CN115636759A - 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
- Publication number
- CN115636759A CN115636759A CN202211330216.5A CN202211330216A CN115636759A CN 115636759 A CN115636759 A CN 115636759A CN 202211330216 A CN202211330216 A CN 202211330216A CN 115636759 A CN115636759 A CN 115636759A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- hexafluoropropane
- hydroxyphenyl
- bis
- amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002608 ionic liquid Substances 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 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 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000005086 pumping Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000012065 filter cake Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- NMRDKGOPQYFYTD-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-nitrophenyl)propan-2-yl]-2-nitrophenol Chemical compound C1=C([N+]([O-])=O)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C([N+]([O-])=O)=C1 NMRDKGOPQYFYTD-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- QEDSJDZDBAIVNZ-UHFFFAOYSA-N 2-methyl-1h-imidazole;trifluoromethanesulfonic acid Chemical group CC1=NC=C[NH2+]1.[O-]S(=O)(=O)C(F)(F)F QEDSJDZDBAIVNZ-UHFFFAOYSA-N 0.000 claims description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- XGBLLQBZRQMYNV-UHFFFAOYSA-N 1-butyl-3-methyl-2H-imidazole nitric acid Chemical compound [N+](=O)(O)[O-].C(CCC)N1CN(C=C1)C XGBLLQBZRQMYNV-UHFFFAOYSA-N 0.000 claims description 2
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical group CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 14
- 239000007791 liquid phase Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- WQGYMABSHOYZOQ-UHFFFAOYSA-N 3-propyl-1h-imidazol-3-ium;acetate Chemical compound CC([O-])=O.CCC[N+]=1C=CNC=1 WQGYMABSHOYZOQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- -1 1-butyl-4-methylpyridine hexafluorophosphate Chemical compound 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KUCWUAFNGCMZDB-UHFFFAOYSA-N 2-amino-3-nitrophenol Chemical compound NC1=C(O)C=CC=C1[N+]([O-])=O KUCWUAFNGCMZDB-UHFFFAOYSA-N 0.000 description 1
- NYWFUNWSRZTOJX-UHFFFAOYSA-N FC(S(=O)(=O)O)(F)F.C(CCC)N1CC=C(C=C1)C Chemical compound FC(S(=O)(=O)O)(F)F.C(CCC)N1CC=C(C=C1)C NYWFUNWSRZTOJX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000000850 deacetylating effect Effects 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which comprises the following steps: adding phenol into the ionic liquid A, then heating to 100 ℃, dropwise adding hexafluoroacetone hemihydrate, then heating for reaction until the reaction of the raw materials is finished, and obtaining bisphenol AF; step two: respectively pumping concentrated nitric acid and an ionic liquid B solution containing bisphenol AF into a pipeline type reactor by using a metering pump under a heating condition according to two feeding modes, and performing complete reaction and post-treatment to obtain 6FNP; step three: and (2) adding a porous nano palladium catalyst into a fixed bed by adopting a fixed bed reactor, dissolving 6FNP into the ionic liquid C, introducing hydrogen, and carrying out reaction post-treatment to obtain the product. The invention keeps the original yield, eliminates the danger, and simultaneously adopts automatic equipment to replace manpower, thereby further reducing the production cost; and in addition, the ionic liquid is used for replacing the conventional solvent in each step, so that the solvent is easy to recycle, and the solvent loss and the environmental pollution are reduced.
Description
Technical Field
The invention belongs to the technical field of synthesis of polyimide monomers, 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 (hereinafter referred to as 6 FAP), white crystalline solid, non-toxic, as a monomer for preparing polyimide special high molecular functional materials, polymers which can maintain mechanical properties such as rigidity, tensile strength and the like and electrical properties and the like at high temperature, and are mainly used as raw materials of heat-resistant polymers, especially electronic materials, such as raw materials of computer chips and the like.
The preparation method of 6FAP has a plurality of published routes, and the following methods are mainly disclosed: 1. reacting bisphenol AF serving as a raw material with dinitrogen pentoxide or nitric acid in dichloroethane to obtain 6FNP; 2. bisphenol AF is used as a raw material, firstly, the bisphenol AF reacts with nitric phosphate to obtain 6FNP, and then 6FAP is obtained through reduction of zinc powder, wherein the total yield of the two steps is 96%; 3. acetylating o-aminophenol serving as a raw material, then reacting with hexafluoroacetone, and finally deacetylating to obtain 6FAP, wherein the total yield of the three steps is 78.89%; 4. halogen benzene is used as a raw material, firstly, halogen bisphenol AF is obtained by reacting with hexafluoroacetone, then, 2-bis (3-amino-4-halogen phenyl) hexafluoropropane is obtained by nitration, then, 6FNP is obtained by reacting with strong base, and finally, 6FAP is obtained by hydrogenation reduction, wherein the total yield of the four steps is 69%.
