of the purified product is characterized, and the result is as follows, specifically shown in fig. 1: 1 H NMR(500MHz，DMSO)δ8.43(d，J＝7.9Hz，2H)，8.24(m，1H)，7.57(m，2H)，6.97(d，J＝2.1Hz，2H)，6.80(dd，J＝8.7，2.2Hz，2H)，5.23(s，4H)。
the molecular structure (III-1) of the diamine prepared in this example is as follows:
example 2
1000g of polyphosphoric acid (PPA) was added to a 2L three-necked flask, 2, 5-pyridinedicarboxylic acid (33.424 g,0.2 mol) and stannous chloride dihydrate (4.513g, 0.02 mol) were added to the polyphosphoric acid, and heated to 60℃with stirring; under the protection of nitrogen atmosphere, 2, 4-diaminophenol dihydrochloride (78.284 g,0.4 mol) is gradually added into the flask, and after the 2, 4-diaminophenol dihydrochloride is added, stirring is continued for 3 hours until HCl is not volatilized any more; then phosphorus pentoxide (P) is added 2 O 5 ) (28.3838 g,0.2 mol) and stirred for 0.5h. Then slowly heating to 150 ℃ and stirring for 3 hours, and then heating to 200 ℃ and reacting for 10 hours; gradually cooling to room temperature after the reaction is completed; then, the pH value of the solution is regulated to about 8-9 by using saturated sodium carbonate solution, the solution is respectively washed three times by using water and ethanol, the crude product of diamine is obtained by filtering and drying, and the light yellow solid is obtained after purification, and the yield is 71%.
The obtained product is subjected to nuclear magnetic characterization, and particularly as shown in fig. 2, the hydrogen spectrum results are as follows: 1 HNMR(500MHz，DMSO)δ9.43(dd，J＝2.1，0.7Hz，1H)，8.65(dd，J＝8.3，2.2Hz，1H)，8.44(dd，J＝8.3，0.6Hz，1H)，7.50(dd，J＝8.6，6.9Hz，2H)，6.94(dd，J＝6.1，2.1Hz，2H)，6.77(ddd，J＝15.0，8.7，2.2Hz，2H)，5.22(d，J＝2.5Hz，4H)。
the molecular structure (III-2) of the diamine prepared in this example is as follows:
example 3
Polyphosphoric acid was heated to 60℃after which 1000g of polyphosphoric acid (PPA) was added to a 2L three-necked flask, followed by 3, 5-pyridinedicarboxylic acid (33.424 g,0.2 mol) and stannous chloride dihydrate (4.513 g,0.02 mol) were added to the polyphosphoric acid, andheating to 60 ℃ and stirring; under the protection of nitrogen atmosphere, 2, 4-diaminophenol dihydrochloride (78.284 g,0.4 mol) is gradually added into the flask, and after the 2, 4-diaminophenol dihydrochloride is added, stirring is continued for 3 hours until HCl is not volatilized any more; then phosphorus pentoxide (P) is added 2 O 5 ) (28.3838 g,0.2 mol) for 0.5h; then slowly heating to 150 ℃ and stirring for 3 hours, and then heating to 200 ℃ and reacting for 10 hours; gradually cooling to room temperature after the reaction is completed; then, the pH value of the solution is regulated to about 8-9 by using saturated sodium carbonate solution, the solution is respectively washed three times by using water and ethanol, the crude product of diamine is obtained by filtering and drying, and the light yellow solid is obtained after purification, and the yield is 73%.
The purified product was subjected to nuclear magnetic characterization, as shown in fig. 3, and the hydrogen spectrum was as follows: 1 H NMR(500MHz，DMSO)δ9.42(d，J＝2.1Hz，2H)，9.00(t，J＝2.1Hz，1H)，7.51(d，J＝8.7Hz，2H)，6.94(d，J＝2.2Hz，2H)，6.76(dd，J＝8.7，2.2Hz，2H)，5.22(s，4H)。
the molecular structure (III-3) of the diamine prepared in this example is as follows:
example 4
To a three-necked flask equipped with mechanical stirring under nitrogen protection was added pyromellitic anhydride PMDA (1.53 g, 0.0070 mol), diamine of the structure shown in formula (III-1) in example 1 (2.40 g, 0.0070 mol), and solvent N, N-dimethylacetamide (35 g), which were reacted at 0℃for 72 hours to obtain a brown polyamic acid solution; coating polyamide acid on a clean glass plate, and drying and thermally imidizing to obtain a polyimide film; the thermal imidization process was 120℃C/1 h,150℃C/1 h,250℃C/1 h,350℃C/1 h,400℃C/1 h.
