CN116283614B - Preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane - Google Patents
Preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane Download PDFInfo
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- CN116283614B CN116283614B CN202310123033.4A CN202310123033A CN116283614B CN 116283614 B CN116283614 B CN 116283614B CN 202310123033 A CN202310123033 A CN 202310123033A CN 116283614 B CN116283614 B CN 116283614B
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- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 96
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 26
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- -1 bisphenol AF diazo compound Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000012954 diazonium Substances 0.000 claims abstract description 3
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- AHSWGWIUVXBWEE-UHFFFAOYSA-N (diazonioamino)benzene Chemical class N#[N+]NC1=CC=CC=C1 AHSWGWIUVXBWEE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 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
- 238000001035 drying Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000012467 final product Substances 0.000 abstract description 7
- 238000006396 nitration reaction Methods 0.000 abstract description 5
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 231100000171 higher toxicity Toxicity 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229920002577 polybenzoxazole Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which comprises the following steps: s1, diazotizing aniline and sodium nitrite under an acidic condition to form diazonium salt solution of aniline, and then performing coupling reaction with bisphenol AF to form an intermediate (I) bisphenol AF diazo compound S2, and reducing the intermediate (I) under the action of a catalyst through azo hydride to obtain 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The invention avoids dangerous nitration reaction, a large amount of acid waste water generated by nitration and hexafluoroacetone gas with higher toxicity are avoided, the byproduct aniline after hydrogenation can be recovered and can be continuously used in the first diazotization reaction, and two amino groups on the final product come from cheap sodium nitrite, so that the invention is more in line with atomic economy, the process is more environment-friendly, the hydrogenation condition is more moderate, and the catalyst can be repeatedly recovered and used.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
Background
2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, an ortho-aminophenol diamine monomer, a white solid, melt phase: 245-248 ℃, molecular formula: c (C) 15 H 12 F 6 N 2 O 2 Relative molecular weight: 366.26, cas No.: 617-475-0 are used in the polyimide and Polybenzoxazole (PBO) fields. The polybenzoxazole is a high-temperature-resistant aromatic heterocyclic polymer with a main chain containing benzoxazole fused heterocyclic repeating units, the polymer is a rod-shaped molecule, is not melted, is dissolved in strong acid such as concentrated sulfuric acid, methanesulfonic acid and the like, is insoluble in organic solvents, is incombustible, is oxidation-resistant, radiation-resistant, and has excellent electrical insulation and mechanical properties, and the working temperature is 300-350 ℃. Mainly preparing fiber, film and molecular composite material. Polybenzoxazole is also a lyotropic liquid crystalline polymer and can produce 10% strength anisotropic nematic in strong acidsA liquid crystal solution and then spinning or casting a film. The tensile strength and tensile modulus of the biaxially stretched film reach 2GPa and 270GPa. The density of the fibers was 1.52g/cm 3 Has excellent high temperature resistance, high strength and high modulus, the tensile modulus is more than 370GPa and is 2.5 times of that of the aramid fiber, and is greatly higher than aerospace carbon fiber, and is mainly used in the fields of structural materials of spaceship and airplane, electronic and electric parts and components and the like.
The presently disclosed synthetic methods of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane mainly include the following two methods:
method 1: for example, chinese patent (CN 111302944) discloses a method for preparing bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and chinese patent (CN 111592510) discloses a method for synthesizing 4,4- (hexafluoroisopropenylene) diphthalic anhydride. The synthesis method takes bisphenol AF as a raw material, and the final product is prepared by nitric acid nitration and then hydrogenation nitroreduction, which relates to a dangerous nitration process, and a large amount of acid wastewater can be generated in the nitration process, which is not friendly to the environment and is not suitable for long-term stable industrial production.
