CN113956135B - Preparation method of high-yield 4,4' -biphenol - Google Patents
Preparation method of high-yield 4,4' -biphenol Download PDFInfo
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- CN113956135B CN113956135B CN202111348966.0A CN202111348966A CN113956135B CN 113956135 B CN113956135 B CN 113956135B CN 202111348966 A CN202111348966 A CN 202111348966A CN 113956135 B CN113956135 B CN 113956135B
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- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000000047 product Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000004065 semiconductor Substances 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 21
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 238000006722 reduction reaction Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 16
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004472 Lysine Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 3
- 238000004042 decolorization Methods 0.000 claims 1
- 239000011858 nanopowder Substances 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 230000036632 reaction speed Effects 0.000 abstract description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- ZBIKORITPGTTGI-UHFFFAOYSA-N [acetyloxy(phenyl)-$l^{3}-iodanyl] acetate Chemical compound CC(=O)OI(OC(C)=O)C1=CC=CC=C1 ZBIKORITPGTTGI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 241000801593 Pida Species 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 4,4 '-biphenol with high yield, which uses a metal-loaded semiconductor material as a catalyst and oxygen as an oxidant to realize the oxidative coupling reaction of 2, 6-di-tert-butylphenol, so that the reaction is carried out at normal temperature, the reaction speed is high, the conversion rate is high, a small amount of byproducts are reduced into 4,4' -biphenol through reduction reaction, purification and filtration are carried out, and finally the filtered products are subjected to efficient tert-butyl removal by using p-toluenesulfonic acid as a catalyst to obtain target products.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 4,4' -biphenol with high yield.
Background
4,4' -biphenol as an important organic intermediate can be used for manufacturing engineering plastics, composite materials thereof and the like. The 4,4' -biphenol has the characteristics of oxidation resistance, aging resistance and no pollution, so that the 4,4' -biphenol is widely applied to food packaging, colorless or light-colored vulcanized rubber products and medical latex products, meanwhile, the 4,4' -biphenol also has the property of high temperature resistance, can be used as modified monomers such as polyester, polycarbonate (PC), polyphenylsulfone, polyurethane, epoxy resin and the like, and can also be used as a raw material of liquid crystal polymers, and is applied to manufacturing high-strength fibers, reinforced optical fibers and the like. 4,4 '-biphenol is used for preparing liquid crystal materials abroad as early as the 70 s of the 20 th century, the application in the rubber industry is not dominant at present, and the high-purity 4,4' -biphenol is mainly applied to the synthesis of liquid crystal polymers.
At present, the synthesis of 4,4' -biphenol mainly comprises the following 4 methods:
(1) Benzidine method: the method has the advantages that the benzidine is used as a raw material, 4' -biphenol can be obtained through diazotization and hydrolysis, the yield is low, and the nitrite used is harmful to human health;
(2) Biphenyl sulfonation alkali dissolution method: the method has the advantages that 4,4' -biphenol is obtained by taking biphenyl as a raw material through sulfonation, alkali dissolution, acidification and the like, the method has acidity and alkalinity, high requirements are put on reaction equipment, and the generated waste acid and alkali pollute the environment;
(3) Biphenyl halogenation high pressure hydrolysis process: the 4,4' -biphenol can be obtained by taking biphenyl as a raw material through halogenation, hydrolysis and other reactions, the method has harsh reaction conditions, high equipment requirements and environmental pollution;
(4) 2, 6-di-tert-butylphenol oxidative coupling method: 2, 6-di-tert-butylphenol is used as a raw material, 4' -biphenol can be obtained through three steps of oxidation, reduction and isobutyl removal, a large amount of aluminum trichloride is needed for tert-butyl removal, and difficulty is brought to product purification. Among them, the oxidizing agents used in the oxidative coupling method of 2, 6-di-t-butylphenol can be classified into 5 types: (1) oxygen, a pressure-resistant reaction vessel, (2) hydrogen peroxide as an oxidizing agent, but in an organic solvent, (3) inorganic salts such as copper sulfate, ferric trichloride and the like, (4) an organic oxidizing system such as iodobenzene diacetate (PIDA).
In the above-mentioned several conventional methods for preparing 4,4 '-biphenol generally use an organic medium as a reaction solvent, after the reaction, the treatment of the organic solvent causes a certain pollution to the environment, and the side reaction in the reaction process can cause low conversion rate, while the oxidative coupling method is used for preparing 4,4' -biphenol, and three steps of oxidation, reduction and isobutyl removal are needed, wherein a large amount of aluminum trichloride is needed in the tert-butyl removal step, which makes the purification of the product difficult.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of 4,4' -biphenol with high yield, which has simple process, high reaction speed and high yield.
The technical scheme adopted by the invention is as follows:
a preparation method of 4,4' -biphenol with high yield comprises the following steps:
s1: using metal source to CeO 2 Carrying out loading to prepare a metal-loaded semiconductor material;
s2: adding the metal-loaded semiconductor material prepared in the step S1 and 2, 6-di-tert-butylphenol into a reaction vessel, introducing oxygen, performing oxidative coupling reaction of the 2, 6-di-tert-butylphenol, filtering a reaction product, and drying to obtain a product A;
s3: adding the product A and ethanol prepared in the step S2 into a reaction vessel, adding a catalyst after complete dissolution, carrying out reduction reaction for 1-3h at 60-80 ℃ under stirring, evaporating ethanol in a spinning way, filtering the residual substances while the residual substances are hot, washing, and finally drying to obtain a product B;
s4: adding a product B, m-xylene and p-toluenesulfonic acid into a reaction vessel, vacuumizing, introducing nitrogen, then raising the temperature to 130-140 ℃, reacting for 4-6 hours, and decolorizing and recrystallizing reactants to obtain 4,4' -biphenol.
Further, in the process of preparing the metal-loaded semiconductor material in S1, 1-3g of CeO is added into a container 2 Mixing nanometer powder and 10-30ml lysine solution with concentration of 0.53mol/L, adding metalAnd (3) transferring the material to a constant temperature reactor at 60-80 ℃, slowly dropwise adding sodium carbonate solution under the condition of stirring, adjusting the pH value of the solution to be neutral, reacting at constant temperature for 2-5 hours, filtering by using a Buchner funnel, washing a filter cake with deionized water for 3-5 times, drying the filter cake in an oven at 60-65 ℃, then placing the dried filter cake in a muffle furnace at 300-500 ℃, calcining for 2-4 hours in a nitrogen atmosphere, and grinding to obtain the metal-loaded semiconductor material.
Further, in S2, firstly adding 2-4g of 2, 6-di-tert-butylphenol into a reaction vessel, then adding 3-6g of water and 0.01-0.1g of sodium dodecyl benzene sulfonate, stirring for 10-30min, then adding 0.05-0.08 g of metal-supported semiconductor catalyst, vacuumizing, introducing oxygen, performing oxidative coupling reaction for 10-20h under the condition of halogen tungsten illumination and stirring, filtering and washing, and then drying a filter cake to obtain a product A.
Further, in S3, firstly, 3-6g of a product A and 40-70g of ethanol are added into a reaction vessel, after the product A and the ethanol are completely dissolved, 0.1-0.3g of a catalyst is added, then the mixture is placed into a constant temperature reactor at 60-80 ℃ to react for 1-3 hours under stirring, then the ethanol is distilled off, the residual substances are filtered while the residual substances are hot, and then the residual substances are washed for 3-5 times by distilled water, and the pure white solid B is obtained after drying.
Further, in S4, 3-5g of white solid B,5-10ml of m-xylene and 0.01-0.03g of p-toluenesulfonic acid are added into a reaction vessel, the temperature is raised to 130-140 ℃ after 3-5 times of vacuumizing and nitrogen introducing, the reaction is carried out for 4-6 hours, the reaction product is dissolved in 40-60g of 50-70 ℃ hot methanol, and then decoloration and recrystallization treatment are carried out, so that 4,4' -biphenol is obtained.
Further, the metal source in S1 is HAuCl with the solution concentration of 0.1mol/L 4 Solution, pdCl 2 Solution and RUCl 3 Any of the solutions.
Further, the metal source loading in the metal-loaded semiconductor material in S1 is 1-3%.
Further, the catalyst in S3 is sodium hyposulfite.
Further, the constant temperature reactor is an oil bath.
Further, after the reactant is dissolved in hot methanol in S4, active carbon is added into the solution for decoloring treatment, and then the solution is recrystallized to obtain 4,4' -biphenol.
The beneficial effects of the invention are as follows:
the preparation method of the invention uses the metal-loaded semiconductor material as a catalyst and oxygen as an oxidant to realize the oxidative coupling reaction of the 2, 6-di-tert-butylphenol, so that the reaction is carried out at normal temperature, the reaction speed is high, the conversion rate is high, then a small amount of byproducts are reduced into 4,4 '-biphenol through the reduction reaction, purification and filtration are carried out, finally the filtered product is subjected to efficient tert-butyl removal by using p-toluenesulfonic acid as a catalyst to obtain the target product, the obtained 4,4' -biphenol has high yield and good quality, the metal-loaded semiconductor material in the invention can be recycled, a large amount of organic medium solvents and a large amount of aluminum trichloride are not used in the preparation process, the environmental pollution is small, the product purification is easy, the whole preparation process of the invention is simple and easy to operate, the reaction condition is mild, the requirement on equipment is low, and the requirement on mass production and the manufacturing requirement is met, and the application prospect is good.
Drawings
FIG. 1 is a preparation flow chart in examples 1-2 of the present invention.
Detailed Description
In order that the invention may be understood more fully, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended claims. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. The various materials used in the examples, unless otherwise indicated, are commonly commercially available products.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The values disclosed in the embodiments of the present invention are approximate values, and are not determined values. Where the error or experimental conditions allow, all values within the error range may be included without limiting the specific values disclosed in the embodiments of the present invention.
The numerical ranges disclosed in the examples of the present invention are intended to represent relative amounts of the components in the mixture, as well as ranges of temperatures or other parameters recited in the examples of other methods.
The preparation method of the 4,4' -biphenol with high yield is characterized by comprising the following steps:
s1: using metal source to CeO 2 Carrying out loading to prepare a metal-loaded semiconductor material;
s2: adding the metal-loaded semiconductor material prepared in the step S1 and 2, 6-di-tert-butylphenol into a reaction vessel, introducing oxygen, performing oxidative coupling reaction of the 2, 6-di-tert-butylphenol, filtering a reaction product, and drying to obtain a product A;
s3: adding the product A and ethanol prepared in the step S2 into a reaction vessel, adding a catalyst after complete dissolution, carrying out reduction reaction for 1-3h at 60-80 ℃ under stirring, evaporating ethanol in a spinning way, filtering the residual substances while the residual substances are hot, washing, and finally drying to obtain a product B;
s4: adding a product B, m-xylene and p-toluenesulfonic acid into a reaction vessel, vacuumizing, introducing nitrogen, then raising the temperature to 130-140 ℃, reacting for 4-6 hours, and decolorizing and recrystallizing reactants to obtain 4,4' -biphenol.
Further, in the process of preparing the metal-loaded semiconductor material in S1, 1-3g of CeO is added into a container 2 Mixing nanometer powder and 10-30ml lysine solution with concentration of 0.53mol/L, adding metal source, transferring to constant temperature reactor with temperature of 60-80deg.C, slowly dripping sodium carbonate solution under stirring, adjusting pH to neutral, constant temperature reacting for 2-5 hr, filtering with Buchner funnel, and washing filter cake with deionized waterAnd (3) 3-5 times, drying the material in an oven at 60-65 ℃, then placing the dried material in a muffle furnace at 300-500 ℃, calcining the calcined material for 2-4 hours in a nitrogen atmosphere, and grinding the calcined material to obtain the metal-loaded semiconductor material.
Further, in S2, firstly adding 2-4g of 2, 6-di-tert-butylphenol into a reaction vessel, then adding 3-6g of water and 0.01-0.1g of sodium dodecyl benzene sulfonate, stirring for 10-30min, then adding 0.05-0.08 g of metal-supported semiconductor catalyst, vacuumizing, introducing oxygen, performing oxidative coupling reaction for 10-20h under the condition of halogen tungsten illumination and stirring, filtering and washing, and then drying a filter cake to obtain a product A.