The properties of the polyimide film prepared in this example were examined, and the results of the examination are shown in FIGS. 4 and 5. As can be seen from FIGS. 4 and 5, the polyimide film prepared in example 4 has a glass transition temperature of more than 445℃and a Coefficient of Thermal Expansion (CTE) of 7.5ppm/K at 50 to 400℃and has a high glass transition temperature and a low coefficient of thermal expansion. Fig. 6 is a drawing-strain curve diagram of the polyimide film prepared in this example, and fig. 6 shows that different strains of the polyimide film under different drawing stresses can be obtained, and as can be seen from fig. 6, the polyimide film prepared in this application has better mechanical properties.
Example 5
3,3', 4' -biphenyltetracarboxylic acid dianhydride BPDA (2.06 g, 0.0070 mol), a diamine of the structure shown in the formula (III-1) in example 1 (2.40 g, 0.0070 mol), and a solvent N, N-dimethylacetamide 40g were charged into a three-neck flask equipped with mechanical stirring under nitrogen protection, and reacted at 0℃for 72 hours to obtain a brown polyamic acid solution; coating polyamide acid on a clean glass plate, and drying and thermally imidizing to obtain a polyimide film; the thermal imidization process was 120℃C/1 h,150℃C/1 h,250℃C/1 h,350℃C/1 h,400℃C/1 h.
Example 6
4,4' -oxydiphthalic anhydride ODPA (2.17 g, 0.0070 mol), a diamine of the structure shown in formula (III-1) in example 1 (2.40 g, 0.0070 mol), and solvent N, N-dimethylacetamide 40g were added to a three-neck flask equipped with mechanical stirring under nitrogen protection, and reacted at 0℃for 72 hours to obtain a brown polyamic acid solution; coating polyamide acid on a clean glass plate, and drying and thermally imidizing to obtain a polyimide film; the thermal imidization process was 120℃C/1 h,150℃C/1 h,250℃C/1 h,350℃C/1 h.
Example 7
Bisphenol A type diether dianhydride BPADA (3.64 g, 0.0070 mol), a diamine of the structure shown in formula (III-1) in example 1 (2.40 g, 0.0070 mol), and a solvent N, N-dimethylacetamide (54 g) were added to a three-necked flask equipped with mechanical stirring under nitrogen protection, and reacted at 0℃for 72 hours to obtain a brown polyamic acid solution; coating polyamide acid on a clean glass plate, and drying and thermally imidizing to obtain a polyimide film; the thermal imidization process was 120℃C/1 h,150℃C/1 h,250℃C/1 h,350℃C/1 h,400℃C/1 h.
Example 8
To a three-necked flask equipped with mechanical stirring under nitrogen protection was added pyromellitic anhydride PMDA (1.53 g, 0.0070 mol), diamine of the structure shown in formula (III-2) in example 2 (2.40 g, 0.0070 mol), and solvent N, N-dimethylacetamide 54g, which were reacted at 0℃for 72 hours to obtain a brown polyamic acid solution; coating polyamide acid on a clean glass plate, and drying and thermally imidizing to obtain a polyimide film; the thermal imidization process was 120℃C/1 h,150℃C/1 h,250℃C/1 h,350℃C/1 h,400℃C/1 h.
Example 9
3,3', 4' -biphenyltetracarboxylic acid dianhydride BPDA (2.06 g, 0.0070 mol), a diamine of the structure shown in the formula (III-2) in example 2 (2.40 g, 0.0070 mol), and a solvent N, N-dimethylacetamide 40g were charged into a three-neck flask equipped with mechanical stirring under nitrogen protection, and reacted at 0℃for 72 hours to obtain a brown polyamic acid solution; coating polyamide acid on a clean glass plate, and drying and thermally imidizing to obtain a polyimide film; the thermal imidization process was 120℃C/1 h,150℃C/1 h,250℃C/1 h,350℃C/1 h,400℃C/1 h.
