CN115894258B - Aromatic diamine monomer, and preparation and application thereof - Google Patents
Aromatic diamine monomer, and preparation and application thereof Download PDFInfo
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- CN115894258B CN115894258B CN202211383638.9A CN202211383638A CN115894258B CN 115894258 B CN115894258 B CN 115894258B CN 202211383638 A CN202211383638 A CN 202211383638A CN 115894258 B CN115894258 B CN 115894258B
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- aromatic diamine
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- phenanthrenehydroquinone
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- 239000000178 monomer Substances 0.000 title claims abstract description 63
- 150000004984 aromatic diamines Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 46
- 239000011737 fluorine Substances 0.000 claims abstract description 46
- 229920001721 polyimide Polymers 0.000 claims abstract description 38
- 239000004642 Polyimide Substances 0.000 claims abstract description 35
- -1 dinitro compound Chemical class 0.000 claims abstract description 20
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 19
- ODUSUXJNDWKJKH-UHFFFAOYSA-N phenanthrene-9,10-diol Chemical compound C1=CC=C2C(O)=C(O)C3=CC=CC=C3C2=C1 ODUSUXJNDWKJKH-UHFFFAOYSA-N 0.000 claims abstract description 13
- HQROXDLWVGFPDE-UHFFFAOYSA-N 1-chloro-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(C(F)(F)F)=C1 HQROXDLWVGFPDE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 9
- 150000004985 diamines Chemical class 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 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 description 21
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 20
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-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
- 230000035484 reaction time Effects 0.000 claims 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 abstract description 4
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 150000001925 cycloalkenes Chemical class 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 230000006978 adaptation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- AUPIFOPXTAGGSW-UHFFFAOYSA-N 4-[4-[9-[4-(4-aminophenoxy)phenyl]fluoren-9-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 AUPIFOPXTAGGSW-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water 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
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a fluorine-containing aromatic diamine monomer with a phenanthrene structure, which comprises the following steps: reacting 9, 10-phenanthrenehydroquinone with 2-chloro-5-nitrobenzotrifluoride under alkaline conditions to obtain a dinitro compound; further carrying out catalytic reduction on the dinitro compound to obtain the novel fluorine-containing aromatic diamine monomer. The obtained aromatic diamine monomer is used for preparing fluorine-containing polyimide, and is copolymerized with cycloolefin binary anhydride and 2- (4) -5-aminobenzimidazole to obtain a structure of a formula (I), and the obtained polyimide has the advantages of ultralow dielectric constant, high heat resistance, low expansion coefficient, high transparency, good fluidity (melt index) and the like by introducing fluorine-containing groups, large rigid side groups, alicyclic and hydrophobic functional structural units to perform synergistic action.
Description
Technical Field
The invention belongs to an aromatic diamine compound, a preparation method thereof and an application thereof in the field of preparing polyimide polymer materials.
Background
Polyimide is used as the material at the top of the pyramid, is the most high-temperature resistant polymer material in practical application at present, has high temperature resistance of more than 400 ℃, long-term use temperature of-200-300 ℃, has higher insulativity, and is applied to the fields of separation membranes, photoelectric functional materials, engineering plastics, aerospace military industry and the like. However, the rigid imide ring structure of the main chain makes dissolution and processing difficult, has higher hygroscopicity and higher dielectric constant, and limits the further development and high-end field application of the polyimide resin. Along with the development of the modern integrated circuit with 5G induction, the dielectric constant of an interlayer insulating material is required to be further reduced at a higher signal transmission speed, and the dielectric constant of the insulating material of the 5G millimeter wave integrated circuit is required to be less than 2, so that the design and synthesis of the novel polyimide with low dielectric constant and excellent dissolution processing performance have important strategic significance.