Further, in S3, firstly, 3-6g of a product A and 40-70g of ethanol are added into a reaction vessel, after the product A and the ethanol are completely dissolved, 0.1-0.3g of a catalyst is added, then the mixture is placed into a constant temperature reactor at 60-80 ℃ to react for 1-3 hours under stirring, then the ethanol is distilled off, the residual substances are filtered while the residual substances are hot, and then the residual substances are washed for 3-5 times by distilled water, and the pure white solid B is obtained after drying.
Further, in S4, 3-5g of white solid B,5-10ml of m-xylene and 0.01-0.03g of p-toluenesulfonic acid are added into a reaction vessel, the temperature is raised to 130-140 ℃ after 3-5 times of vacuumizing and nitrogen introducing, the reaction is carried out for 4-6 hours, the reaction product is dissolved in 40-60g of 50-70 ℃ hot methanol, and then decoloration and recrystallization treatment are carried out, so that 4,4' -biphenol is obtained.
Further, the metal source in S1 is HAuCl with the solution concentration of 0.1mol/L 4 Solution, pdCl 2 Solution and RUCl 3 Any of the solutions.
Further, the metal source loading in the metal-loaded semiconductor material in S1 is 1-3%.
Further, the catalyst in S3 is sodium hyposulfite.
Further, the constant temperature reactor is an oil bath.
Further, after the reactant is dissolved in hot methanol in S4, active carbon is added into the solution for decoloring treatment, and then the solution is recrystallized to obtain 4,4' -biphenol.
According to the preparation method, the metal-loaded semiconductor material is used as a catalyst, oxygen is used as an oxidant to realize the oxidative coupling reaction of the 2, 6-di-tert-butylphenol, so that the reaction is carried out at normal temperature, the reaction speed is high, the conversion rate is high, a small amount of byproducts are reduced into 4,4 '-biphenol through reduction reaction, purification and filtration are carried out, finally, the filtered product is subjected to efficient tert-butyl removal by using p-toluenesulfonic acid as a catalyst to obtain a target product, the obtained 4,4' -biphenol is high in yield and good in quality, the metal-loaded semiconductor material in the invention can be recycled, a large amount of organic medium solvents and a large amount of aluminum trichloride are not used in the preparation process, the environmental pollution is small, the product purification is easy, the whole preparation process is simple, the operation is easy, the reaction condition is mild, the requirement on equipment is low, and the mass production and manufacturing requirements are met, so that the preparation method has a good application prospect.
The following are specific examples of the present application:
example 1
S1: 2g of CeO was weighed in a beaker 2 The nanometer powder is added with 20ml of lysine solution (the concentration is 0.53 mol/L), and after being evenly mixed, 12ml of PdCl with the concentration of 0.1mol/L is added 2 Transferring the solution to an oil bath pot at 60 ℃, slowly dripping 0.5mol/L sodium carbonate solution until the pH value is 7 under stirring, filtering with a Buchner funnel after keeping constant temperature for 3 hours, washing a filter cake with deionized water for 3 times, placing the filter cake in an oven at 60 ℃ for drying, and finally placing the dried catalyst in N 2 Calcining for 3 hours in a muffle furnace at 450 ℃ under protection, and grinding to obtain a noble metal-loaded semiconductor catalyst;
s2: firstly, adding 2g of 2, 6-di-tert-butylphenol, then adding 5g of water and 0.2g of sodium dodecyl benzene sulfonate into a 25mL three-neck flask, stirring for 20min, then adding 0.02g of noble metal supported semiconductor catalyst, vacuumizing and then introducing O 2 Performing oxidative coupling reaction for 15 hours under the illumination and stirring of a halogen tungsten lamp, filtering and drying to obtain a product A;
s3: adding 4g of a product A and 50g of ethanol into a 100ml three-neck flask, adding 0.1g of sodium hyposulfite after the product A and the ethanol are completely dissolved, then placing the mixture into an oil bath at 60 ℃ for reaction for 2 hours under stirring, evaporating the ethanol from pale yellow to white, filtering the residual substances while the solution is hot, washing the residual substances with distilled water for three times, and drying to obtain pure white solid B;
s4: into a three-necked flask, 4g of a white solid B,6ml of m-xylene, 0.01g of p-toluenesulfonic acid was charged, and the flask was evacuated to N 2 Repeating the reaction for three times, then raising the temperature to 130 ℃, reacting for 5 hours, releasing isobutene in the reaction process, dissolving the obtained filter cake in 40g of 70 ℃ hot methanol, adding 0.1g of activated carbon for decoloring treatment, and recrystallizing the solution to obtain 4,4' -biphenol.