Example 10
4,4' -oxydiphthalic anhydride ODPA (2.17 g, 0.0070 mol), the diamine of formula (III-2) of example 2 (2.40 g, 0.0070 mol), and solvent N, N-dimethylacetamide 40g were added to a three-neck flask equipped with mechanical stirring under nitrogen protection and reacted at 0℃for 72 hours to obtain a brown polyamic acid solution; the polyamide acid is coated on a clean glass plate, and is dried and thermally imidized to obtain the polyimide film. The thermal imidization process was 120℃C/1 h,150℃C/1 h,250℃C/1 h,350℃C/1 h.
Example 11
Bisphenol A type diether dianhydride BPADA (3.64 g, 0.0070 mol), a diamine of the structure shown in formula (III-2) in example 2 (2.40 g, 0.0070 mol), and a solvent N, N-dimethylacetamide (54 g) were added to a three-necked flask equipped with mechanical stirring under nitrogen protection, and reacted at 0℃for 72 hours to obtain a brown polyamic acid solution; coating polyamide acid on a clean glass plate, and drying and thermally imidizing to obtain a polyimide film; the thermal imidization process was 120℃C/1 h,150℃C/1 h,250℃C/1 h,350℃C/1 h,400℃C/1 h.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A polyimide film prepared from an aromatic dianhydride and a diamine selected from one or more of structures represented by formula (iii-1), formula (iii-2), formula (iii-3) and formula (iii-4);
2. the polyimide film according to claim 1, wherein the aromatic dianhydride is selected from one or more of structures shown in formula (iv 1), formula (iv 2), formula (iv 3), formula (iv 4), formula (iv 5), formula (iv 6) and formula (iv 7);
3. the polyimide film according to claim 1, wherein the molar ratio of the dianhydride to the aromatic diamine is 0.9:1 to 1:0.9.
4. The method for preparing a polyimide film according to claim 1, comprising the steps of:
mixing aromatic dianhydride and diamine in a solvent and then polymerizing to obtain polyamic acid solution;
the polyamic acid solution is cast into a film, and then is dried and thermally imidized in sequence to obtain a polyimide film;
the diamine is selected from one or more of structures shown as a formula (III-1), a formula (III-2), a formula (III-3) and a formula (III-4);
5. the process according to claim 4, wherein the molar ratio of the aromatic dianhydride to the diamine is 0.9:1 to 1:0.9.
6. The process according to claim 4, wherein the polymerization is carried out at a temperature of-5 to 50℃for a period of 5 to 108 hours.
7. The process according to claim 4, wherein the aromatic diamine is further selected from one or more of structures represented by the formula (V1), the formula (V2), the formula (V3) and the formula (V4);
wherein X is selected from O, S, sulfone, carbonyl or C (CF) 3 ) 2 ；
Y is selected from O, N or S.
8. The process according to claim 4, wherein the process for producing the diamine comprises the steps of:
mixing a compound shown in a formula (I) and a compound shown in a formula (II) in a solvent, and reacting after heating to obtain diamine;
wherein R is 1 And R is 2 Independently selected from carboxylic acids or acid chlorides.