Fluorine atoms are introduced into the molecular structure of the fluorine-containing polyimide, so that the stacking efficiency is effectively reduced, the intermolecular spacing is increased, the intermolecular interaction force is weakened, the polymer solubility is improved, and the dielectric constant is reduced. In recent years, fluorine-containing polyimide becomes a research hot spot, various novel fluorine-containing diamine monomers and fluorine-containing dianhydride monomers are continuously appeared, but the dielectric constant of the material is still not smaller than 2, so that the polarization rate effect, the hydrophobicity effect and the free volume effect are comprehensively considered, and the fluorine-containing polyimide with the ultralow dielectric constant is obtained.
Currently, a great deal of work has been done with low dielectric polyimides:
Chinese patent application CN101113205A is polyimide obtained by copolymerizing 9, 9-bis [4- (4-aminophenoxy) phenyl ] fluorene and dianhydride, and large side groups are introduced into the molecular structure to break the regularity and symmetry of molecular chains, increase the molecular spacing, improve the solubility, reduce the dielectric constant to some extent, but still be more than or equal to 2.3.
Chinese patent application CN103408442A synthesizes monomer containing trifluoromethyl, diisopropyl and fluorenyl diamine, and then carries out copolymerization with dianhydride to obtain fluorine-containing polyimide, and fluorine-containing groups and large side groups are introduced to realize good film forming solubility and lower dielectric constant, but has poor transparency, dimensional stability and fluidity.
Chinese patent application CN105837819B obtains polyimide with trifluoromethyl and oligomeric silsesquioxane structure through polycondensation of 4,4' -diphenyl ether tetracarboxylic dianhydride and aromatic diamine monomer with trifluoromethyl structure, which improves the dissolution film forming property, dielectric property and optical transparency to a certain extent, but the addition of oligomeric silsesquioxane has the problems of uneven dispersion, poor fluidity and polymer mechanics defect.
Therefore, the prior art does not see an effective and feasible method to obtain the ultralow dielectric polyimide with high transparency, thermal stability, good fluidity and excellent processability.
Disclosure of Invention
The invention aims to provide an aromatic diamine monomer containing a bistrifluoromethyl group and a phenanthrene structure and a preparation method thereof. According to the monomer, the phenanthrene side group is introduced into the fluorine-containing diamine monomer for the first time, and can be connected into a polymer main chain through two amine functional groups to cooperatively regulate and control the structure and the performance of the polymer.
The invention also aims to provide the application of the aromatic diamine monomer in the field of preparing fluorine-containing polyimide. The prepared fluorine-containing polyimide has excellent dissolution processability, ultra-low dielectric constant, high heat resistance and stability, low expansion coefficient, high transparency, good fluidity and the like, and can be used as a modern microelectronic integrated circuit insulating material by copolymerizing the aromatic diamine monomer with alicyclic dianhydride and other diamine monomers, preferably 2- (4-) 5-aminobenzimidazole (2- (4-aminophenyl) -5-aminobenzimidazole) solution.
In order to achieve the above object, the present invention has the following technical scheme:
the invention provides an aromatic diamine monomer, which contains a bistrifluoromethyl and phenanthryl structure and has the structural formula as follows:
The invention also provides a preparation method of the aromatic diamine monomer, which comprises the following specific steps:
(1) Under the protection of nitrogen, 9, 10-phenanthrenehydroquinone and 2-chloro-5-nitrobenzotrifluoride are reacted for 8-24 hours at the temperature of 100-140 ℃ under the alkaline condition, the reaction is ended, reactants are poured into water, a large amount of solid powder is separated out, and the crude product is further recrystallized after suction filtration and drying to obtain a dinitro compound;
in the step (1), the alkaline condition is an alkaline condition system formed by dissolving potassium carbonate or sodium carbonate in an organic solvent, wherein the mass of the organic solvent is 2-4 times of the total mass of 9, 10-phenanthrenehydroquinone and 2-chloro-5-nitrobenzotrifluoride, and the mole number of the potassium carbonate or the sodium carbonate is 1.5-3.0 times of the mole number of the 9, 10-phenanthrenehydroquinone.