Method 2: for example, chinese patent (CN 114805094) discloses a process for preparing bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The synthesis method takes o-chlorophenol as a raw material, condenses with hexafluoroacetone, and performs ammoniation to prepare a final product, wherein hexafluoroacetone gas with high toxicity is used in the first step, a palladium ligand catalyst with high toxicity is used in the second step, the palladium ligand catalyst cannot be recycled and reused, and the conditions are harsh, for example, ammonia water closed tank reaction at 105 ℃ is needed, so that the synthesis method is not suitable for industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which aims to solve the problems of the prior art that the preparation method is dangerous, high in cost, harsh in reaction condition, complex in operation and the like.
In order to achieve the above object, the present invention provides a method for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, comprising the steps of:
s1, diazotizing aniline with sodium nitrite under an acidic condition to form diazonium salt solution of aniline, and then performing coupling reaction with bisphenol AF to form an intermediate (1), namely a bisphenol AF diazo compound:
s2, carrying out hydrogenation reduction on the intermediate (I) obtained in the step S1 under the action of a catalyst to obtain 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane:
preferably, the molar ratio of aniline to sodium nitrite is 1:0.95-1.05.
Preferably, the acid used in the acidic condition is 36% hydrochloric acid or 98% sulfuric acid; when 36% hydrochloric acid is used, the molar ratio of aniline to the hydrochloric acid is 1:2.0-3.0; when 98% sulfuric acid is used, the molar ratio of aniline to the sulfuric acid is 1:1.0-1.5.
Preferably, the molar ratio of bisphenol AF to aniline in the coupling reaction in the step S1 is 1:2.0-2.5; the alkali used in the coupling reaction is sodium hydroxide or potassium hydroxide, and the molar ratio of the alkali to bisphenol AF is 4-10:1.
Preferably, the diazotization reaction conditions in the step S1 comprise a temperature of 0-10 ℃; the conditions for the coupling reaction include a temperature of 0 to 20℃and a pH of 4 to 7.
Preferably, the solvent used for hydrogenation in the step S2 is methanol or ethanol, and the weight ratio of the solvent to the intermediate (I) is 3-10:1; the catalyst is palladium carbon or platinum carbon, and the weight ratio of the catalyst dosage to the intermediate (I) is 0.5% -5%;
preferably, in the step S2, the hydrogenation reduction condition includes that under the hydrogen atmosphere, the reaction is carried out at 60-70 ℃ and 0.3-0.5 MPa until no hydrogen is absorbed, and then the mixture is concentrated under reduced pressure and added into water for crystallization.
Preferably, the aniline recovery mode is 45-50 ℃ or below, the alcohol solvent is distilled off under reduced pressure, and the mixture is left to stand, and the lower aniline phase is separated to recover aniline.
Preferably, the preparation method of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane comprises the following steps:
s1: stirring and dissolving 0.759mol of sodium nitrite and 96g of water to obtain an aqueous solution of sodium nitrite; 0.773mol of aniline and 348g of water are added with stirring to 1.716mol of 36% concentrated hydrochloric acid until the aniline is dissolved; dropwise adding the sodium nitrite aqueous solution into aniline for dissolution at the temperature of 8-10 ℃ to obtain aniline diazonium salt solution; dripping aniline diazonium salt solution into a solution consisting of 0.365mol of bisphenol AF, 2.0mol of sodium hydroxide and 615g of water, after the reaction is finished, dripping 36% hydrochloric acid at the temperature of 10-20 ℃ until the pH value of an aqueous phase is 5-6, filtering, rinsing with water, adding 615g of methanol into a filter cake, pulping for 2.5 hours at room temperature, filtering, rinsing with methanol, and vacuum drying at the temperature of 75-80 ℃ to obtain an intermediate (I) bisphenol AF diazo compound;
s2, adding 887g of ethanol and 1.77g of 5% palladium-carbon into 0.325mol of intermediate (I) bisphenol AF diazo compound, replacing 3 times by nitrogen, replacing 3 times by hydrogen, reacting at 65-70 ℃ under 0.4-0.5 MPa until no hydrogen is absorbed, continuously maintaining the pressure for 30 minutes, replacing 3 times by nitrogen, filtering hydrogenation reaction liquid, collecting filtrate, concentrating under reduced pressure to about 350mL, adding into 887g of water, stirring for 30 minutes, filtering, rinsing with water, and drying in vacuum at 65-70 ℃ to obtain 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
Preferably, the preparation method of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane comprises the following steps:
s1, stirring and dissolving 0.759mol of sodium nitrite and 96g of water to obtain an aqueous solution of sodium nitrite; 0.794mol of aniline and 348g of water are added dropwise with stirring to 0.860mol of 98% sulfuric acid until the aniline is dissolved; dropwise adding the sodium nitrite aqueous solution into the aniline solution at the temperature of 0-10 ℃ and stirring to obtain brown transparent aniline diazonium salt solution; dropwise adding an aniline diazonium salt solution into a solution consisting of 0.365mol of bisphenol AF, 1.996mol of potassium hydroxide and 615g of water at the temperature of 0-10 ℃, and dropwise adding 98% sulfuric acid at the temperature of 0-20 ℃ until the pH of a water phase is reached: 4-7, filtering, rinsing with water, adding 615g of methanol, pulping for 2-3 hours at room temperature, filtering, rinsing with methanol, and vacuum drying for 12 hours at 70-80 ℃ to obtain a dark red intermediate (I) bisphenol AF diazo compound;
s2, adding 875g of methanol and 1.75g of 5% platinum carbon into 0.321mol of bisphenol AF diazo compound obtained in the step S1, using nitrogen to replace 3 times, using hydrogen to replace 3 times, reacting at 50-60 ℃ under 0.3-0.5 MPa until no hydrogen is absorbed, maintaining the pressure for 30 minutes, using nitrogen to replace 3 times, filtering hydrogenation reaction liquid, concentrating filtrate under reduced pressure to about 350mL, adding 875g of water, stirring until white solid is separated out, filtering, rinsing with water, and vacuum drying at 60-70 ℃ for 12 hours to obtain 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method avoids dangerous processes such as nitrification and the like in the existing preparation process, avoids a large amount of acid wastewater generated by nitrification, has mild reaction conditions, is easy to operate and is more environment-friendly.
(2) The byproduct aniline after hydrogenation can be recovered and can be continuously used in the first diazotization step, and two amino groups on the final product come from cheap sodium nitrite, so that the method is more in line with the atomic economy and the process is more green.
(3) The hydrogenation condition is mild, the catalyst can be repeatedly recycled, and the cost is saved.
(4) The invention realizes conversion through two steps of reactions, the two-step molar yield is 82%, the operation is simple, and the reaction is mild.
Drawings
FIG. 1 is a LC-MS spectrum of an intermediate produced by the preparation method of the present invention;
FIG. 2 is a LC-MS spectrum of the final product of the process of the present invention.
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited in any way.
Example 1:
step (1): sodium nitrite (52.4 g,0.759 mol), water (96 g) were added to a 250mL beaker and dissolved with stirring to obtain an aqueous sodium nitrite solution. Aniline (72 g,0.773 mol) and water (348 g) were added to a 1L three-necked flask (R1), and 36% concentrated hydrochloric acid (174 g, 1.716mol) was added thereto with stirring to dissolve the aniline. And (3) reducing the internal temperature of R1 to 0-5 ℃, controlling the internal temperature of R1 to 0-10 ℃, dripping the prepared sodium nitrite aqueous solution into R1, wherein the heat release is obvious, dripping is completed for about 2 hours, stirring is completed for 20 minutes, and obtaining brown transparent aniline diazonium salt solution, and storing at 0-10 ℃ for later use. Bisphenol AF (123 g,0.365 mol), sodium hydroxide (80 g,2.0 mol) and water (615 g) were added to a 2L three-necked flask (R2), and the mixture was stirred and dissolved, and the temperature was lowered to 0 to 5 ℃. And (3) controlling the internal temperature of R2 to be 0-10 ℃, dripping the prepared aniline diazonium salt solution into R2, slightly releasing heat, finishing dripping about 45 minutes, and stirring for 2-3 hours. Controlling the internal temperature of R2 to be 0-20 ℃, and dropwise adding 36% hydrochloric acid until the pH value of the water phase in R2 is: 4-7, after the dripping is finished, stirring for 30 minutes, and re-measuring the pH value to obtain a dark red solid-liquid mixture. The wet product was filtered and rinsed with a small amount of water. Returning the wet product to R2, adding methanol (615 g), pulping for 2-3 hours at room temperature, filtering, and rinsing the wet product with a small amount of methanol. The wet product is placed in an oven for vacuum drying at 70-80 ℃ for 12 hours, 177.4g of a dark red intermediate (I) bisphenol AF diazo compound is obtained, the purity is 99.3 percent, and the molar yield is 89.0 percent. As shown in figure 1, the characterization spectrogram of the bisphenol AF diazo compound of the intermediate (1) shows that the structure is correct in mass spectrum.