9. The method of claim 8, wherein the solvent is selected from one or more of boric acid, polyphosphoric acid, and concentrated sulfuric acid, and the reaction is performed in a reduction system; the molar ratio of the compound shown in the formula (I) to the compound shown in the formula (II) is 1:2.0 to 1.0:0.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211475433.3A CN115716990B (en) | 2022-11-23 | 2022-11-23 | Diamine, preparation method thereof, polyimide film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211475433.3A CN115716990B (en) | 2022-11-23 | 2022-11-23 | Diamine, preparation method thereof, polyimide film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115716990A CN115716990A (en) | 2023-02-28 |
| CN115716990B true CN115716990B (en) | 2024-02-13 |
Family
ID=85256114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211475433.3A Active CN115716990B (en) | 2022-11-23 | 2022-11-23 | Diamine, preparation method thereof, polyimide film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115716990B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040164A (en) * | 2019-12-24 | 2020-04-21 | 威海新元科盛新材料有限公司 | Colorless transparent non-fluorine polyimide film with low thermal expansion coefficient and preparation method and application thereof |
| CN112048063A (en) * | 2020-09-04 | 2020-12-08 | 吉林奥来德光电材料股份有限公司 | High-performance transparent polyimide film and preparation method thereof |
| CN112500568A (en) * | 2020-12-24 | 2021-03-16 | 中国科学院长春应用化学研究所 | Polyimide film and preparation method thereof |
| CN112980014A (en) * | 2019-12-14 | 2021-06-18 | 上海市合成树脂研究所有限公司 | Blended polyimide film, preparation method thereof and application thereof in flexible display substrate |
| CN114015091A (en) * | 2021-11-12 | 2022-02-08 | 中国科学院长春应用化学研究所 | Polyimide film with low thermal expansion coefficient and preparation method thereof |
-
2022
- 2022-11-23 CN CN202211475433.3A patent/CN115716990B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112980014A (en) * | 2019-12-14 | 2021-06-18 | 上海市合成树脂研究所有限公司 | Blended polyimide film, preparation method thereof and application thereof in flexible display substrate |
| CN111040164A (en) * | 2019-12-24 | 2020-04-21 | 威海新元科盛新材料有限公司 | Colorless transparent non-fluorine polyimide film with low thermal expansion coefficient and preparation method and application thereof |
| CN112048063A (en) * | 2020-09-04 | 2020-12-08 | 吉林奥来德光电材料股份有限公司 | High-performance transparent polyimide film and preparation method thereof |
| CN112500568A (en) * | 2020-12-24 | 2021-03-16 | 中国科学院长春应用化学研究所 | Polyimide film and preparation method thereof |
| CN114015091A (en) * | 2021-11-12 | 2022-02-08 | 中国科学院长春应用化学研究所 | Polyimide film with low thermal expansion coefficient and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115716990A (en) | 2023-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102471861B1 (en) | Polyamic acid solution and transparent polyimide film using the same | |
| KR101385279B1 (en) | Asymmetric diamine compounds containing two functional groups, and polymers therefrom | |
| EP3290461B1 (en) | Polyimide resin and film using same | |
| CN111117241B (en) | High-transparency low-expansion polyimide film and preparation method thereof | |
| KR101506611B1 (en) | Polyimide Film | |
| Chung et al. | Novel organosoluble fluorinated polyimides derived from 1, 6-bis (4-amino-2-trifluoromethylphenoxy) naphthalene and aromatic dianhydrides | |
| JPH04325523A (en) | Manufacture of siloxane-modified polyimide resin | |
| KR20130076155A (en) | Manufacturing method of polyamic acid composition, polyamic acid composition, polyimide film and substrateused for display device using the same | |
| JP3702593B2 (en) | Fluorine-containing polyimide, substrate laminate and polyamic acid solution | |
| CN110818951A (en) | Modified graphene oxide, slurry, composite film, and preparation method and application thereof | |
| CN114349962A (en) | Low-dielectric-constant polyimide film and preparation method thereof | |
| CN115716990B (en) | Diamine, preparation method thereof, polyimide film and preparation method thereof | |
| KR101259543B1 (en) | Polyimide film having excellent heat-stability | |
| KR101232587B1 (en) | Polyimde Film and Method for Preparing the Same | |
| TW201815891A (en) | Method for preparing adamantane-containing polyimide having properties such as low dielectric constant, high glass transition temperature (Tg) and good processability | |
| JPH047333A (en) | New polyimide | |
| KR101248019B1 (en) | Polyimide film having excellent heat-stability and preparing thereof | |
| KR102439488B1 (en) | Method for producing polyimide film with excellent transparency and flexibility | |
| CN111234218B (en) | Preparation method of soluble polyimide containing amino phenylsulfonyl hexafluoropropane structure | |
| CN111574426B (en) | Diamine monomer containing isoindigo structure and black polyimide synthesized by diamine monomer | |
| KR101259544B1 (en) | Polyimide film | |
| KR102319883B1 (en) | Diamine compound, and polyimide precursor and polyimide film prepared by using the same | |
| CN112480093B (en) | Dianhydride containing amide and imide structures, and preparation method and application thereof | |
| KR101971078B1 (en) | Polyamic acid and polyimide | |
| JPS6119634A (en) | Production of organic solvent-soluble polyimide compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |