CN114478291A - Preparation method of monomer diamine compound of polyimide - Google Patents
Preparation method of monomer diamine compound of polyimide Download PDFInfo
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- CN114478291A CN114478291A CN202210234439.5A CN202210234439A CN114478291A CN 114478291 A CN114478291 A CN 114478291A CN 202210234439 A CN202210234439 A CN 202210234439A CN 114478291 A CN114478291 A CN 114478291A
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- -1 diamine compound Chemical class 0.000 title claims abstract description 87
- 239000004642 Polyimide Substances 0.000 title claims abstract description 21
- 229920001721 polyimide Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 28
- FIBBSIRCVZWBML-UHFFFAOYSA-N 4-nitro-2-phenylphenol Chemical group OC1=CC=C([N+]([O-])=O)C=C1C1=CC=CC=C1 FIBBSIRCVZWBML-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 20
- 238000005886 esterification reaction Methods 0.000 claims abstract description 18
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- BOFRXDMCQRTGII-UHFFFAOYSA-N 619-08-9 Chemical compound OC1=CC=C([N+]([O-])=O)C=C1Cl BOFRXDMCQRTGII-UHFFFAOYSA-N 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 14
- DLJPNXLHWMRQIQ-UHFFFAOYSA-N 2-chloro-1-methoxy-4-nitrobenzene Chemical compound COC1=CC=C([N+]([O-])=O)C=C1Cl DLJPNXLHWMRQIQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 11
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000010511 deprotection reaction Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 6
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 4
- 230000001035 methylating effect Effects 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000012022 methylating agents Substances 0.000 claims description 9
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000007868 Raney catalyst Substances 0.000 claims description 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 2
- ATEPEOFRDZUVAG-UHFFFAOYSA-N ClP(C1(C(C=C(C=C1)N(C)C)C(C)(C)C)C(C)(C)C)Cl Chemical compound ClP(C1(C(C=C(C=C1)N(C)C)C(C)(C)C)C(C)(C)C)Cl ATEPEOFRDZUVAG-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 24
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 6
- 150000001875 compounds Chemical group 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 229940061334 2-phenylphenol Drugs 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- KJRJBBVVHYGROV-UHFFFAOYSA-N ClP(C1=CC=C(C=C1)N(C)C)(C(C)(C)C)(C(C)(C)C)Cl Chemical compound ClP(C1=CC=C(C=C1)N(C)C)(C(C)(C)C)(C(C)(C)C)Cl KJRJBBVVHYGROV-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of a monomer diamine compound of polyimide, which comprises the following steps: adding o-chloro-p-nitrophenol and a first inorganic base into a mixed system of dioxane and water, and then adding a methylating reagent for reaction, extraction and liquid separation to obtain an o-chloro-p-nitroanisole solution; adding potassium carbonate, phenylboronic acid and tetrabutylammonium bromide into an o-chloro-p-nitrotoluene ether solution to perform Suzuki coupling reaction, adding a second inorganic base for alkaline hydrolysis, and performing deprotection reaction to obtain 2-hydroxy 5-nitrobiphenyl; carrying out esterification reaction on 2-hydroxy 5-nitrobiphenyl, triethylamine, an esterification catalyst and p-nitrobenzoyl chloride to obtain 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester; and (3) carrying out hydrogenation reaction on the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester and the second reaction solvent. The preparation process of the invention adopts classical reaction and conventional operation, the reaction is safe and simple, and the high selectivity and high quality synthesis of the product are realized.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of a monomer diamine compound of polyimide.
Background
Generally, Polyimide (PI) resins have excellent mechanical strength, abrasion resistance, dimensional stability, corrosion resistance and other excellent properties in addition to high heat resistance, and are widely used in the field of electronic materials such as flexible printed circuit boards, and are widely used in advanced technical fields such as aviation, aerospace, construction, automobiles, separation membranes, nano-meter and laser in addition to the field of electronic devices, and thus have been receiving wide attention from researchers.