The organic solvent is selected from N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
Preferably, the solvent used for recrystallization is a mixed solvent of N, N-dimethylformamide and methanol, and the volume ratio of the N, N-dimethylformamide to the methanol in the mixed solvent is 3-5:1.
(2) And (3) reacting the fluorine-containing dinitro compound obtained in the step (1) with a catalyst and a reducing agent under a reflux condition, preferably for 4-20 h, and further recrystallizing the product to obtain the fluorine-containing diamine monomer.
In the step (2), the catalyst is palladium carbon with the mass fraction of 5% -10% of palladium, and the catalyst dosage is 1% -4% of the mass of the dinitro compound.
The reducing agent is hydrazine hydrate solution with the solute mass fraction of 80 percent, and the consumption of the hydrazine hydrate is 4-12 times of the mole number of the dinitro compound.
Preferably, the recrystallization solvent is ethanol, and the dosage is 5-10 times of the mass of the dinitro compound.
The specific synthetic route of the invention is shown in the following formula:
Based on the novel fluorine-containing diamine monomer, the invention designs and synthesizes the transparent, thermally stable, good in fluidity and excellent in processability ultralow dielectric fluorine-containing polyimide, and the specific steps for preparing polyimide by using the fluorine-containing diamine monomer include:
Under the protection of nitrogen, the fluorine-containing aromatic diamine monomer, alicyclic dianhydride and hydrophobic functional diamine monomer which are prepared by the invention are dissolved in a solvent which is preferably m-cresol or p-chlorophenol solvent, wherein the molar ratio of the two diamine monomers (aromatic diamine: 2- (4-) -5-aminobenzimidazole molar ratio=1:7-3:1) to alicyclic dianhydride monomer is 1:1-1.1, isoquinoline is added as a catalyst, water is carried by nitrogen flow, and after the reaction is carried out for 10-20 hours at 185-200 ℃, the reaction solution is poured into methanol or ethanol, thus obtaining the fibrous fluorine-containing polyimide polymer.
Preferably, the amount of m-cresol or p-chlorophenol is 4 to 6 times the total mass of diamine and dianhydride monomers.
The alicyclic dianhydride may be any of the following structures:
The hydrophobic functional diamine monomer can be any one of the following:
preferably, the isoquinoline is used in an amount of 2 to 4 times the moles of the two diamine monomers.
The structural formula of the ultralow dielectric fluorine-containing polyimide is
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a preparation method of a fluorine-containing diamine monomer containing a bistrifluoromethyl group and a phenanthrene structure, which has the advantages of simple synthetic route, relatively economical initial raw materials, easy purification and separation of products, stability at normal temperature, and capability of endowing new performances of fluorine-containing materials by introducing phenanthrene side groups into the fluorine-containing diamine monomer for the first time;
(2) The fluorine-containing polyimide is prepared by copolymerizing fluorine-containing diamine monomer containing double trifluoromethyl and phenanthrene structures and alicyclic dianhydride and 2- (4-) -5-aminobenzimidazole, and a rigid large-volume side group, a fluorine-containing structural unit, an alicyclic structure and a hydrophobic chain segment structure are introduced into the structure, wherein the rigid side group improves heat resistance, has a non-coplanar structure and increases free volume in a molecular structure; the alicyclic ring has low molar polarizability, breaks the planarity of a molecular chain, inhibits load transmission and is tightly packed; the fluorine structure and imidazole simultaneously provide strong hydrophobicity, so that the processability of the obtained polymer is improved, and the polymer has the characteristics of ultralow dielectric constant, high heat resistance, stability, low expansion coefficient, excellent fluidity and transparency.
Drawings
FIG. 1 is a 1 H NMR spectrum of a fluorine-containing diamine monomer.
Detailed Description
The following examples will further illustrate the method provided by the present invention for a better understanding of the technical solution of the present invention, but the present invention is not limited to the examples listed but should also include any other known modifications within the scope of the claims of the present invention.
