CN113845432A - Preparation method of 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane - Google Patents
Preparation method of 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane Download PDFInfo
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- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000010992 reflux Methods 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- -1 4-nitrophenoxyphenyl Chemical group 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000001294 propane Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims 1
- ZVDYLUNNDJVEOC-UHFFFAOYSA-N 1-(4-nitrophenoxy)-4-propylbenzene Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 ZVDYLUNNDJVEOC-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005859 coupling reaction Methods 0.000 abstract description 8
- 239000012024 dehydrating agents Substances 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000009151 chronic rhinitis Diseases 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 206010039083 rhinitis Diseases 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
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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 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, wherein the coupling reaction in the step 1 is carried out by taking bisphenol A and p-nitrochlorobenzene as initial raw materials; under the action of polar aprotic solvent, decompressing and dehydrating, mixing with p-nitrochlorobenzene, and carrying out reflux reaction to obtain 2,2 '-bis [4- (4-nitrophenoxy) phenyl ] propane (BNPP), wherein the reaction of the step 2 is to dissolve BNPP in the polar aprotic solvent, react by taking silicon dioxide loaded transition metal as catalyst and hydrogen as reducing agent to obtain 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, and the catalyst can be used indiscriminately without treatment. According to the preparation method provided by the invention, a solvent is used as a dehydrating agent at the same time, and the dehydration is carried out at a reduced pressure and a low temperature, so that the coupling reaction is realized; reducing by using hydrogen to obtain a target product. The method has the advantages of simple operation, mild reaction conditions, less three-waste discharge, good product quality, high yield and the like.
Description
Technical Field
The invention relates to organic synthesis of propane, in particular to a preparation method of 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane.
Background
2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP) and diphenyl ether 3,3',4,4' -tetracarboxylic dianhydride (ODPA) or Benzophenone Tetracarboxylic Dianhydride (BTDA) and 6FDA are taken as dianhydride monomers, and the prepared polyimide is a typical high-performance polymer, has better mechanical property, higher thermal stability, superior radiation resistance, dielectric property and the like, and is expected to be used in very severe environments, such as the high-tech fields of atomic energy industry, aerospace, military and the like.
At present, the synthesis method of BAPP mainly comprises DMF (dimethyl formamide), potassium carbonate and toluene serving as a dehydrating agent, which are applicable to preparation of BNPP (N-BNP) in a preparation method of 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane published by No. 2 chemical and adhesive Caolon et al, volume 32, 2010, and the like. Patent CN1472193A discloses a method for preparing BNPP by using a salt forming agent and a dehydrating agent, and then reducing the BNPP by using ferric chloride hexahydrate, activated carbon and hydrazine hydrate to obtain BAPP.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a relatively environment-friendly preparation method of 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane.
The invention provides the following technical scheme:
the preparation method of the 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane provided by the invention comprises the following steps:
s1, coupling reaction: bisphenol A and p-nitrochlorobenzene are used as initial raw materials, under the action of a polar aprotic solvent, a salt forming agent is added, the bisphenol A is salified and dehydrated, then the salt forming agent and the p-nitrochlorobenzene are mixed, the reflux temperature is 150-162 ℃, 5-20% of solvent is extracted while refluxing, and the reflux reaction is carried out to obtain 2,2' -bis [4- (4-nitrophenoxyphenyl) ] propane;
s2, the reduction reaction is as follows: 2,2 '-bis [4- (4-nitrophenoxyphenyl) ] propane is dissolved in a polar aprotic solvent, silicon dioxide loaded transition metal is used as a catalyst, hydrogen is introduced at the temperature of 100 ℃ and 120 ℃ for reduction reaction to obtain 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane, and then the product is obtained by refining.
The solvent described in the present invention is a polar aprotic solvent and is also a dehydrating agent. The polar aprotic solvent is N, N-dimethylformamide, dimethylacetamide or dimethylsulfoxide, preferably N, N-dimethylformamide.
Preferably, the salt forming agent is potassium carbonate.
In the invention, the mass ratio of the bisphenol A, the solvent, the p-nitrochlorobenzene and the salt forming agent is (9-12) to (1.3-1.4): (0.65-0.8).