The most important raw materials for polyimides are aromatic diamines and aromatic dianhydrides, of which 4,4' -diaminodiphenyl ether (ODA) and 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) are the most widely used.
One new class of polyimide monomeric diamine compounds is currently available: 4-aminobenzoic acid-5-aminobiphenyl-2-yl phenol ester (4-Amino-benzoic acid 5-Amino-phenyl-2-yl ester) has also received much attention, and the compound structure thereof is shown below:
the molecular formula of the compound is C19H16N2O2CAS No.: 2152614-82-7.
Studies have shown that this compound results in improvements in many properties of the polyimide product compared to conventional diamine ODA use: the introduction of ester bonds reduces the toxicity of diamine compounds, and has low thermal expansion coefficient and low water absorption; the introduction of the phenyl group leads to the improvement of the solubility and the melt-forming property of the final product.
Japanese technology introduces a synthesis method of the compound, which takes 2-phenylphenol (CAS NO.90-43-7) as a raw material to carry out nitration reaction, esterification and hydrogenation, the first step of the technical route adopts nitration reaction, the selectivity of the reaction is poor, the yield is low, the post-treatment is complex, the amount of three wastes is large, and the quality of the product obtained according to the process can hardly meet the actual requirement.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a monomer diamine compound of polyimide, which solves the problems of complex preparation process and low yield existing in the preparation method of the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing a monomeric diamine compound of polyimide, comprising the steps of:
step 1: adding o-chloro-p-nitrophenol and a first inorganic base into a mixed system of dioxane and water, then adding a methylating reagent for reaction, and extracting and separating liquid to obtain an o-chloro-p-nitroanisole solution;
step 2: adding potassium carbonate, phenylboronic acid and tetrabutylammonium bromide into the o-chloro-p-nitrotoluene ether solution prepared in the step 1, performing Suzuki coupling reaction under the catalysis of a palladium catalyst, adding a second inorganic base after the reaction is finished, performing alkaline hydrolysis, and performing deprotection reaction to obtain 2-hydroxy-5-nitrobiphenyl;
and step 3: carrying out esterification reaction on the 2-hydroxy 5-nitrobiphenyl prepared in the step 2, an esterification catalyst and p-nitrobenzoyl chloride to obtain 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester;
and 4, step 4: and (3) carrying out hydrogenation reaction on the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester prepared in the step (3) and a second reaction solvent under the catalysis of a catalyst to prepare 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester.
Further, in the step 1, the o-chloro-p-nitrophenol and the first inorganic base are added into a mixed system of dioxane and water, the temperature is raised to 40-50 ℃, then the methylating agent is added, and the temperature is raised to 80-90 ℃ for heat preservation reaction.
Furthermore, in the step 1, after the methylating agent is added for reaction, the temperature of the reaction solution is adjusted to 30-60 ℃, and toluene is added for extraction.
Illustratively, in the step 1, the methylating agent is one of methyl iodide, dimethyl carbonate and dimethyl sulfate, preferably methyl iodide; the first inorganic base is one of sodium hydroxide, potassium carbonate, potassium hydroxide and sodium hydride, preferably potassium carbonate.
Further, in the step 2, after the deprotection reaction is finished, removing the lower-layer water phase, washing with water, cooling to 0-5 ℃ after washing with water, crystallizing, and filtering to obtain the 2-hydroxy 5-nitrobiphenyl.
Illustratively, the palladium catalyst in step 2 is one of palladium on carbon, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) dichloride, dichloro-di-tert-butyl- (4-dimethylaminophenyl) palladium (II), preferably tetrakis (triphenylphosphine) palladium (0); the second inorganic base is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.
Further, in the step 3, the 2-hydroxy 5-nitrobiphenyl and the esterification catalyst are firstly dissolved in the first reaction solvent, and then the paranitrobenzoyl chloride is added for reaction. Illustratively, the esterification catalyst is triethylamine or pyridine, preferably triethylamine; the first reaction solvent is one of DCM, DCE, acetonitrile and THF, preferably acetonitrile.