The main raw material sources in the following examples and comparative examples are as follows:
a) 2-chloro-5-nitrobenzotrifluoride, 2- (4-) -5-aminobenzimidazole (2- (4-aminophenyl) -5-aminobenzimidazole) is purchased through aletin;
b) The alicyclic dianhydride monomer III can be selected from X15 in China patent CN 113024807;
c) 9, 10-phenanthrenehydroquinone is purchased through SAGECHEM;
d) Other common reagents used may be purchased commercially.
Preparing a fluorine-containing diamine monomer:
Example 1
(1) Adding 0.1mol of 9, 10-phenanthrenehydroquinone, 0.2mol of 2-chloro-5-nitrobenzotrifluoride, 0.15mol of potassium carbonate and 132g of N, N-dimethylformamide into a 250ml dry three-neck flask respectively, stirring at 100 ℃ for reaction for 24 hours, cooling, pouring into an ice-water bath, precipitating a large amount of yellow solid, and recrystallizing at 60 ℃ with a mixed solvent of N, N-dimethylformamide/methanol (volume ratio of 3:1) to obtain light yellow crystal powder which is a dinitro compound with the yield of 86%;
The melting point of the dinitro monomer is 206-209 ℃ (obtained by DSC test, and the temperature rising rate is high 10℃/min).FTIR(KBr)v/cm-1：2962,2923,2856(C-H),1532,1341(-NO2),1275(C-O-C),1149,1118(C-F).
(2) Adding 0.05mol of the dinitro compound obtained in the step (1), 0.5g of 5% (palladium mass fraction) palladium-carbon catalyst and 250ml of ethanol into a 500ml three-neck flask respectively, and heating to a reflux state under stirring; then 12.5g of 80% (solute mass fraction, the same applies below) hydrazine hydrate solution is dripped in a constant pressure dropping funnel for 30min, reflux reaction is continued for 20h, palladium carbon is removed by hot filtration, concentration and water precipitation are carried out, and the crude product is recrystallized by ethanol at 60 ℃ to obtain diamine monomer with the yield of 84%.
The diamine monomer has a melting point of 185-190 deg.C (obtained by DSC measurement), and a heating rate 10℃/min).FTIR(KBr)v/cm-1：3476,3390(-NH2),2968,2922,2876(C-H),1268,1229(C-O-C),1130(C-F).
Example 2
(1) Adding 0.1mol of 9, 10-phenanthrenehydroquinone, 0.23mol of 2-chloro-5-nitrobenzotrifluoride, 0.3mol of potassium carbonate and 218.25g of N, N-dimethylacetamide into a 250ml dry three-neck flask respectively, stirring at 140 ℃ for reaction for 10 hours, cooling, pouring into an ice-water bath, precipitating a large amount of yellow solid, and recrystallizing at 60 ℃ with a mixed solvent of N, N-dimethylformamide/methanol (volume ratio of 5:1) to obtain light yellow crystal powder which is a dinitro compound with the yield of 88%;
(2) Adding 0.05mol of the dinitro compound obtained in the step (1), 0.882g of 5% (palladium mass fraction) palladium-carbon catalyst and 250ml of ethanol into a 500ml three-neck flask respectively, and heating to reflux under stirring; then 25g of 80% hydrazine hydrate solution is dripped in a constant pressure dropping funnel for 30min, reflux reaction is continued for 15h, palladium carbon is removed by hot filtration, concentration and water precipitation are carried out, and the crude product is recrystallized by ethanol at 60 ℃ to obtain diamine monomer with the yield of 85%.