Step (2): adding the intermediate (I) bisphenol AF diazo compound (177.4 g,0.325 mol) obtained in the step (1) into a 2L stainless steel hydrogenation kettle, adding ethanol (887 g), 5% palladium-carbon (1.77 g), covering a kettle cover, screwing down a screw, using nitrogen to replace 3 times, using hydrogen to replace 3 times, reacting at 60-70 ℃ for about 3 hours under 0.3-0.5 MPa until no hydrogen is absorbed, continuously maintaining pressure for 30 minutes, removing residual hydrogen in the hydrogenation kettle, using nitrogen to replace 3 times, opening the kettle cover, filtering a hydrogenation reaction liquid, collecting a filtrate, singly collecting the filtered catalyst, and using the catalyst for the next batch reaction, concentrating the filtrate to about 350mL under reduced pressure, adding the filtrate into water (887 g), precipitating a large amount of white solid, stirring for 30 minutes, filtering the filter cake, using a small amount of water to rinse, placing a wet product in an oven at 60-70 ℃ for vacuum drying for 12 hours, obtaining a white final product 110.3g, wherein the purity is 99.7%, the step (2) has a total mole yield of 92.4% -mole percent, and the total yield is shown as a 2-hydroxy-2-3-phenyl-hexa-2-3-hydroxy-3-mole-3-phase spectrum.
And (3) aniline recovery: and (3) carrying out hydrogenation post-treatment on the mother liquor in the step (2), controlling the internal temperature to be lower than 50 ℃, decompressing and distilling ethanol to obtain a mixed solution of water and aniline, standing, separating out a lower aniline phase, and obtaining 57g of recovered aniline, wherein the recovery rate is: 79.1%.
Example 2:
step (1): sodium nitrite (52.4 g,0.759 mol), water (96 g) were added to a 250mL beaker and dissolved with stirring to obtain an aqueous sodium nitrite solution. The aniline (57 g,0.612 mol) recovered in example 1 and water (348 g) were charged into a 1L three-necked flask (R1), fresh aniline (17 g,0.182 mol) was added, 98% sulfuric acid (86 g,0.860 mol) was slowly dropped with stirring, and aniline and water were dissolved in each other. And (3) reducing the internal temperature of R1 to 0-5 ℃, controlling the internal temperature of R1 to 0-10 ℃, dripping the prepared sodium nitrite aqueous solution into R1, wherein the heat release is obvious, dripping is completed for about 2 hours, stirring is completed for 20 minutes, and obtaining brown transparent aniline diazonium salt solution, and storing at 0-10 ℃ for later use. Bisphenol AF (123 g,0.365 mol), potassium hydroxide (112 g,1.996 mol) and water (615 g) were put into a 2L three-necked flask (R2), and dissolved by stirring, and cooled to 0 to 5 ℃. And (3) controlling the internal temperature of R2 to be 0-10 ℃, dripping the prepared aniline diazonium salt solution into R2, slightly releasing heat, finishing dripping about 45 minutes, stirring for 2-3 hours, and finishing the intermediate reaction of the central control bisphenol AF and the single-side coupling. Controlling the internal temperature of R2 to be 0-20 ℃, and dripping 98% sulfuric acid until the pH value of the water phase in R2 is: 4-7, the dropping is finished and stirring is carried out for 30 minutes, and the pH is retested. A dark red solid-liquid mixture was obtained. The wet product was filtered and rinsed with a small amount of water. Returning the wet product to R2, adding methanol (615 g), pulping for 2-3 hours at room temperature, filtering, and rinsing the wet product with a small amount of methanol. The wet product is placed in an oven for vacuum drying at 70-80 ℃ for 12 hours, thus obtaining 175.1g of the dark red intermediate (I) bisphenol AF diazo compound with the purity of 99.1 percent and the molar yield of 87.9 percent.