Further, after the esterification reaction in the step 3 is finished, cooling to below 0 ℃ for filtering, then adding water for pulping, performing suction filtration to obtain a pulped product, then adding ethanol into the pulped product for boiling and washing, and performing suction filtration to obtain the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester.
Further, after the hydrogenation reaction in the step 4 is finished, filtering and negative pressure concentrating are carried out, methanol is added for pulping, the temperature is reduced to 0-5 ℃, filtering and drying are carried out, and the 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester is obtained.
Illustratively, the catalyst in the step 4 is one of palladium carbon, raney nickel and platinum carbon, preferably palladium carbon; the second reaction solvent is one of methanol, ethanol, isopropanol, DMAC, THF, ethyl acetate and acetonitrile, and preferably isopropanol.
Compared with the prior art, the invention has the following beneficial effects: the preparation method of the monomer diamine compound of the polyimide avoids the problems of nitration reaction with high pollution and high risk, troublesome post-treatment and low yield, adopts the classical reaction and the conventional operation in the preparation process, has safe and simple reaction, realizes the synthesis of products with high selectivity and high quality, has high solubility and melt formability in an organic solvent, and provides a new choice for realizing the performance improvement of the polyimide compound.
Drawings
FIG. 1 is an MS spectrum of 2-hydroxy-5-nitrobiphenyl as an intermediate in the preparation process of the present invention;
FIG. 2 is an MS spectrum of 4-aminobenzoic acid-5 aminobiphenyl 2 phenol ester prepared by the present invention;
FIG. 3 is an HPLC chromatogram of 4-aminobenzoic acid-5 aminobiphenyl 2 phenol ester prepared according to the present invention.
Detailed Description
The invention discloses a preparation method of a monomer diamine compound of polyimide, which comprises the following steps:
more specifically, the present invention discloses a method for preparing a monomeric diamine compound of polyimide, comprising the steps of:
step 1: adding o-chloro-p-nitrophenol and a first inorganic base into a mixed system of dioxane and water, then adding a methylating reagent for reaction, and extracting and separating liquid to obtain an o-chloro-p-nitroanisole solution;
further, the mol ratio of the o-chloro-p-nitrophenol to the first inorganic base is 1:1-1.5, preferably 1: 1.2; the molar ratio of the o-chloro-p-nitrophenol to the methylating agent is 1:1-1.5, preferably 1: 1.3. The dioxane and the water are used as solvents, can be determined according to the adding amount and the solubility of the o-chloro-p-nitrophenol and the first inorganic base, and can be arranged in an excessive amount.
Further, in the step 1, adding o-chloro-p-nitrophenol and first inorganic base into a mixed system of dioxane and water, heating to 40-50 ℃, adding a methylating agent, heating to 80-90 ℃, and carrying out heat preservation reaction.
Furthermore, in step 1, after the methylation reagent is added to complete the reaction, the temperature of the reaction solution is adjusted to 30-60 ℃, and toluene is added to perform extraction. Specifically, the mass-to-volume ratio of the o-chloro-p-nitrophenol to the toluene is (1:3-5) kg/L, and preferably (1:4) kg/L.
In step 1, the methylating agent may be one of methyl iodide, dimethyl carbonate and dimethyl sulfate, preferably methyl iodide; the first inorganic base is one of sodium hydroxide, potassium carbonate, potassium hydroxide and sodium hydride, preferably potassium carbonate.
Step 2: adding potassium carbonate, phenylboronic acid and tetrabutylammonium bromide into the o-chloro-p-nitrotoluene ether solution prepared in the step 1, performing Suzuki coupling reaction in the presence of a palladium catalyst, adding a second inorganic base for alkaline hydrolysis after the reaction is finished, and performing deprotection reaction to obtain 2-hydroxy-5-nitrobiphenyl;
further, the mol ratio of the o-chloro-p-nitroanisole to the potassium carbonate is 1:1-1.5, preferably 1: 1.2; the mol ratio of the o-chloro-p-nitroanisole to the phenylboronic acid is 1:1-1.3, preferably 1: 1.1; the mol ratio of the o-chloro-p-nitroanisole to the tetrabutylammonium bromide is 1:0.1-0.5, preferably 1: 0.3; the mol ratio of the o-chloro-p-nitroanisole to the palladium catalyst is 1:0.0005-0.0015, preferably 1: 0.001; the mol ratio of the o-chloro-p-nitroanisole to the second inorganic base is 1:1.5-3, preferably 1: 2.