In the above method, the conventional nitrification and hydrogenation methods are the most convenient and fast methods with the highest yield, but the two reactions are easy to generate uncontrollable safety accidents such as deflagration and the like, and the nitrification and hydrogenation processes are listed in 18 dangerous chemical process catalogues which are mainly regulated by the national safety supervision administration, so the kettle type nitrification and hydrogenation reaction is about to be forbidden and eliminated. While other routes, which avoid hazardous processes, involve multiple reactions, resulting in reduced yields.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which can reduce production safety and improve product yield.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane comprises the following three steps:
the method comprises the following steps: adding phenol into the ionic liquid A, then heating to 100 ℃, dropwise adding hexafluoroacetone hemihydrate, then heating for reaction until the raw materials are reacted, cooling, adding the reaction solution into water, filtering, recovering the ionic liquid A from the water phase, and washing the filter cake with water to obtain bisphenol AF;
step two: adopting a pipeline reactor, firstly adding bisphenol AF into ionic liquid B, then setting the flow rate and the residence time, and respectively pumping concentrated nitric acid and ionic liquid B solution containing bisphenol AF into the pipeline reactor by using a metering pump according to a two-strand feeding mode under a heating condition; the materials completely react in the pipeline type reactor and then flow into a receiving bottle filled with distilled water, the materials are filtered, the ionic liquid B is recovered from the filtrate, and 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane, referred to as 6FNP for short, is obtained after the filter cake is washed with water;
step three: adopting a fixed bed reactor, firstly adding a porous nano palladium catalyst into the fixed bed, then dissolving 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane into an ionic liquid C, adjusting the flow rate, simultaneously introducing hydrogen, setting the pressure and the retention time, after complete reaction, allowing the reaction liquid to flow into a receiving bottle through an outlet, adding ionic resin, and filtering; then adding ultrapure water, separating out a product, filtering, recovering the ionic liquid C from the filtrate, washing the filter cake with water, and refining the filter cake with a solvent to obtain a pure product 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which is called 6FAP for short.
Further, the ionic liquid a, the ionic liquid B and the ionic liquid C used in the three steps are any one of imidazole type, pyridine type, piperidine type, quaternary ammonium salt type and morpholine type.
Further, the ionic liquid A, the ionic liquid B and the ionic liquid C used in the three steps are imidazole type.
Further, the ionic liquid A in the step one is methylimidazole trifluoromethanesulfonic acid, the ionic liquid B in the step two is 1-butyl-3-methylimidazole nitrate, and the ionic liquid C in the step three is 1-ethyl-3-methylimidazole acetate.
Further, the molar ratio of phenol to hexafluoroacetone hemihydrate in the first step is 1: (1-3), preferably in a molar ratio of 1:2; the mass ratio of phenol to ionic liquid A is 1: (4-8), preferably 1:6.
further, the reaction temperature in the first step is 150-200 ℃, preferably 180 ℃.
Further, the flow rate of the ionic liquid B solution containing bisphenol AF in the second step is as follows: 5-20g/min, preferably 10g/min.
Further, the residence time of the materials in the second step in the channel of the pipeline reactor is 100-600s, preferably 420s; the reaction temperature is 5 to 60 ℃ and preferably 45 ℃.
Further, the flow rate of the ionic liquid C containing the 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane in the third step is 5 to 15g/min, preferably 10g/min; the flow rate of the hydrogen is 1000-1500ml/min, preferably 1200ml/min; the pressure is 0.1-5MPa, preferably 1MPa.
Further, the residence time of the materials in the third step in the channel of the fixed bed reactor is 100-600s, preferably 300s.
Compared with the prior art, the preparation method of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane has the following advantages:
the nitration dangerous process related in the prior art is changed into a pipeline type reactor for carrying out; the hydrogenation process is changed into a fixed bed reactor, the changed process not only keeps the original yield, but also eliminates the danger, and meanwhile, automatic equipment is adopted to replace the labor, so that the production cost is further reduced; and in the second step, the ionic liquid is used for replacing the conventional solvent, so that the solvent is easy to recycle, and the solvent loss and the environmental pollution are reduced.