Step (2): the intermediate (I) bisphenol AF diazo compound (175.1 g,0.321 mol) obtained in the step (1) is added into a 2L stainless steel hydrogenation kettle, methanol (875 g), 5% platinum carbon (1.75 g) is added, a kettle cover is covered, screws are screwed, nitrogen is used for replacing 3 times, hydrogen is used for replacing 3 times, the reaction is carried out for about 3 hours at 50-60 ℃ and 0.3-0.5 MPa without hydrogen absorption, and the pressure is kept for 30 minutes. And (3) discharging residual hydrogen in the hydrogenation kettle, replacing 3 times by using nitrogen, opening a kettle cover, filtering hydrogenation reaction liquid, collecting filtrate, and independently collecting the filtered catalyst, so that the catalyst can be used for the next batch of reaction. Concentrating the filtrate under reduced pressure to about 350mL, adding the concentrated filtrate into water (875 g), precipitating a large amount of white solid, stirring for 30 minutes, filtering, rinsing the filter cake with a small amount of water, and placing the wet product in an oven at 60-70 ℃ for vacuum drying for 12 hours to obtain 109.5g of white final product with the purity of 99.3%, wherein the molar yield of the step (2): 92.9%. The total molar yield of the two steps is: 81.6%.
And (3) aniline recovery: and (3) carrying out reduced pressure distillation on the mother liquor treated after hydrogenation in the step (2) by controlling the internal temperature below 50 ℃ to obtain a mixed mother liquor of water and aniline, standing for layering, separating an aniline phase, and obtaining 55g of recovered aniline, wherein the recovery rate is: 74.3%.
Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art without departing from the scope of the technology, or the technology can be modified to be equivalent. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which is characterized by comprising the following steps:
s1, diazotizing aniline with sodium nitrite under an acidic condition to form diazonium salt solution of aniline, and then carrying out coupling reaction with bisphenol AF to form an intermediate (I), namely a bisphenol AF diazo compound:
s2, carrying out hydrogenation reduction on the intermediate (I) obtained in the step S1 under the action of a catalyst to obtain 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane:
2. the process for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein the molar ratio of aniline to sodium nitrite is 1:0.95-1.05.
3. The process for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein said acid used under acidic conditions is 36% hydrochloric acid or 98% sulfuric acid; when 36% hydrochloric acid is used, the molar ratio of aniline to the hydrochloric acid is 1:2.0-3.0; when 98% sulfuric acid is used, the molar ratio of aniline to the sulfuric acid is 1:1.0-1.5.
4. The process for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein the molar ratio of bisphenol AF to aniline in the coupling reaction in step S1 is 1:2.0 to 2.5; the alkali used in the coupling reaction is sodium hydroxide or potassium hydroxide, and the molar ratio of the alkali to bisphenol AF is 4-10:1.
5. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein the diazotization reaction conditions in step S1 are at a temperature of 0 to 10 ℃; the condition of the coupling reaction is that the temperature is 0-20 ℃, and the pH is adjusted to 4-7.