And further, in the step 2, alkaline hydrolysis is carried out, after deprotection reaction is finished, a lower-layer water phase is removed, water washing is carried out again, the temperature is reduced to 0-5 ℃ after water washing, crystallization is carried out, and the 2-hydroxy 5-nitrobiphenyl is obtained after filtration.
Illustratively, the palladium catalyst in step 2 is one of palladium on carbon, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) dichloride, dichloro-di-tert-butyl- (4-dimethylaminophenyl) palladium (II), preferably tetrakis (triphenylphosphine) palladium (0); the second inorganic base is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.
And step 3: carrying out esterification reaction on the 2-hydroxy 5-nitrobiphenyl prepared in the step 2, an esterification catalyst and p-nitrobenzoyl chloride to obtain 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester;
further, the mass volume ratio of the 2-hydroxy 5-nitrobiphenyl to the esterification catalyst is (1:5-10) kg/L, preferably (1:8) kg/L; the molar ratio of 2-hydroxy 5-nitrobiphenyl to p-nitrobenzoyl chloride is 1:1 to 1.5, preferably 1: 1.2.
Further, in the step 3, the 2-hydroxy 5-nitrobiphenyl and the esterification catalyst are firstly dissolved in the first reaction solvent, and then the p-nitrobenzoyl chloride is added for reaction. Illustratively, the esterification catalyst is triethylamine or pyridine, preferably triethylamine; the first reaction solvent is one of DCM, DCE, acetonitrile and THF, and acetonitrile is preferred.
Further, after the esterification reaction in the step 3 is finished, cooling to below 0 ℃, filtering, adding water for pulping, performing suction filtration to obtain a pulped product, adding ethanol into the pulped product for boiling and washing, and performing suction filtration to obtain the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester.
And 4, step 4: and (3) carrying out hydrogenation reaction on the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester prepared in the step (3) and a second reaction solvent in the presence of a catalyst to prepare 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester, namely the monomer diamine compound of the polyimide to be prepared.
Further, the mass volume ratio of the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenol ester to the second reaction solvent is (1:5-10) kg/L, preferably (1:8) kg/L; the mass ratio of the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenol ester to the palladium carbon is 1:0.005-0.02, and preferably 0.01.
Further, after the hydrogenation reaction in the step 4 is finished, filtering and concentrating under negative pressure, adding methanol for pulping, cooling to 0-5 ℃, filtering and drying to obtain the 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester.
Illustratively, the catalyst in step 4 is one of palladium carbon, raney nickel and platinum carbon, preferably palladium carbon; the second reaction solvent is one of methanol, ethanol, isopropanol, DMAC, THF, ethyl acetate and acetonitrile, and preferably isopropanol.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The embodiment discloses a preparation method of a monomer diamine compound of polyimide, which specifically comprises the following steps:
step 1: adding 174ml of water, 348ml of dioxane, 173.6g of o-chloro-p-nitrophenol and 165.6g of potassium carbonate into a reaction device in sequence, heating the system to 43 ℃, then adding 184.6g of methyl iodide, heating the system to 80-90 ℃ for heat preservation reaction, cooling the system to 40 ℃ after the reaction is finished, adding 348ml of water into the system, extracting and washing with water by using 695ml of toluene, separating liquid to obtain an o-chloro-p-nitrophenol methyl ether solution, wherein the content is 98.5% by HPLC (high performance liquid chromatography) detection, and the yield is 100%;
step 2: adding the p-o-chloro-p-nitrotoluene ether solution prepared in the step 1, 165.5g of potassium carbonate, 134.2g of phenylboronic acid and 96.7g of tetrabutylammonium bromide into a reaction device in sequence, adding 1.16g of tetrakis (triphenylphosphine) palladium (0) and 348ml of purified water, starting stirring, heating the system to 80 ℃ for reaction, keeping the temperature for 5 hours, cooling the system to 55 ℃ after the reaction is finished, adding 80g of sodium hydroxide into the system, continuously keeping the temperature for 55 ℃ for reaction for 5 hours, separating a lower aqueous phase from the system after the reaction is finished, washing the organic phase twice, cooling to 4 ℃, filtering and drying to obtain 182.5g of 2-hydroxy-5-nitrobiphenyl, wherein the content is 99.2% by HPLC (high performance liquid chromatography), and the yield is 84.8%;