Example 2
S1: 1g of CeO was weighed in a beaker 2 The nanometer powder is added with 10ml of lysine solution (the concentration is 0.53 mol/L), and 15ml of RUCl with 0.1mol/L is added after the mixture is evenly mixed 3 Transferring the solution to an oil bath pot at 70 ℃, slowly dripping 0.5mol/L sodium carbonate solution until the pH value is 7 under stirring, filtering with a Buchner funnel after keeping constant temperature for 4 hours, washing a filter cake with deionized water for 3 times, placing the filter cake in an oven at 60 ℃ for drying, and finally putting the dried catalyst in N 2 Calcining for 4 hours in a muffle furnace at 350 ℃ under protection, and grinding to obtain a noble metal-loaded semiconductor catalyst;
s2: firstly, adding 4g of 2, 6-di-tert-butylphenol, then adding 6g of water and 0.2g of sodium dodecyl benzene sulfonate into a 25mL three-neck flask, stirring for 20min, then adding 0.1g of noble metal supported semiconductor catalyst, vacuumizing and then introducing O 2 Performing oxidative coupling reaction for 20 hours under the illumination and stirring of a halogen tungsten lamp, filtering and drying to obtain a product A;
s3: adding 5g of a product A and 60g of ethanol into a 100ml three-neck flask, adding 0.2g of sodium hyposulfite after the product A and the 60g of ethanol are completely dissolved, then placing the mixture into an oil bath at 70 ℃ for reaction for 2 hours under stirring, evaporating the ethanol from pale yellow to white in a rotary way, filtering the residual substances while the solution is hot, washing the residual substances with distilled water for three times, and drying to obtain pure white solid B;
s4: into a three-necked flask, 3g of a white solid B,5ml of m-xylene and 0.01g of p-toluene were chargedSulfonic acid, vacuumize and lead to N 2 Repeating the reaction for three times, then raising the temperature to 140 ℃, reacting for 3 hours, releasing isobutene in the reaction process, dissolving the obtained filter cake in 50g of 60 ℃ hot methanol, adding 0.1g of activated carbon for decoloring treatment, and recrystallizing the solution to obtain 4,4' -biphenol.
The above preparation methods of examples 1-2 were tested and compared with yields obtained by preparing 4,4' -biphenol by a conventional gas-solid phase method, and the test results are shown in the following table:
as can be seen from the table, the noble metal catalyst is introduced in the oxidative coupling process, and the monomer can be selectively subjected to oxidative coupling by a photocatalysis method, so that side reactions are reduced, the reaction condition is mild, and the yield is high; the noble metal catalyst can be recycled, so that the reaction is more environment-friendly; the reaction speed can be effectively controlled by adjusting the dosage of the noble metal catalyst, so that the reaction process is safer. Compared with an organic solvent, the preparation method has the advantages of no toxicity, no solvent residue, low cost, easy obtainment, no environmental pollution and the like, effectively solves a series of problems of long reaction time, complex process, large pollution and the like in the preparation process of the 4,4 '-biphenol in the prior art, simultaneously, the preparation method can be used for adjusting the dosage of the noble metal photocatalyst and the reagent ratio in the preparation process by introducing the photocatalytic reaction in the monomer oxidative coupling process and preparing the noble metal photocatalyst, optimizing the reaction temperature and the reaction time, greatly improving the yield of the 4,4' -biphenol, has simple technological process, is easy and convenient to operate, has no special equipment in the preparation process, can meet the requirements of industrialized production and manufacture, and has good application prospect.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (6)
1. A method for preparing 4,4' -biphenol with high yield, which is characterized by comprising the following steps:
s1: using metal source to CeO 2 Carrying out loading to prepare a metal-loaded semiconductor material;