The salt-forming dehydration of the bisphenol A is decompression dehydration under the condition of vacuum degree of-0.1 to-0.09 MPa, and the dehydration temperature is 100-120 ℃, and the preferable temperature is 100-110 ℃.
The reflux temperature of the coupling reaction of the invention begins to extract 10-20% of the added solvent. And about 1-2% is extracted every 0.5 h.
The water content of the mixed solution after the salifying and dehydrating of the bisphenol A is less than 0.5-1%, and preferably less than 0.5%.
The reflux temperature of the coupling reaction is preferably 160-162 ℃.
The 1 st step coupling reaction route of the invention is as follows: equation (X) -equation (X)
The reaction of the step 1 of the invention also comprises treatment after the reaction is finished, firstly, hot filter pressing is carried out, salt is removed, the reaction liquid is cooled, then, pure water is dripped into the reaction liquid, and the temperature is reduced and crystallization is carried out; carrying out solid-liquid separation to obtain the 2,2' -bis [4- (4-nitrophenoxy) phenyl ] propane (BNPP).
The reduction reaction of the step 2 of the invention is that BNPP is dissolved in polar aprotic solvent, and the reduction reaction is catalyzed by silicon dioxide loaded palladium metal and hydrogen to obtain 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane.
The catalyst is a silica supported nickel, palladium, rhodium and ruthenium transition metal catalyst, and preferably silica supported palladium carbon is used as the catalyst.
The dosage of the palladium carbon catalyst is 0.1-2% of the mass of 2,2' -bis [4- (4-nitrophenoxy) phenyl ] propane, and the optimal dosage is 1%. The palladium-carbon composite material can be continuously used for 10-20 times.
The pressure in the reduction reaction is 0.1-0.3 MPa, and the temperature of the reduction reaction is 100-120 ℃. The preferable reaction temperature is 110-120 ℃.
The 2 nd step reduction reaction route of the invention is as follows: can be used for treating chronic rhinitis
The invention also comprises solid-liquid separation after the reaction in the step 2, and the used catalyst palladium carbon is used for mechanical application. And dropwise adding pure water into the reaction solution, and cooling and crystallizing to obtain the 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane.
Compared with the prior art, the invention has the beneficial effects that: according to the preparation method provided by the invention, the coupling reaction in the step 1 is to use N, N-dimethylformamide as a solvent, salify the bisphenol A, decompress and dehydrate, extract part of N, N-dimethylformamide as a water-carrying agent while reacting, and extract DMF water which can be repeatedly used after rectification, so that the using amount of the solvent is reduced, and the use of a dehydrating agent toluene is avoided.
And 2, the reduction reaction is carried out by taking palladium carbon as a catalyst and hydrogen as a reducing agent to obtain a target product. The reaction operation is simple, the environment is friendly, the reaction time is short, and the post-treatment is easy.
The preparation method has the advantages of single solvent, low pressure reduction dehydration temperature, short reaction time, less three wastes, simple post-treatment and environmental friendliness, and uses transition metal as a catalyst and hydrogen as a reducing agent.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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 1:
100g of bisphenol A, 1000ml of DMF and 66.5g of potassium carbonate were put into a 2000ml reaction flask, and the mixture was subjected to distillation under reduced pressure and stirred. Vacuumizing by a vacuum pump to-0.09 MPa, starting heating, refluxing to extract DMF, and stopping extraction when the water content of the DMF extracted by the central control is less than 0.5%. And cooling to 70-80 ℃, transferring the mixed solution into a reaction bottle with 139.5g of p-nitrochlorobenzene, and refluxing to the extraction device. Heating to 160-162 ℃, extracting DMF (dimethyl formamide) 10-16 g every 0.5h, extracting 90g in total, and continuing to react for 1h to finish the reaction. Separating solid salt in the reaction solution by using hot filtration, transferring the filtrate into a new glass bottle, dropwise adding 125g of pure water into the bottle, cooling and crystallizing after dropwise adding is finished for 0.5h, cooling to 0-5 ℃, preserving heat for 1h, performing solid-liquid separation, and washing a filter cake by using 10g of pure water. 230g of wet 2 '-bis [4- (4-nitrophenoxy) phenyl ] propane (BNPP) was obtained, and dried by air blowing to obtain 202g of dry 2' -bis [4- (4-nitrophenoxy) phenyl ] propane (BNPP), the molar yield was 98.1%, and the purity was 99.76%.