and step 3: then taking another reaction device, sequentially adding 1460ml of acetonitrile, 182.5g of 2-hydroxy 5-nitrobiphenyl, 111.6g of triethylamine and 188.9g of p-nitrobenzoyl chloride, starting stirring, controlling the temperature of the system to be 45 ℃, preserving heat for reaction for 4 hours, finishing the reaction, cooling the system to 0 ℃, filtering and drying to obtain 265.4g of refined 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester, wherein the content is 99.5% by HPLC (high performance liquid chromatography), and the yield is 85.9%;
and 4, step 4: and (2) adding 2123ml of isopropanol into a reaction device again, sequentially adding 265.4g of 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester and 2.65g of palladium carbon, starting stirring, replacing the system with hydrogen twice, controlling the temperature of the system to carry out hydrogenation reaction at 35 ℃, reacting for 24 hours, filtering the system to remove the palladium carbon after the reaction is finished, carrying out organic phase decompression concentration, adding methanol to precipitate a product, drying to obtain 210.6g of fine 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester, wherein the content is 99.8% by HPLC (high performance liquid chromatography), and the yield is 95%.
Example two
This example discloses a method for preparing a monomeric diamine compound of polyimide, which includes the steps of:
step 1: adding 174ml of water, 348ml of dioxane, 173.6g of o-chloro-p-nitrophenol and 40.0g of sodium hydroxide into a reaction device in sequence, adjusting the temperature of the system to 40 ℃, adding 126.1g of dimethyl sulfate, heating the system to 80 ℃ for heat preservation reaction, cooling the system to 40 ℃ after the reaction is finished, adding 348ml of water and 695ml of toluene into the system for extraction and water washing, separating liquid to obtain an o-chloro-p-nitrophenol methyl ether solution, wherein the content is 97.8 percent through HPLC detection, and the yield is 100 percent;
step 2: adding 165.5g of p-o-chloro-p-nitrotoluene ether solution prepared in the step 1, 165.5g of potassium carbonate, 134.2g of phenylboronic acid and 96.7g of tetrabutylammonium bromide into a reaction device in sequence, adding 1.06g of palladium catalyst bis (triphenylphosphine) palladium (II) dichloride and 348ml of purified water, starting stirring, heating the system to 84 ℃ for reaction, keeping the temperature for reaction for 4.5h, cooling the system to 51 ℃ after the reaction is finished, adding 80.0g of sodium hydroxide into the system, keeping the temperature for reaction for 5h at 52 ℃, separating a lower water phase from the system after the reaction is finished, washing an organic phase twice, cooling to 2 ℃, filtering and drying to obtain 172.5g of 2-hydroxy-5-nitrobiphenyl, wherein the content is 99.1% through HPLC (high performance liquid chromatography), and the yield is 80.2%;
and step 3: adding excessive DCM 1380ml into another reaction device, adding 172.5g of 2-hydroxy 5-nitrobiphenyl, 81.1g of triethylamine and 148.8g of paranitrobenzoyl chloride, starting stirring, controlling the system temperature at 48 ℃, preserving heat for reaction for 4 hours, finishing the reaction, cooling the system to 3 ℃, filtering, drying to obtain 240.9g of refined 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester, wherein the content is 99.3 percent through HPLC (high performance liquid chromatography), and the yield is 82.5 percent;
and 4, step 4: pouring 1927ml of isopropanol serving as a solvent into a reaction device again, adding 240.9g of 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester and 4.8g of raney nickel, starting stirring, replacing the system with hydrogen twice, controlling the temperature of the system to carry out hydrogenation reaction at 38 ℃, reacting for 24 hours, filtering the system to remove raney nickel after the reaction is finished, carrying out reduced pressure concentration on the organic phase, adding methanol to precipitate a product, and drying to obtain 190.2g of refined 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester, wherein the content is 99.7% through HPLC detection, and the yield is 94.5%.