6. The process for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein the solvent used for the hydrogenation in step S2 is methanol or ethanol, and the weight ratio of the solvent to the intermediate (I) is 3 to 10:1; the catalyst is palladium carbon or platinum carbon, and the weight percentage of the catalyst dosage and the intermediate (I) is 0.5% -5%;
7. the method for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein in the step S2, the hydrogenation and reduction conditions are that hydrogen is not absorbed in the atmosphere, the reaction is carried out at 60-70 ℃ and 0.3-0.5 MPa, and the mixture is concentrated under reduced pressure and then added into water for crystallization.
8. The process for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, further comprising a step of recovering aniline, wherein the recovery of aniline is 45 to 50 ℃ or lower, distilling the alcohol solvent under reduced pressure, standing, separating out a lower aniline phase, and recovering aniline.
9. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, comprising the steps of:
s1, stirring and dissolving 0.759mol of sodium nitrite and 96g of water to obtain an aqueous solution of sodium nitrite; 0.773mol of aniline and 348g of water are added with stirring to 1.716mol of 36% concentrated hydrochloric acid until the aniline is dissolved; dropwise adding the sodium nitrite aqueous solution into the aniline solution at the temperature of 8-10 ℃ to obtain aniline diazonium salt solution; dripping aniline diazonium salt solution into a solution consisting of 0.365mol of bisphenol AF, 2.0mol of sodium hydroxide and 615g of water, after the reaction is finished, dripping 36% hydrochloric acid at 10-20 ℃ until the pH of an aqueous phase is 5-6, filtering, rinsing with water, adding 615g of methanol, pulping for 2.5 hours at room temperature, filtering, rinsing with methanol, and vacuum drying at 75-80 ℃ to obtain an intermediate (I) bisphenol AF diazo compound;
s2, adding 0.325mol of an intermediate (I) bisphenol AF diazo compound into 887g ethanol and 1.77g 5% palladium-carbon, replacing 3 times by nitrogen, replacing 3 times by hydrogen, reacting at 65-70 ℃ under 0.4-0.5 MPa until no hydrogen is absorbed, maintaining the pressure for 30 minutes, replacing 3 times by nitrogen, filtering hydrogenation reaction liquid, collecting filtrate, concentrating under reduced pressure to about 350mL, adding into 887g water, stirring for 30 minutes, filtering, rinsing with water, and drying in vacuum at 65-70 ℃ to obtain 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
10. The method for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, comprising the steps of:
s1, stirring and dissolving 0.759mol of sodium nitrite and 96g of water to obtain an aqueous solution of sodium nitrite; 0.794mol of aniline and 348g of water are added dropwise with stirring to 0.860mol of 98% sulfuric acid until the aniline is dissolved; dropwise adding the sodium nitrite aqueous solution into the aniline solution at the temperature of 0-10 ℃ and stirring to obtain brown transparent aniline diazonium salt solution; dropwise adding an aniline diazonium salt solution into a solution consisting of 0.365mol of bisphenol AF, 1.996mol of potassium hydroxide and 615g of water at the temperature of 0-10 ℃, and dropwise adding 98% sulfuric acid at the temperature of 0-20 ℃ until the pH of a water phase is reached: 4-7, filtering, rinsing with water, adding 615g of methanol, pulping for 2-3 hours at room temperature, filtering, rinsing with methanol, and vacuum drying for 12 hours at 70-80 ℃ to obtain a dark red intermediate (I) bisphenol AF diazo compound;
s2, adding 875g of methanol and 1.75g of 5% platinum carbon into 0.321mol of bisphenol AF diazo compound obtained in the step S1, using nitrogen to replace 3 times, using hydrogen to replace 3 times, reacting at 50-60 ℃ under 0.3-0.5 MPa until no hydrogen is absorbed, maintaining the pressure for 30 minutes, using nitrogen to replace 3 times, filtering hydrogenation reaction liquid, concentrating filtrate under reduced pressure to about 350mL, adding 875g of water, stirring until white solid is separated out, filtering, rinsing with water, and vacuum drying at 60-70 ℃ for 12 hours to obtain 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
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