And (3) carrying out reduction reaction, namely adding 200g of BNPP into a reaction kettle, adding DMF1000g and 2g of catalyst silicon dioxide loaded metal palladium dry basis into the reaction kettle, loading the reaction kettle, carrying out leakage test, and carrying out nitrogen replacement for 3 times. And filling hydrogen gas to 0.2MPa, heating to 110-112 ℃, carrying out heat preservation reaction, keeping the hydrogen gas pressure to 0.2-0.25 MPa, and finishing the reaction for about 2-3h when the pressure is not reduced any more. The catalyst was filtered off thermally. Pouring the reaction filtrate into a clean reaction bottle, dropwise adding 200g of pure water into the bottle, and finishing dropwise adding after 0.5 h. Cooling to 0-5 ℃, and carrying out heat preservation and crystallization for 1 h. Filtering, top washing the filter cake with 20g pure water to obtain crude wet 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane product, and vacuum drying to obtain 171.8g crude dry product with molar yield 98.5% and purity over 99.5%. Refining with 15% DMF water solution, and oven drying to obtain 170g refined dry product with molar yield of 99% and purity of 99.78%.
Example 2:
100g of bisphenol A, 900g of DMF and 75g of potassium carbonate were put into a 2000ml reaction flask, and the mixture was distilled under reduced pressure with stirring. Vacuumizing by a vacuum pump to-0.09 MPa, starting heating, and extracting DMF under reflux, wherein the extraction is stopped when the water content of the DMF extracted by the central control is less than 1%. And cooling to 70-80 ℃, transferring the mixed solution into a reaction bottle filled with 136.5g of p-nitrochlorobenzene, and refluxing to obtain the device. Heating to 160-162 ℃, extracting DMF (10-16 g) every 0.5h, extracting 70g in total, and continuing to react for 1h to finish the reaction. Separating solid salt in the reaction solution by using hot filtration, transferring the filtrate into a new glass bottle, dropwise adding 125g of pure water into the bottle, cooling and crystallizing after dropwise adding is finished for 0.5h, cooling to 0-5 ℃, preserving heat for 1h, performing solid-liquid separation, and washing a filter cake by using 10g of pure water. 225g of wet 2' -bis [4- (4-nitrophenoxy) phenyl ] propane (BNPP) was obtained, and dried by air blowing to obtain 200.8g of a dry product, the molar yield was 97.5%, and the purity was 99.60%.
And (3) carrying out reduction reaction, namely adding 190g of BNPP into a reaction kettle, adding 875g of DMF, adding 0.5g of silica supported metal palladium obtained by filtering in the previous batch and the total dry basis of the supplementary catalyst, loading the mixture into the reaction kettle, carrying out leakage test, and carrying out nitrogen replacement for 3 times. And (3) flushing hydrogen gas at 0.2MPa, heating to 110-112 ℃, carrying out heat preservation reaction, keeping the hydrogen gas pressure at 0.2-0.25 MPa, and finishing the reaction for about 2-3h when the pressure is not reduced any more. The palladium on carbon is thermally filtered off. The reaction filtrate was poured into a clean reaction flask, and 175g of pure water was added dropwise thereto over 0.5 hour. Cooling to 0-5 ℃, and carrying out heat preservation and crystallization for 1 h. Filtering, top washing the filter cake with 17.5g pure water to obtain crude wet 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane product, and vacuum drying to obtain 162g crude dry product with molar yield of 97.8% and purity of over 99.5%. Refining with 15% DMF water solution, and oven drying to obtain 159.9g refined dried product with molar yield 98.7% and purity 99.72%.