EXAMPLE III
This example discloses a method for preparing a monomeric diamine compound of polyimide, which includes the steps of:
step 1: adding excessive water 174ml and dioxane 348ml into a reaction device, uniformly stirring, sequentially adding 173.5g of o-chloro-p-nitrophenol and 84.0g of potassium hydroxide, adjusting the temperature of the system to 50 ℃, then adding 117.0g of dimethyl carbonate, heating the system to 90 ℃ for heat preservation reaction, cooling the system to 50 ℃ after the reaction is finished, adding 348ml of water and 695ml of toluene for extraction and washing, separating liquid to obtain an o-chloro-p-nitroanisole solution, wherein the content is 98.3% by HPLC (high performance liquid chromatography), and the yield is 100%;
step 2: adding the p-o-chloro-p-nitrotoluene ether solution prepared in the step 1, 165.5g of potassium carbonate, 134.2g of phenylboronic acid and 96.7g of tetrabutylammonium bromide into a reaction device in sequence, adding 0.71g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphorus palladium (II) and 348ml of purified water, starting stirring, heating the system to 80 ℃ for reaction, keeping the temperature for 5 hours, cooling the system to 55 ℃ after the reaction is finished, adding 84.0g of potassium hydroxide into the system, continuing keeping the temperature for reaction at 52 ℃ for 6 hours, separating a lower water phase out of the system after the reaction is finished, washing the organic phase twice, cooling to 5 ℃, filtering and drying to obtain 181.9g of 2-hydroxy-5-nitrobiphenyl, wherein the content is 99.1% by HPLC (high performance liquid chromatography), and the yield is 84.5%;
and step 3: and adding 1455ml of DCE into another reaction device, and then adding 181.9g of 2-hydroxy 5-nitrobiphenyl, 128.3g of triethylamine and 235.3g of p-nitrobenzoyl chloride. Starting stirring, controlling the temperature of the system to be 47 ℃, preserving heat for reaction for 5 hours, after the reaction is finished, cooling the system to be 3 ℃, filtering and drying to obtain 264.1g of refined 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenol ester, wherein the content is 99.5 percent through HPLC detection, and the yield is 85.7 percent;
and 4, step 4: pouring 2113ml of ethyl acetate serving as a solvent into a reaction device again, adding 264.1g of 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester and 5.28g of platinum carbon, starting stirring, replacing the system with hydrogen twice, controlling the temperature of the system to carry out hydrogenation reaction at 37 ℃, reacting for 20 hours, filtering the system to remove the platinum carbon after the reaction is finished, carrying out reduced pressure concentration on the organic phase, adding methanol to precipitate a product, drying to obtain 209.1g of refined 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester, wherein the content is 99.8 percent through HPLC detection, and the yield is 94.8 percent.
The MS spectrum of the intermediate product 2-hydroxy 5-nitrobiphenyl in the preparation process of the embodiment of the invention is shown in figure 1, and can be seen from the following:
the fragment information of the molecular ion peak in the GC-MS spectrogram is consistent with the GC-MS characteristic peak of the 2-hydroxy 5-nitrobiphenyl, which indicates that the 2-hydroxy 5-nitrobiphenyl prepared by the synthesis method has an accurate structure.