Example 3
1) Adding 0.1mol of 9, 10-phenanthrenehydroquinone, 0.21mol of 2-chloro-5-nitrobenzotrifluoride, 0.2mol of sodium carbonate and 273g of N-methylpyrrolidone into a 250ml dry three-neck flask respectively, stirring at 120 ℃ for reaction for 20 hours, cooling, pouring into an ice-water bath, precipitating a large amount of yellow solid, and recrystallizing at 60 ℃ with a mixed solvent of N, N-dimethylformamide/methanol (volume ratio of 4:1) to obtain light yellow crystal powder which is a dinitro compound with the yield of 87%;
(2) Adding 0.05mol of the dinitro compound obtained in the step (1), 1.176g of 10% (palladium mass fraction) palladium-carbon catalyst and 250ml of ethanol into a 500ml three-neck flask respectively, and heating to a reflux state under stirring; then, 37.5g of 80% hydrazine hydrate solution is dripped in a constant pressure dropping funnel for 30min, reflux reaction is continued for 4h, palladium carbon is removed by hot filtration, concentration and water precipitation are carried out, and the crude product is recrystallized by ethanol at 60 ℃ to obtain diamine monomer with the yield of 85%.
Preparation of a fluorine-containing polyimide polymer:
Example 1
Into a 50ml three-necked round bottom flask which was dried and purged with nitrogen gas, 2mmol (1.008 g) of the fluorine-containing diamine monomer obtained in example 1, 4mmol (1.752 g) of alicyclic dianhydride III and 2mmol (0.448 g) of 2- (4-) -5-aminobenzimidazole were added, 12.832g (4 times) of m-cresol and 8mmol (1.032 g) of isoquinoline were each added, and after the reaction system was heated to 185℃and stirred for 20 hours, the reaction was terminated and cooled to room temperature, and then the polymer solution was poured into an excessive amount of methanol to obtain a fibrous polyimide polymer, which was suction-filtered, washed and dried at 120℃for 24 hours to obtain a product A1.
FTIR (KBr) v/cm -1: 1780,1703 (c=o of imide ring), 1579,1452 (benzene ring skeleton), 1350 (C-N), 1170 (C-F), 769 (c=o).
Example 2
Into a 50ml three-necked round bottom flask which was dried and purged with nitrogen gas, 1mmol (0.504 g) of the diamine monomer obtained in example 2, 4.2mmol (1.840 g) of alicyclic dianhydride III and 3mmol (0.672 g) of 2- (4-) -5-aminobenzimidazole were added, 18.096g (6 times) of m-cresol and 12mmol (1.548 g) of isoquinoline were added respectively, the reaction system was heated to 190℃and stirred for 18 hours, after the reaction was completed and cooled to room temperature, the polymer solution was poured into methanol to obtain a fibrous polyimide polymer, which was suction-filtered, washed and dried at 120℃for 24 hours to obtain the product A2.
Example 3
Into a 50ml three-necked round bottom flask which was dried and purged with nitrogen gas, 3mmol (1.512 g) of the diamine monomer obtained in example 3, 4.4mmol (1.927 g) of alicyclic dianhydride III and 1mmol (0.2243 g) of 2- (4-) -5-aminobenzimidazole were added, 18.3165g (5 times) of m-cresol and 10mmol (1.29 g) of isoquinoline were added respectively, the reaction system was heated to 195℃and stirred for 15 hours, after the reaction was completed and cooled to room temperature, the polymer solution was poured into ethanol to obtain a fibrous polyimide polymer, which was suction-filtered, washed and dried at 120℃for 24 hours to obtain the product A3.
Example 4
Into a50 ml three-necked round bottom flask which was dried and filled with nitrogen gas, 0.5mmol (0.252 g) of the diamine monomer obtained in example 1, 4.3mmol (1.8834 g) of alicyclic dianhydride III and 3.5mmol (0.784 g) of 2- (4-) -5-aminobenzimidazole were added, 16.0567g (5.5 times) of m-cresol and 16mmol (2.064 g) of isoquinoline were added respectively, the reaction system was heated to 200℃and stirred for 10 hours, after completion of the reaction and cooling to room temperature, the polymer solution was poured into ethanol to obtain a fibrous polyimide polymer, which was suction-filtered, washed and dried at 120℃for 24 hours to obtain the product A4.