Example 3:
100g of bisphenol A, 1000g of DMF and 70g of potassium carbonate were put into a 2000ml reaction flask, and the mixture was subjected to distillation under reduced pressure and stirred. Vacuumizing by a vacuum pump to-0.09 MPa, starting heating, and extracting DMF under reflux, wherein the extraction is stopped when the water content of the DMF extracted by the central control is less than 0.5%. And cooling to 70-80 ℃, transferring the mixed solution into a reaction bottle with 134g of p-nitrochlorobenzene, and refluxing to the extraction device. Heating to 153-158 ℃, extracting DMF (dimethyl formamide) 10-16 g every 0.5h, extracting 90g in total, and continuing to react for 1h to finish the reaction. Separating solid salt in the reaction solution by using hot filtration, transferring the filtrate into a new glass bottle, dropwise adding 125g of pure water into the bottle, cooling and crystallizing after dropwise adding is finished for 0.5h, cooling to 0-5 ℃, preserving heat for 1h, performing solid-liquid separation, and washing a filter cake by using 10g of pure water. 226g of wet 2 '-bis [4- (4-nitrophenoxy) phenyl ] propane (BNPP) was obtained, and dried by air blowing to obtain 199g of dry 2' -bis [4- (4-nitrophenoxy) phenyl ] propane (BNPP), the molar yield was 96.6%, and the purity was 99.56%.
And (3) carrying out reduction reaction, namely adding 180g of BNPP into a reaction kettle, adding DMF900g into the reaction kettle, adding 1.8g of silica-supported metal palladium dry basis into the reaction kettle, loading the reaction kettle, carrying out leakage test, and replacing nitrogen for 3 times. And (3) flushing hydrogen gas at 0.2MPa, heating to 115-120 ℃, carrying out heat preservation reaction, keeping the hydrogen gas pressure at 0.25-0.3 MPa, and finishing the reaction for about 2-3h when the pressure is not reduced any more. The catalyst was filtered off thermally. Pouring the reaction filtrate into a clean reaction bottle, dropwise adding 180g of pure water into the bottle, and finishing dropwise adding after 0.5 h. Cooling to 0-5 ℃, and carrying out heat preservation and crystallization for 1 h. The filtrate was filtered and the cake was top-washed with 18g of pure water to give a crude wet product of 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, which was dried under vacuum to give 152.8g of a crude dry product with a molar yield of 97.4% and a purity of > 99.5%. Refining with 15% DMF water solution, and oven drying to obtain 149.5g refined dried product with molar yield of 97.8% and purity of 99.75%.
According to the preparation method provided by the invention, the coupling reaction in the step 1 is carried out by taking DMF as a solvent, salifying bisphenol A, decompressing and dehydrating, reacting while extracting partial DMF as a water-carrying agent, and rectifying the extracted DMF water for repeated use, so that the use amount of the solvent is reduced, and the use of a dehydrating agent toluene is avoided.
And 2, the reduction reaction is carried out by taking palladium carbon as a catalyst and hydrogen as a reducing agent to obtain a target product. The reaction operation is simple, the environment is friendly, the reaction time is short, and the post-treatment is easy.
The molar yield of the obtained product is more than 97 percent and the purity is more than 99.7 percent in the whole preparation method.
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)
- A process for producing 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, characterized by comprising the steps of:s1, adding a salt forming agent into bisphenol A and p-nitrochlorobenzene serving as starting raw materials under the action of a polar aprotic solvent, salifying and dehydrating the bisphenol A, mixing the bisphenol A and the p-nitrochlorobenzene, refluxing at the reflux temperature of 150 ℃ and 162 ℃, extracting 5-20% of the solvent while refluxing, and performing reflux reaction to obtain 2,2' -bis [4- (4-nitrophenoxyphenyl) ] propane;s2, 2 '-bis [4- (4-nitrophenoxyphenyl) ] propane is dissolved in a polar aprotic solvent, silicon dioxide supported transition metal is used as a catalyst, hydrogen is introduced at the temperature of 100-120 ℃ for reduction reaction to obtain 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane, and then the product is obtained by refining.
- 2. The process for producing 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, according to claim 1, characterized in that: the polar aprotic solvent is N, N-dimethylformamide, dimethylacetamide or dimethylsulfoxide.