Drawings
FIG. 1 is a liquid phase diagram of bisphenol AF in example 1;
FIG. 2 is a liquid phase diagram of 6FNP in example 1;
fig. 3 is a liquid phase diagram of 6FAP in example 1;
fig. 4 is a nuclear magnetic diagram of 6FAP in example 1.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are all conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Example 1:
step one, preparation method of bisphenol AF
Adding 47g of phenol into 282g of ionic liquid A methylimidazole trifluoromethanesulfonic acid, then heating to 100 ℃, dropwise adding 184g of hexafluoroacetone hemihydrate, then heating to 180 ℃ for reaction until the reaction of the raw materials is finished. Cooling, adding the reaction solution into water, filtering, and recovering the ionic liquid A from the water phase; the filter cake was washed with water and dried to give 80.2g of bisphenol AF as an off-white powder. Yield: 95.48 percent and 99.14 percent (see figure 1).
Step two, 6FNP (2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane) preparation method
Adopting a micro-well pipeline type reactor, firstly dissolving 33.6g of bisphenol AF in 101g of ionic liquid B1-butyl-3-methylimidazole nitrate, stirring to form uniform material A, adjusting a metering pump 1 to enable the flow rate of the material A to be 10g/min, and feeding the material A into the micro-well pipeline type reactor preheated to 45 ℃; adjusting a metering pump 2 to ensure that the flow rate of 68 percent concentrated nitric acid is 3.1g/min and the concentrated nitric acid and the material A enter the micro-well pipeline type reactor together; the material stays for 420S in the micro-well pipeline type reactor, then flows into a receiving bottle filled with distilled water of a stirring and cooling system to separate out solid, the solid is filtered, the ionic liquid B is recovered from filtrate, and the filter cake is washed and dried to obtain 41.3g of 6FNP, the yield is 96.95 percent, and the liquid phase content is 99.43 percent (shown in figure 2).
Step three, 6FAP (2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane) preparation method
A fixed bed reactor is adopted, firstly, a porous nano palladium catalyst is added into the fixed bed, and then 42.6g of 6FNP is dissolved into 170g of ionic liquid C1-ethyl-3-methylimidazolium acetate to be stirred to form a uniform substanceAdjusting the metering pump 3 to ensure that the flow rate of the material B is 10g/min, adjusting the flow rate of a hydrogen gas flow meter to be 1200ml/min, firstly introducing hydrogen into a fixed bed reactor which is preheated to 50 ℃ in advance for pressure to be 1.0MPa, then introducing the material B, keeping the time for 300S, and enabling the reaction liquid to enter a receiving tank through an outlet; finally, adding ionic resin into the reaction solution taken out, and filtering; then adding ultrapure water to precipitate a product. Filtering, recovering ionic liquid C from filtrate, washing filter cake with water, refining and pulping EA to obtain pure product 6FAP,35.8 g, white powder, yield 97.8%, melting point: 245-247 deg.C, liquid phase content of 99.88% (see figure 3), chroma of 6.6, and B value of 4.5.H 1 NMR (DMSO, see figure 4): 4.65 (4H, s), 6.42 (2H, d), 6.58 (2H, s), 6.66 (2H, d), 9.36 (2H, s).
Example 2:
step one, preparation method of bisphenol AF
Adding 47g of phenol into 188g of ionic liquid A, namely methylimidazole trifluoromethanesulfonic acid, then heating to 100 ℃, dropwise adding 92g of hexafluoroacetone hemihydrate, then heating to 150 ℃ for reaction until the reaction of the raw materials is finished. Cooling, adding the reaction solution into water, filtering, and recovering the ionic liquid A from the water phase; the cake was washed with water and dried to give 73.5g of bisphenol AF as an off-white powder. Yield: 87.5 percent and the content is 98.46 percent.