Comparative example 1
In a 50ml three-neck round bottom flask which is dried and filled with nitrogen, 4.3mmol (1.8834 g) of alicyclic dianhydride III and 4mmol (0.896 g) of 2- (4-) -5-aminobenzimidazole are added, 16.0567g of m-cresol and 16mmol (2.064 g) of isoquinoline are respectively added, the reaction system is heated to 200 ℃ and stirred for reaction for 10 hours, after the reaction is finished and cooled to room temperature, a polymer solution is poured into ethanol to obtain a fibrous polyimide polymer, and the fibrous polyimide polymer is subjected to suction filtration, washing and drying at 120 ℃ for 24 hours to obtain a product B1.
Comparative example 2
Into a 50ml three-neck round bottom flask which was dried and filled with nitrogen gas, 4mmol (2.016 g) of the diamine monomer obtained in example 1, 4.3mmol (1.8834 g) of alicyclic dianhydride III, 16.0567g of m-cresol and 16mmol (2.064 g) of isoquinoline were added respectively, the reaction system was heated to 200℃and stirred for 10 hours, after the reaction was completed and cooled to room temperature, the polymer solution was poured into ethanol to obtain a fibrous polyimide polymer, which was suction-filtered, washed and dried at 120℃for 24 hours to obtain a product B2.
Performance testing
1. Glass transition temperature test (T g, c):
taking 5-10 mg of fluorine-containing polyimide sample by a differential scanning calorimeter, placing the sample into a crucible pool, heating the sample from 30 ℃ to 400 ℃ at the speed of 10 ℃/min, and recording curve change.
2. Water absorption measurement:
And (3) soaking a fluorine-containing polyimide film sample (5 cm multiplied by 0.005 cm) in deionized water for 24 hours at room temperature, taking out the film sample, wiping and weighing the surface moisture, and calculating according to the weight difference before and after soaking to obtain the water absorption of the sample.
3. Coefficient of Thermal Expansion (CTE):
the thermal expansion coefficient of the film at 50-250 ℃ is measured by a thermo-mechanical analyzer (manufactured by TMA, TAInstrument company, model Q400) under the test condition of 5 ℃/min and is heated to 350 ℃. The temperature was raised and lowered three times, and the average value of the second and third times was calculated.
4. Visible light region transmittance:
The average light transmittance of the film in the wavelength range of 380 to 780nm was calculated by measurement with an ultraviolet spectrophotometer (model U-3900, manufactured by Hitachi Corp.).
5. Dielectric properties:
And (5) based on an Agilent 4294A impedance analyzer, testing the front and back metal spraying of the sample to manufacture an electrode.
6. Melt index:
the fluorine-containing polyimide product to be measured is placed in a small groove by adopting XNR-400W, after being heated to 320 ℃, the upper end is pressed downwards by a weight of 1.2Kg, and the weight of the product extruded within 10 minutes is measured.
7. Infrared spectroscopic analysis (FTIR):
The infrared analysis of the samples was performed using a Bruker Vertex 70 model infrared spectrometer from Bruker corporation.
The performance test results of the fluorine-containing polyimides prepared in examples and comparative examples are shown in Table 1.