s2: adding the metal-loaded semiconductor material prepared in the step S1 and 2, 6-di-tert-butylphenol into a reaction vessel, introducing oxygen, performing oxidative coupling reaction of the 2, 6-di-tert-butylphenol, filtering a reaction product, and drying to obtain a product A;
s3: adding the product A and ethanol prepared in the step S2 into a reaction vessel, adding a catalyst after complete dissolution, carrying out reduction reaction for 1-3h at 60-80 ℃ under stirring, evaporating ethanol in a spinning way, filtering the residual substances while the residual substances are hot, washing, and finally drying to obtain a product B;
s4: adding a product B, m-xylene and p-toluenesulfonic acid into a reaction vessel, vacuumizing, introducing nitrogen, then raising the temperature to 130-140 ℃, reacting for 4-6 hours, and decolorizing and recrystallizing reactants to obtain 4,4' -biphenol;
wherein, in the process of preparing the metal-loaded semiconductor material in S1, 1-3g of CeO is added into a container 2 Mixing nano powder and 10-30ml of lysine solution with the concentration of 0.53mol/L, adding a metal source, then moving the mixture into a constant temperature reactor with the temperature of 60-80 ℃, slowly dripping sodium carbonate solution under the stirring condition, adjusting the pH value of the solution to be neutral, performing constant temperature reaction for 2-5 hours, filtering by using a Buchner funnel, washing a filter cake with deionized water for 3-5 times, then placing the filter cake in an oven with the temperature of 60-65 ℃ for drying, then placing the filter cake in a muffle furnace with the temperature of 300-500 ℃, calcining for 2-4 hours under the nitrogen atmosphere, and grinding to obtain the metal-loaded semiconductor material;
in S2, firstly adding 2-4g of 2, 6-di-tert-butylphenol into a reaction vessel, then adding 3-6g of water and 0.1-0.3g of sodium dodecyl benzene sulfonate, stirring for 10-30min, then adding 0.01-0.1g of metal-supported semiconductor catalyst, vacuumizing, introducing oxygen, performing oxidative coupling reaction for 10-20h under the condition of halogen tungsten illumination and stirring, filtering and washing, and then drying a filter cake to obtain a product A;
wherein the metal source in S1 is PdCl with the solution concentration of 0.1mol/L 2 Solutions and/or RUCl 3 A solution;
wherein the catalyst in S3 is sodium hyposulfite.
2. The process for producing 4,4' -biphenol of claim 1 wherein in S3, 3 to 6g of the product a and 40 to 70g of ethanol are added in a reaction vessel, 0.1 to 0.3g of a catalyst is added after the product a and 40 to 70g of ethanol are completely dissolved, the mixture is placed in a constant temperature reactor at 60 to 80 ℃ and reacted for 1 to 3 hours under stirring, the ethanol is distilled off, the remaining materials are filtered while still hot, and the mixture is washed 3 to 5 times with distilled water and dried to obtain pure white solid B.
3. The process for producing 4,4 '-biphenol in high yield according to claim 1, wherein in S4, 3-5g of white solid B,5-10ml of meta-xylene, 0.01-0.03g of p-toluene sulfonic acid are added to a reaction vessel, the vacuum pumping is repeated 3-5 times, nitrogen is introduced, the temperature is raised to 130-140 ℃, the reaction is carried out for 4-6 hours, the reaction product is dissolved in 40-60g of 50-70 ℃ hot methanol, and then the decoloring and recrystallization treatment are carried out to obtain 4,4' -biphenol.
4. The method for preparing 4,4' -biphenol with high yield according to claim 1, wherein the metal source loading in the metal-loaded semiconductor material in S1 is 1-3%.
5. The method for producing 4,4' -biphenol in high yield according to claim 1 or 2, wherein the isothermal reactor is an oil bath.
6. The method for preparing 4,4 '-biphenol with high yield according to claim 1, wherein after the reactant is dissolved in hot methanol in S4, activated carbon is added into the solution to perform decolorization treatment, and then the solution is recrystallized to obtain 4,4' -biphenol.
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