Step two, 6FNP (2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane) preparation method
Adopting a micro-well pipeline type reactor, firstly dissolving 33.6g of bisphenol AF in 101g of ionic liquid B1-butyl-3-methylimidazole nitrate, stirring to form uniform material A, adjusting a metering pump 1 to enable the flow rate of the material A to be 7g/min, and feeding the material A into the micro-well pipeline type reactor which is preheated to 50 ℃; regulating a metering pump 2 to ensure that the flow rate of 68 percent concentrated nitric acid is 4g/min and the concentrated nitric acid and the material A enter the micro-well pipeline type reactor together; the material stays for 500S in the micro-well pipeline type reactor, then flows into a receiving bottle of distilled water provided with a stirring and cooling system to precipitate solid, the solid is filtered, the ionic liquid B is recovered from the filtrate, and the filter cake is washed and dried to obtain 40.8g 6FNP with the yield of 95.81 percent and the liquid phase content of 98.17 percent.
Preparation method of step three, 6FAP (2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane)
Adopting a fixed bed reactor, firstly adding a porous nano palladium catalyst into the fixed bed, then dissolving 42.6g of 6FNP into 170g of ionic liquid C1-ethyl-3-methylimidazolium acetate, stirring to form uniform material B, adjusting a metering pump 3 to ensure that the flow rate of the material B is 15g/min, adjusting the flow rate of a hydrogen gas flow meter to be 1500ml/min, firstly introducing hydrogen into the fixed bed reactor which is preheated to 30 ℃ for pressure of 2.0MPa, then introducing the material B, keeping the time for 390S, and allowing reaction liquid to enter a receiving tank through an outlet; finally, adding ionic resin into the reaction solution which is taken out, and filtering; then adding into ultrapure water, separating out the product, and filtering. Recovering ionic liquid C from filtrate, washing filter cake with water, refining and pulping EA to obtain pure product 6FAP,35.96 g of white powder, the yield is 98.25%, and the melting point is as follows: 246-247 deg.C, 99.27% of liquid phase content, 6.2 of chroma, 4.1 of B value.
Example 3:
step one, preparation method of bisphenol AF
47g of phenol is added into 376g of ionic liquid A methylimidazole trifluoromethanesulfonic acid, then the temperature is raised to 100 ℃, 276g of hexafluoroacetone hemihydrate is added dropwise, and then the temperature is raised to 200 ℃ for reaction until the reaction of the raw materials is finished. Cooling, adding the reaction solution into water, filtering, and recovering the ionic liquid A from the water phase; the filter cake was washed with water and dried to give 78.1g of bisphenol AF as an off-white powder. Yield: 92.98 percent and the content is 99.11 percent.
Step two, 6FNP (2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane) preparation method
Adopting a micro-well pipeline reactor, firstly dissolving 33.6g of bisphenol AF in 101g of ionic liquid B1-butyl-3-methylimidazole nitrate, stirring to form a uniform material A, adjusting a metering pump 1 to enable the flow rate of the material A to be 12g/min, and feeding the material A into the micro-well pipeline reactor preheated to 45 ℃; adjusting the metering pump 2 to ensure that the flow rate of the 68 percent concentrated nitric acid is 5g/min and the 68 percent concentrated nitric acid and the material A enter the micro-well pipeline reactor together; the material stays for 350S in the micro-well pipeline reactor, then flows into a receiving bottle of distilled water provided with a stirring and cooling system to precipitate solid, the solid is filtered, the ionic liquid B is recovered from the filtrate, and the filter cake is washed and dried to obtain 40.92g of 6FNP, the yield is 96.07 percent, and the liquid phase content is 98.62 percent.
Preparation method of step three, 6FAP (2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane)
Adopting a fixed bed reactor, firstly adding a porous nano palladium catalyst into the fixed bed, then dissolving 42.6g 6FNP into 170g ionic liquid C1-ethyl-3-methylimidazole acetate, stirring to form uniform material B, adjusting the flow rate of the material B to 8g/min by adjusting the metering pump 3, adjusting the flow rate of a hydrogen gas flow meter to 1100ml/min, firstly introducing hydrogen into the fixed bed reactor which is preheated to 60 ℃ for standby pressure to 0.6MPa, then introducing the material B, keeping the material B for 520S, and introducing reaction liquid into a receiving tank through an outlet; finally, adding ionic resin into the reaction solution which is taken out, and filtering; then adding ultrapure water to precipitate a product. Filtering, recovering ionic liquid C from filtrate, washing filter cake with water, refining and pulping EA to obtain pure product 6FAP,34.95 g and white powder, the yield is 95.49%, and the melting point is as follows: 246-247 deg.C, liquid phase content 98.43%, chroma 7.5, B value 5.9.