TABLE 1 Performance test data sheet for fluorine-containing polyimides
As can be seen from the data in the table, by introducing fluorine atoms of high electronegativity, low polarizability; the phenanthrene type large-steric-hindrance side group damages the regularity of the molecular chain and prevents the molecular chain from being closely stacked; alicyclic dianhydride, inhibit the intramolecular electron conjugation; benzimidazole, rigid hydrophobic, co-construction of ultra-low dielectric fluorine-containing polyimide resin with ultra-high thermal stability, good fluidity, excellent processability and high transparency, can be applied to high-demand integrated circuit electronic devices and the like.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (14)
1. An aromatic diamine monomer, characterized in that: the aromatic diamine monomer contains a bistrifluoromethyl and phenanthrenehydroquinone structure, and the structural formula of the monomer is
2. The method for producing an aromatic diamine monomer according to claim 1, wherein: the preparation method comprises the following steps of
(1) Under the protection of nitrogen, reacting 9, 10-phenanthrenehydroquinone with 2-chloro-5-nitrobenzotrifluoride under alkaline conditions to obtain a fluorine-containing dinitro compound;
(2) And (3) reacting the fluorine-containing dinitro compound obtained in the step (1) with a catalyst and a reducing agent under a reflux condition to obtain the fluorine-containing aromatic diamine monomer.
3. The method according to claim 2, characterized in that: in the step (1), the mol ratio of the 9, 10-phenanthrenehydroquinone to the 2-chloro-5-nitrobenzotrifluoride is 1:2.0-2.3, and/or the reaction temperature is 100-140 ℃ and the reaction time is 8-24 h.
4. A method of preparation according to claim 2 or 3, characterized in that: the alkaline condition in the step (1) is that potassium carbonate or sodium carbonate is dissolved in an organic solvent to form an alkaline condition system, wherein the mass of the organic solvent is 2-4 times of the total mass sum of 9, 10-phenanthrenehydroquinone and 2-chloro-5-nitrobenzotrifluoride, and the mole number of the potassium carbonate or the sodium carbonate is 1.5-3.0 times of the mole number of the 9, 10-phenanthrenehydroquinone.
5. The method of manufacturing according to claim 4, wherein: the organic solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
6. A method of preparation according to claim 2 or 3, characterized in that: in the step (2), the catalyst is palladium carbon with the mass fraction of 5% -10% of palladium, and the catalyst dosage is 1% -4% of the mass of the fluorine-containing dinitro compound.
7. A method of preparation according to claim 2 or 3, characterized in that: in the step (2), the reducing agent is hydrazine hydrate solution with the solute mass fraction of 80%, wherein the amount of hydrazine hydrate is 4-12 times of the mole number of the fluorine-containing dinitro compound.
8. The process according to claim 2, wherein the reaction is carried out in step (2) under reflux conditions for 4 to 20 hours.
9. The use of an aromatic diamine monomer according to claim 1 or an aromatic diamine monomer produced by the production method according to any one of claims 2 to 8 for producing a fluorine-containing polyimide polymer having the structural formula,
10. The use of an aromatic diamine monomer according to claim 9, wherein: the preparation method of the fluorine-containing polyimide polymer comprises the following steps:
Under the protection of nitrogen, dissolving an aromatic diamine monomer, an alicyclic dianhydride monomer and a hydrophobic functional diamine monomer in a solvent, adding a catalyst, carrying out water through nitrogen flow, reacting for a period of time, and pouring the reaction solution into methanol or ethanol to obtain the fibrous fluorine-containing polyimide polymer.
11. The use according to claim 10, characterized in that: the hydrophobic functional diamine monomer is 2- (4-) -5-aminobenzimidazole.
12. The use according to claim 10, characterized in that: the aromatic diamine monomer and the alicyclic dianhydride monomer and the hydrophobic functional diamine monomer are dissolved in m-cresol or p-chlorophenol solvent.
13. The use according to claim 10, characterized in that: carrying out water by nitrogen flow, and reacting for 10-20 h at 185-200 ℃.
14. The use according to claim 10, characterized in that: isoquinoline is used as a catalyst, and the dosage of the isoquinoline is 2-4 times of the mole number of two diamine monomers; and/or the molar ratio of the aromatic diamine monomer to the hydrophobic functional monomer 2- (4-) -5-aminobenzimidazole to the alicyclic dianhydride monomer is 1:1-1.1; wherein the molar ratio of the aromatic diamine monomer to the 2- (4-) -5 aminobenzimidazole is 1:7-3:1.
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