- 3. The process for producing 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, according to claim 1, characterized in that: the salt forming agent is potassium carbonate.
- 4. The process for producing 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, according to claim 1, characterized in that: the mass ratio of the bisphenol A, the solvent, the p-nitrochlorobenzene and the salt forming agent is (9-12) to (1.3-1.4): (0.6-0.8).
- 5. The process for producing 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, according to claim 1, characterized in that: the salt-forming dehydration of the bisphenol A is decompression dehydration under the condition of vacuum degree of-0.1 to-0.09 MPa, and the dehydration temperature is 100 to 120 ℃.
- 6. The process for producing 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, according to claim 1, characterized in that: the water content of the mixed solution after the bisphenol A salifying and dehydrating is lower than 0.5-1%.
- 7. The process for producing 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, according to claim 1, characterized in that: the catalyst is silica supported nickel, palladium, rhodium, ruthenium transition metal catalyst.
- 8. The process for producing 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, according to claim 7, characterized in that: the catalyst is silica supported palladium carbon.
- 9. The process for producing 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, according to claim 1, characterized in that: the adding amount of the catalyst is 0.1-2% of the mass of the 2,2' -bis [4- (4-nitrophenoxyphenyl) ] propane.
- 10. The process for producing 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane, according to claim 1, characterized in that: in step S2, the solvent used for crude product refining is a 15-20% dimethylformamide solution.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114933537A (en) * | 2022-03-24 | 2022-08-23 | 天津众泰材料科技有限公司 | Preparation method of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane |
| CN115286519A (en) * | 2022-08-08 | 2022-11-04 | 浙江清和新材料科技有限公司 | Preparation method of 4,4' -bis (3-aminophenoxy) biphenyl |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0537589A2 (en) * | 1991-10-16 | 1993-04-21 | BASF Aktiengesellschaft | Process for the preparation of dinitro- and diaminophenoxy compounds |
| CN102633662A (en) * | 2012-03-27 | 2012-08-15 | 湖北大学 | Preparation method of 2,2-di[4-(4'-aminophenoxy)phenyl]propane |
| CN105294461A (en) * | 2015-10-21 | 2016-02-03 | 烟台海川化学制品有限公司 | Preparation method of 4,4'-bis(4-aminophenoxy)biphenyl |
| US20180022872A1 (en) * | 2014-09-05 | 2018-01-25 | Government Of The United States, As Represented By The Secretary Of The Air Force | Bis(azobenzene) diamines and photomechanical polymers made therefrom |
-
2021
- 2021-11-08 CN CN202111315122.6A patent/CN113845432A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0537589A2 (en) * | 1991-10-16 | 1993-04-21 | BASF Aktiengesellschaft | Process for the preparation of dinitro- and diaminophenoxy compounds |
| CN102633662A (en) * | 2012-03-27 | 2012-08-15 | 湖北大学 | Preparation method of 2,2-di[4-(4'-aminophenoxy)phenyl]propane |
| US20180022872A1 (en) * | 2014-09-05 | 2018-01-25 | Government Of The United States, As Represented By The Secretary Of The Air Force | Bis(azobenzene) diamines and photomechanical polymers made therefrom |
| CN105294461A (en) * | 2015-10-21 | 2016-02-03 | 烟台海川化学制品有限公司 | Preparation method of 4,4'-bis(4-aminophenoxy)biphenyl |
Non-Patent Citations (2)
| Title |
|---|
| C. GENIES ET AL.,: "Soluble sulfonated naphthalenic polyimides as materials for proton exchange membranes", POLYMER, vol. 42, pages 360 * |
| RSC ADV.: "Thermo-mechanical and surface properties of POSS reinforced structurally different diamine cured epoxy nanocomposites", K. SETHURAMAN ET AL.,, vol. 4, pages 45434 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114933537A (en) * | 2022-03-24 | 2022-08-23 | 天津众泰材料科技有限公司 | Preparation method of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane |
| CN115286519A (en) * | 2022-08-08 | 2022-11-04 | 浙江清和新材料科技有限公司 | Preparation method of 4,4' -bis (3-aminophenoxy) biphenyl |
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