Example 4
Step one, preparation method of bisphenol AF
Adding 47g of phenol into 329g of ionic liquid A methacryloxypropyltrimethyl ammonium chloride, heating to 95 ℃, dropwise adding 206g of hexafluoroacetone hemihydrate, heating to 180 ℃ for reaction until the reaction of the raw materials is finished. Cooling, adding the reaction solution into water, filtering, and recovering the ionic liquid A from the water phase; the filter cake was washed with water and dried to give bisphenol AF as a white powder, 56.8g. Yield: 67.62 percent and the content is 91.36 percent.
Step two, 6FNP (2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane) preparation method
Dissolving 50g of ionic liquid tetramethylammonium nitrate in 80g of cosolvent acetic acid aqueous solution by adopting a micro-well pipeline type reactor, uniformly stirring, dissolving 33.6g of bisphenol AF in the mixed solution to form a uniform material A, adjusting a metering pump 1 to ensure that the flow rate of the material A is 6g/min, and feeding the material A into the micro-well pipeline type reactor preheated to 55 ℃; adjusting a metering pump 2 to ensure that the flow rate of 68 percent concentrated nitric acid is 5g/min and the material A enters the micro-well pipeline type reactor together; the material stays for 500S in the micro-well pipeline type reactor, then flows into a receiving bottle of distilled water provided with a stirring and cooling system to separate out solid, the solid is filtered, the ionic liquid B is recovered from the filtrate, and the filter cake is washed and dried to obtain 27.9g of 6FNP, wherein the yield is 65.49 percent, and the content of the liquid phase is 90.36 percent.
Preparation method of step three, 6FAP (2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane)
Adopting a fixed bed reactor, firstly adding a porous nano palladium catalyst into the fixed bed, then dissolving 42.6g 6FNP into 170g ionic liquid C tetramethyl ammonium hydroxide, stirring to form uniform material B, adjusting the flow rate of the material B to 11g/min by adjusting a metering pump 3, adjusting the flow rate of a hydrogen gas flow meter to 1400ml/min, firstly introducing hydrogen into the fixed bed reactor which is preheated to 60 ℃ for pressure to 0.6MPa, then introducing the material B, keeping the time for 480S, and allowing reaction liquid to enter a receiving tank through an outlet; finally, adding ionic resin into the reaction solution which is taken out, and filtering; then adding ultrapure water to precipitate a product. Filtering, recovering ionic liquid C from filtrate, washing filter cake with water, refining and pulping EA to obtain pure product 6FAP,19.3 g, white powder, yield 52.73%, melting point: 246-249 ℃, 93.27% of liquid phase content, 13.5 of chroma and 17.9 of B value.
Example 5
Step one, preparation method of bisphenol AF
At 282g of ionic liquid A: 47g of phenol is added into 1-butyl-4-methylpyridine hexafluorophosphate, then the temperature is raised to 130 ℃, 136g of hexafluoroacetone hemihydrate are added dropwise, and then the temperature is raised to 200 ℃ for reaction until the reaction of the raw materials is finished. Cooling, adding the reaction solution into water, filtering, and recovering the ionic liquid A from the water phase; the filter cake was washed with water and dried to give bisphenol AF as a white powder, 36.4g. Yield: 43.33 percent and the content is 89.15 percent.
Step two, 6FNP (2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane) preparation method
A micro-well pipeline type reactor is adopted, and 30g of bisphenol AF is firstly dissolved in 260g of ionic liquid B: stirring the N-butyl-4-methylpyridine trifluoromethanesulfonate to form a uniform material A, adjusting a metering pump 1 to enable the flow rate of the material A to be 7g/min, and feeding the material A into a micro-well pipeline type reactor which is preheated to 60 ℃; adjusting a metering pump 2 to ensure that the flow rate of 68 percent concentrated nitric acid is 6g/min and the material A enters the micro-well pipeline type reactor together; the material stays in the micro-well pipeline reactor for 560S, then flows into a receiving bottle of distilled water provided with a stirring and cooling system to precipitate solid, the solid is filtered, the ionic liquid B is recovered from the filtrate, and the filter cake is washed and dried to obtain 18.2g of 6FNP, the yield is 42.72 percent, and the liquid phase content is 88.27 percent.