The MS spectrum and the HPLC spectrum of the finally prepared product 4-aminobenzoic acid-5-aminobiphenyl 2 phenol ester of the present invention are shown in fig. 2 and 3, respectively, from which it can be known that:
the fragment information of the molecular ion peak in a GC-MS spectrogram is consistent with the GC-MS characteristic peak of the 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester, so that the 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester synthesized by the method has a correct structure, and the HPLC spectrogram shows that the content of the 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester synthesized by the method exceeds 99.8 percent, and the use requirement of the polyimide monomer is met.
It should be noted that, in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for producing a monomeric diamine compound of polyimide, characterized by comprising the steps of:
step 1: adding o-chloro-p-nitrophenol and a first inorganic base into a mixed system of dioxane and water, then adding a methylating reagent for reaction, and extracting and separating liquid to obtain an o-chloro-p-nitroanisole solution;
and 2, step: adding potassium carbonate, phenylboronic acid and tetrabutylammonium bromide into the o-chloro-p-nitrotoluene ether solution prepared in the step 1, performing Suzuki coupling reaction under the catalysis of a palladium catalyst, adding a second inorganic base for alkaline hydrolysis after the reaction is finished, and performing deprotection reaction to obtain 2-hydroxy 5-nitrobiphenyl;
and step 3: carrying out esterification reaction on the 2-hydroxy 5-nitrobiphenyl prepared in the step 2, an esterification catalyst and p-nitrobenzoyl chloride to obtain 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester;
and 4, step 4: and (3) carrying out hydrogenation reaction on the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenolic ester prepared in the step (3) and a second reaction solvent under the catalysis of a catalyst to prepare 4-aminobenzoic acid-5-aminobiphenyl 2 phenolic ester.
2. The method according to claim 1, wherein in step 1, o-chloro-p-nitrophenol and the first inorganic base are added into a mixed system of dioxane and water, the temperature is raised to 40-50 ℃, the methylating agent is added, and the temperature is raised to 80-90 ℃ for the heat preservation reaction.
3. The method according to claim 1 or 2, wherein in the step 1, after the addition of the methylating agent is completed, the temperature of the reaction solution is adjusted to 30 to 60 ℃ and toluene is added for extraction.
4. The method of claim 1, wherein in step 1, the methylating agent is one of methyl iodide, dimethyl carbonate and dimethyl sulfate; the first inorganic base is one of sodium hydroxide, potassium carbonate, potassium hydroxide and sodium hydride.
5. The preparation method according to claim 1, wherein in the step 2, after the deprotection reaction is finished, the lower aqueous phase is removed, and then water washing is carried out, after the water washing is finished, the temperature is reduced to 0-5 ℃, crystallization is carried out, and the 2-hydroxy 5-nitrobiphenyl is obtained by filtering.
6. The method according to claim 1, wherein the palladium catalyst in step 2 is one of palladium on carbon, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) dichloride, dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphonium palladium (II); the second inorganic base is sodium hydroxide or potassium hydroxide.
7. The method according to claim 1, wherein in step 3, the 2-hydroxy-5-nitrobiphenyl and the esterification catalyst are dissolved in a first reaction solvent, and then p-nitrobenzoyl chloride is added to react, wherein the first reaction solvent is one of DCM, DCE, acetonitrile and THF.
8. The preparation method according to claim 1 or 7, wherein the esterification reaction in the step 3 is completed, the temperature is reduced to below 0 ℃, the filtration is performed, then water is added for pulping, the pumping filtration is performed to obtain a pulping product, ethanol is added into the pulping product for boiling and washing, and the pumping filtration is performed after the boiling and washing to obtain the 4-nitrobenzoic acid-5-nitrobiphenyl 2 phenol ester.
9. The preparation method according to claim 1, wherein the 4-aminobenzoic acid-5-aminobiphenyl 2 phenol ester is obtained by filtering, concentrating under negative pressure, pulping by adding methanol, cooling to 0-5 ℃, filtering and drying after the hydrogenation reaction in the step 4 is completed.
10. The method of claim 1 or 9, wherein the catalyst in step 4 is one of palladium on carbon, raney nickel, and platinum on carbon; the second reaction solvent is one of methanol, ethanol, isopropanol, DMAC, THF, ethyl acetate and acetonitrile.
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