Preparation method of step three, 6FAP (2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane)
Adopting a fixed bed reactor, firstly adding a porous nano palladium catalyst into the fixed bed, then dissolving 17g 6FNP into 130g of ionic liquid C1-butyl-4-methylpyridine hexafluorophosphate and stirring to form a uniform material B, adjusting the flow rate of the material B to be 6g/min by adjusting a metering pump 3, adjusting the flow rate of a hydrogen gas flow meter to be 1000ml/min, firstly introducing hydrogen into the fixed bed reactor which is preheated to 70 ℃ for standby pressure of 0.6MPa, then introducing the material B, keeping the material B for 500S, and introducing reaction liquid into a receiving tank through an outlet; finally, adding ionic resin into the reaction solution taken out, and filtering; then adding ultrapure water to precipitate a product. Filtering, recovering ionic liquid C from filtrate, washing filter cake with water, refining and pulping EA to obtain pure product 6FAP,5.6 g, white powder, yield 40.4%, melting point: 246-249 ℃, 76.5 percent of liquid phase content, 19.3 chroma and 22.4B value.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is characterized by comprising the following steps: the method comprises the following three steps:
the method comprises the following steps: adding phenol into the ionic liquid A, then heating to 100 ℃, dropwise adding hexafluoroacetone hemihydrate, then heating for reaction until the raw materials are reacted, cooling, adding the reaction solution into water, filtering, recovering the ionic liquid A from the water phase, and washing the filter cake with water to obtain bisphenol AF;
step two: adopting a pipeline reactor, firstly adding bisphenol AF into ionic liquid B, then setting the flow rate and the residence time, and respectively pumping concentrated nitric acid and ionic liquid B solution containing bisphenol AF into the pipeline reactor by using a metering pump according to a two-strand feeding mode under a heating condition; after the materials completely react in the pipeline type reactor, the materials flow into a receiving bottle filled with distilled water, the materials are filtered, the ionic liquid B is recovered from the filtrate, and 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane is obtained after the filter cake is washed with water;
step three: adopting a fixed bed reactor, firstly adding a porous nano palladium catalyst into the fixed bed, then dissolving 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane into an ionic liquid C, adjusting the flow rate, simultaneously introducing hydrogen, setting the pressure and the retention time, after complete reaction, allowing the reaction liquid to flow into a receiving bottle through an outlet, adding ionic resin, and filtering; then adding ultrapure water, precipitating the product, filtering, recovering ionic liquid C from the filtrate, washing the filter cake with water, and refining the solvent to obtain the pure 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
2. The process for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the ionic liquid A, the ionic liquid B and the ionic liquid C used in the three steps are any one of imidazole type, pyridine type, piperidine type, quaternary ammonium salt type and morpholine type.
3. The process for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the ionic liquid A, the ionic liquid B and the ionic liquid C used in the three steps are imidazole type.
4. The process for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in any one of claims 1 to 3, wherein: the ionic liquid A in the step one is methylimidazole trifluoromethanesulfonic acid, the ionic liquid B in the step two is 1-butyl-3-methylimidazole nitrate, and the ionic liquid C in the step three is 1-ethyl-3-methylimidazole acetate.
5. The process for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the molar ratio of phenol to hexafluoroacetone hemihydrate in the first step is 1: (1-3), preferably in a molar ratio of 1:2; the mass ratio of phenol to ionic liquid A is 1: (4-8), preferably 1:6.
6. the process for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the reaction temperature in the first step is 150-200 ℃, and preferably 180 ℃.
7. The process for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the flow rate of the ionic liquid B solution containing the bisphenol AF in the second step is as follows: 5-20g/min, preferably 10g/min.
8. The process for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the residence time of the materials in the channel of the pipeline reactor in the step two is 100-600s, preferably 420s; the reaction temperature is 5 to 60 ℃ and preferably 45 ℃.
9. The process for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as claimed in claim 1, wherein: the flow rate of the ionic liquid C containing 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane in the third step is 5-15g/min, preferably 10g/min; the flow rate of the hydrogen is 1000-1500ml/min, preferably 1200ml/min; the pressure is 0.1-5MPa, preferably 1MPa.
10. The process for producing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane according to claim 1, wherein: the residence time of the material in the passage of the fixed bed reactor in the third step is 100-600s, preferably 300s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211330216.5A CN115636759B (en) | 2022-10-27 | Preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211330216.5A CN115636759B (en) | 2022-10-27 | Preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115636759A true CN115636759A (en) | 2023-01-24 |
| CN115636759B CN115636759B (en) | 2024-06-11 |
Family
ID=
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108570019A (en) * | 2018-05-31 | 2018-09-25 | 大连理工大学 | A kind of novel acid ionic liquid and its catalytic applications |
| CN111302944A (en) * | 2020-03-31 | 2020-06-19 | 上海如鲲新材料有限公司 | Preparation method of bis (3-amino-4-hydroxyphenyl) hexafluoropropane |
| CN112409125A (en) * | 2020-11-30 | 2021-02-26 | 山东华夏神舟新材料有限公司 | Method for continuously preparing diaryl hexafluoropropane |
| CN113105331A (en) * | 2021-04-09 | 2021-07-13 | 海南夸克科技有限公司 | Method for preparing 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane by using microchannel reactor |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108570019A (en) * | 2018-05-31 | 2018-09-25 | 大连理工大学 | A kind of novel acid ionic liquid and its catalytic applications |
| CN111302944A (en) * | 2020-03-31 | 2020-06-19 | 上海如鲲新材料有限公司 | Preparation method of bis (3-amino-4-hydroxyphenyl) hexafluoropropane |
| CN112409125A (en) * | 2020-11-30 | 2021-02-26 | 山东华夏神舟新材料有限公司 | Method for continuously preparing diaryl hexafluoropropane |
| CN113105331A (en) * | 2021-04-09 | 2021-07-13 | 海南夸克科技有限公司 | Method for preparing 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane by using microchannel reactor |
Non-Patent Citations (2)
| Title |
|---|
| 刘岳明等: "离子液体催化芳烃硝化反应研究进展", 《煤炭与化工》, vol. 43, no. 12, pages 111 * |
| 吴志峰，蒋和雁: "膦功能化离子液体稳定的纳米钯催化硝基化合物高选择性加氢", 《中国化学会·第八届有机化学学术会议暨首届重庆有机化学国际研讨会》, pages 1343 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102070491A (en) | Method for preparing xylylene diisocyanate based on salification-phosgenation reaction | |
| CN109810074B (en) | Reaction device for continuously synthesizing 2-mercaptobenzothiazole | |
| CN113402395A (en) | Method for continuously and efficiently synthesizing m-phenylenediamine based on fixed bed microreactor | |
| CN106800512B (en) | A kind of preparation method and preparation facilities of 3,5- dinitro o methyl benzoic acid | |
| CN111116313A (en) | Preparation method of deuterated methanol | |
| CN113429295A (en) | Method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on fixed bed microreactor | |
| CN102030899B (en) | High-molecular supported type catalyst as well as preparation and application thereof | |
| CN114671770A (en) | Production method of 4,4' -diaminodiphenyl ether | |
| CN115636759B (en) | Preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane | |
| CN115636759A (en) | Preparation method of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane | |
| CN104496761A (en) | Bisphenol A preparation method | |
| CN1313473C (en) | Preparation of acetylacetone cobalt | |
| CN108586477B (en) | A kind of method of micro passage reaction synthesis 5- Isosorbide Mononitrate | |
| CN101525292A (en) | Preparation method of paranitrobenzoic acid | |
| CN112321399B (en) | Preparation method of chemical intermediate | |
| CN114105905A (en) | Preparation method and synthesis system of N-tertiary butyl-2-benzothiazole sulfonamide | |
| CN110511182B (en) | Method for synthesizing 7-nitro-1,2,3,4-tetrahydroquinoline by continuous flow reaction | |
| CN111018706B (en) | Synthesis method of 4, 4' -diphenyl ether dicarboxylic acid | |
| CN113831281A (en) | Industrial method for preparing nitro compound as intermediate of proton pump inhibitor | |
| CN109320412B (en) | Preparation method of 2,4, 6-trimethyl benzoic acid | |
| CN101844996B (en) | Method for preparing 2,5-di(p-chloroanilino)-terephthalic acid (DpCTA) | |
| CN112125806A (en) | Method for preparing p-phenylenediamine by using microreactor | |
| CN106866378B (en) | Synthetic process of phloroglucinol | |
| CN115636763B (en) | Continuous preparation process of 4-carbamoyl benzoyl chloride and process for preparing 4-cyano benzoyl chloride by using same | |
| CN115448929B (en) | Preparation method and application of compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |