CN117776875A - Preparation process of 4,4' -dihydroxybiphenyl - Google Patents
Preparation process of 4,4' -dihydroxybiphenyl Download PDFInfo
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- CN117776875A CN117776875A CN202311700985.4A CN202311700985A CN117776875A CN 117776875 A CN117776875 A CN 117776875A CN 202311700985 A CN202311700985 A CN 202311700985A CN 117776875 A CN117776875 A CN 117776875A
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- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 239000013067 intermediate product Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 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 16
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- 239000006184 cosolvent Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 239000000047 product Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 10
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical class [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 238000010025 steaming Methods 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 235000010290 biphenyl Nutrition 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- -1 derivative of copper salt Chemical class 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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- 239000004636 vulcanized rubber Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation process of 4,4' -dihydroxybiphenyl, which takes 2, 6-di-tert-butylphenol as a raw material, and is oxidized and coupled into an intermediate product I in a reaction kettle with a circulating filter device under the conditions of self-made catalyst and a first solvent; then, the intermediate product I is subjected to hydrogenation catalyst, cosolvent and second solvent to obtain an intermediate product II; and finally, cooling and collecting the byproduct isobutene generated by steaming the intermediate product II in a high-temperature reaction kettle with a condensation receiving device while reacting, and distilling under reduced pressure to obtain the 4,4' -dihydroxybiphenyl. The invention realizes the circulating filtration through the self-made catalyst which can be dissolved in the reaction solvent, thereby realizing the continuous reaction and the catalyst application, and has the advantages of high reaction speed, high yield, high purity and simple operation process, and can effectively reduce the emission of three wastes and the production cost.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a preparation process of 4,4' -dihydroxybiphenyl.
Background
4,4' -dihydroxybiphenyl is a very important organic compound and is an important organic synthesis intermediate. Because of the good heat resistance, no pollution, oxidation resistance and aging resistance, the modified monomer is widely used for preparing engineering composite materials, polyester, polyurethane, polyphenylsulfone, epoxy resin and other modified monomers with excellent performance in the chemical industry, and rubber and latex, especially light-colored vulcanized rubber products, food packaging rubber and medical latex products; in addition, 4' -dihydroxybiphenyl can be used as a dye intermediate, and a photosensitive material and the like can be synthesized.
At present, three main methods exist in China: 1) A benzidine method; 2) A biphenyl sulfonation alkali fusion method; 3) The biphenyl halogenation hydrolysis method adopts benzidine highly toxic raw materials, and is forbidden to use; the method has the advantages that the amount of the disulfuric acid wastewater is excessive, and the reaction conditions are harsh; the third method needs high-pressure reaction, and the reaction uses highly toxic bromine as a raw material; the three methods have the advantages of reasonable reaction conditions and uncomplicated process conditions, but the purity of the product is difficult to reach more than 99%, so the product is only used as a general chemical raw material and an anti-aging agent.
At present, the method for oxidative coupling, reduction and dealkylation of 2, 6-di-tert-butylphenol is widely adopted abroad, and has the advantages of long process route, complex operation and high energy consumption. The method for synthesizing and preparing the 4,4' -dihydroxybiphenyl is the current development trend from the aspects of product quality, safety in the production process and treatment of three wastes. However, the high purity product of 4,4' -dihydroxybiphenyl is still dependent on import at present due to the limitations of technology, process and the like.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a preparation process of 4,4' -dihydroxybiphenyl, which realizes cyclic filtration by self-made catalyst capable of being dissolved in reaction solvent, thereby realizing continuous reaction and catalyst application, and has the advantages of fast reaction speed, high yield, high purity, simple operation process, and capability of effectively reducing the emission of three wastes and production cost.
In order to achieve the above and other related objects, the present invention provides a process for preparing 4,4' -dihydroxybiphenyl, wherein the reaction route is as follows:
the method comprises the following specific steps:
a) Adding 2, 6-di-tert-butylphenol, a catalyst I and a first solvent into a reaction kettle, heating and continuously introducing air, carrying out heat preservation reaction until the reaction is finished, and purifying to obtain an intermediate product I;
b) Adding the intermediate product I, the catalyst II, the cosolvent and the second solvent obtained in the step a) into a reactor, sequentially carrying out nitrogen and hydrogen replacement, then carrying out reaction, and purifying to obtain an intermediate product II;
c) And c), heating the intermediate product II obtained in the step b) to react, collecting a byproduct isobutene until the reaction is completed, and distilling under reduced pressure to obtain the 4,4' -dihydroxybiphenyl.
In one technical scheme, the reaction kettle used in the step a) is a reaction kettle with a circulating filter device, and comprises a reaction kettle body, a filter and a circulating pump, wherein a ventilation pipeline is arranged at the top end of the reaction kettle body, an inlet at the top end of the reaction kettle body is communicated with an outlet at the bottom of the filter, an outlet at the bottom of the reaction kettle body is communicated with an inlet at the top end of the filter through a pipeline, the circulating pump is arranged on the pipeline, and a stirring paddle is arranged in the reaction kettle body.
Working principle: various raw materials are added into a reaction kettle, air is continuously introduced through a vent pipe at the top end of the reaction kettle, the obtained reactant is conveyed into a filter through an outlet at the bottom end of the reaction kettle by a circulating pump for filtering, an intermediate product I obtained through filtering is remained in the filter, unreacted raw materials, a catalyst and a solvent after filtering are circulated back into the reaction kettle through an outlet at the bottom of the filter for continuous reaction, the intermediate product I in the filter is accumulated to a certain amount for closing circulation, the filter is discharged for purification, and new raw materials can be added into the reaction kettle for continuous reaction.
In one technical scheme, in the step a), the catalyst I is a self-made catalyst; the mass ratio of the catalyst I to the 2, 6-di-tert-butylphenol is 5: 100-10: 100; the first solvent is selected from at least one of methanol, ethanol, isopropanol or n-butanol, preferably methanol; the mass ratio of the first solvent to the 2, 6-di-tert-butylphenol is 4:1 to 10:1, a step of; the temperature of the reaction is 40-45 ℃; and when brown intermediate is precipitated in the reaction kettle, starting a circulating filtering device of the reaction kettle and continuing until the reaction is finished.
In one technical scheme, the preparation steps of the self-made catalyst are as follows: copper chloride, tetramethyl ethylenediamine and methanol are mixed according to the mass ratio of 13.4:11.6: (100-150), heating to 60 ℃, stirring for 2 hours, filtering out insoluble matters, and obtaining a self-made catalyst methanol solution which is directly used.
The self-made catalyst in the invention can be dissolved in a solvent for reaction, so that the generated product can be filtered out by a filter in time, side reactions are reduced, and then the system keeps a homogeneous system all the time, thereby being beneficial to mass transfer and heat transfer. The self-made catalyst is directly added into methanol solution without purification.
In one technical scheme, in the step a), the temperature is reduced to 20-25 ℃ before purification; the purification step comprises pulping and washing the obtained product with methanol at 0-10 ℃, carrying out centrifugal filtration and airing to obtain an intermediate I.
In one embodiment, in step b), the catalyst II is selected from at least one of modified raney nickel catalysts RAN1000, RAN 1300; the usage amount of the catalyst II is 10% -15% of the weight of the intermediate product I; the second solvent is selected from at least one of methanol, ethanol or isopropanol; the use amount of the second solvent is 1.5-2 times of the weight of the intermediate product I; the cosolvent is selected from at least one of dichloromethane, dichloroethane and tetrahydrofuran; the amount of the cosolvent is 1 time of the weight of the second solvent.
In one technical scheme, in the step b), after hydrogen replacement, the reaction is started under the hydrogen pressure of 0.1-0.3 MPa, and the reaction temperature is 40-45 ℃.
In one embodiment, in step b), the purification step is: and filtering to remove the catalyst II under nitrogen atmosphere, and removing the solvent to obtain an intermediate II.
In one technical scheme, in the step c), the reaction is carried out in a high-temperature reaction kettle with a condensation receiving device, wherein the temperature of the reaction is 280-330 ℃; the pressure of the reduced pressure distillation is 50 Pa to 300Pa; the temperature of the reduced pressure distillation is 60-120 ℃.
Compared with the prior art, the preparation process of the 4,4' -dihydroxybiphenyl realizes circulating filtration through the self-made catalyst which can be dissolved in the reaction solvent, thereby realizing continuous reaction and catalyst application, and has the advantages of high reaction speed, high yield of the obtained finished product, high purity, simple operation process, capability of effectively reducing the emission of three wastes and production cost; the self-made catalyst adopted in the step a) can be dissolved in a corresponding reaction solvent, and compared with other catalysts, the self-made catalyst can realize separation of raw materials and intermediates, realize multi-batch application and is simple to operate; the hydrogenation catalyst adopted in the step b) is low in price compared with palladium and platinum catalysts, and is beneficial to reducing the cost.
Drawings
FIG. 1 is a schematic diagram of the reactor with circulating filtration apparatus described in step a).
FIG. 2 is a liquid spectrum of the product prepared in example 1.
In the drawing, 1 is a vent pipe, 2 is a reaction kettle body, 3 is a circulating pump, and 4 is a filter.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form and/or modification thereof.
In the present invention, the equipment, materials, etc. used are commercially available or are commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Preparation of self-made catalyst: 13.4 g of copper chloride is added into 11.6 g of tetramethyl ethylenediamine and 100 g of methanol, the temperature is raised to 60 ℃, the mixture is stirred for 2 hours, insoluble matters are filtered out, and a self-made catalyst methanol solution is obtained and is directly used.
Example 1
Methanol (800 g), self-made catalyst (mainly copper salt derivative) (10 g) and 2, 6-di-tert-butylphenol (206 g,1 mol) are added into a 1L reaction kettle (structure shown in figure 1, comprising a vent pipe 1, a reaction kettle body 2, a circulating pump 3 and a filter 4), stirred and dissolved, heated to 40-45 ℃ and air is introduced at 40-45 ℃. Continuously introducing air for 2-3 hours to precipitate brown intermediates, starting circulating filtration until the sample-feeding detection raw material 2, 6-di-tert-butylphenol is converted, stopping circulating, cooling the solid materials in the filter to 20-25 ℃, pulping and washing the discharged materials with cold methanol (0-10 ℃) and then carrying out throwing filtration, and airing the obtained brown intermediates at room temperature to obtain 410g of 3, 5-tetra-tert-butyl-4, 4-diphenoquinone intermediates.
3, 5-tetra-tert-butyl-4, 4-diphenyl quinone (408.63 g,1 mol) is added into an autoclave, methylene dichloride (600 g) is added for dissolving, methanol (600 g) is added, a modified Raney nickel catalyst RAN1300 (41 g) is added, nitrogen is replaced for three times, hydrogen is replaced for three times, the reaction is carried out under the pressure of 0.1-0.3 Mpa at 40-45 ℃, after the conversion of raw materials is finished, the reaction is stopped, the catalyst is filtered out under the nitrogen atmosphere, the solvent is removed under reduced pressure, and 410.6g of 3, 5-tetra-tert-butyl-4, 4-diphenyl diphenol is obtained, and the following reaction is carried out for standby.
3, 5-tetra-tert-butyl-4, 4-biphenol (410 g,1 mol) is added into a 1L high-temperature reaction kettle with a condensation receiving device, the temperature is increased to 280-330 ℃ for reaction, isobutene which is a byproduct generated by steaming out during the reaction is cooled and collected until the reaction is completed, and the product is purified by vacuum distillation to obtain 180g of 4,4' -dihydroxybiphenyl product. (total molar yield 96%, purity 99.6%)
Example 2
Ethanol (800 g), self-made catalyst (mainly copper salt derivative) (10 g) and 2, 6-di-tert-butylphenol (206 g,1 mol) are added into a 1L reaction kettle (structure shown in figure 1, comprising a vent pipe 1, a reaction kettle body 2, a circulating pump 3 and a filter 4), stirred and dissolved, heated to 40-45 ℃ and air is introduced at 40-45 ℃. Continuously introducing air for 2-3 hours to precipitate brown intermediates, starting circulating filtration until the sample-feeding detection raw material 2, 6-di-tert-butylphenol is converted, stopping circulating, cooling the solid materials in the filter to 20-25 ℃, pulping and washing the discharged materials with cold ethanol (0-10 ℃), and then carrying out throwing filtration to obtain 390g of 3, 5-tetra-tert-butyl-4, 4-diphenoquinone intermediates after the brown intermediates are dried at room temperature.
3, 5-tetra-tert-butyl-4, 4-diphenyl quinone (390 g,0.95 mol) is added into an autoclave, methylene dichloride (600 g) is added for dissolving, methanol (600 g) is added, a modified Raney nickel catalyst RAN1300 (41 g) is added, nitrogen is replaced for three times, hydrogen is replaced for three times, the hydrogen pressure is between 0.1 and 0.3Mpa for 40 and 45 ℃ for reaction, after the conversion of raw materials is finished, the reaction is stopped, the catalyst is filtered out under the nitrogen atmosphere, the solvent is removed under reduced pressure, and 391g of 3, 5-tetra-tert-butyl-4-diphenyl diphenol is obtained, and the following reaction is carried out for standby.
3, 5-tetra-tert-butyl-4, 4-biphenol (391 g,0.95 mol) is added into a 1L high-temperature reaction kettle with a condensation receiving device, the temperature is increased to 280-330 ℃ for reaction, isobutene which is a byproduct formed by steaming out during the reaction is cooled and collected until the reaction is completed, and the product is purified by vacuum distillation to obtain 171g of 4,4' -dihydroxybiphenyl product. (total molar yield 92%, purity 99.7%)
Example 3
Isopropyl alcohol (800 g), self-made catalyst (mainly copper salt derivative) (10 g) and 2, 6-di-tert-butylphenol (206 g,1 mol) are added into a 1L reaction kettle (structure shown in figure 1, comprising a vent pipe 1, a reaction kettle body 2, a circulating pump 3 and a filter 4), stirred and dissolved, heated to 40-45 ℃ and air is introduced at 40-45 ℃. Continuously introducing air for 2-3 hours to precipitate brown intermediates, starting circulating filtration until the sample-feeding detection raw material 2, 6-di-tert-butylphenol is converted, stopping circulating, cooling the solid materials in the filter to 20-25 ℃, pulping and washing the discharged materials with cold ethanol (0-10 ℃) and then carrying out throwing filtration, and airing the obtained brown intermediates at room temperature to obtain the 3831 g of 3, 5-tetra-tert-butyl-4, 4-diphenoquinone intermediates.
3, 5-tetra-tert-butyl-4, 4-diphenyl quinone (3831 g,0.93 mol) is added into an autoclave, methylene dichloride (600 g) is added for dissolving, methanol (600 g) is added, a modified Raney nickel catalyst RAN1300 (40 g) is added, nitrogen is replaced for three times, hydrogen is replaced for three times, the hydrogen pressure is between 0.1 and 0.3Mpa and is reacted at a temperature of between 40 and 45 ℃, after the conversion of raw materials is finished, the reaction is stopped, the catalyst is filtered out under the nitrogen atmosphere, the solvent is removed under reduced pressure, 382g of 3, 5-tetra-tert-butyl-4, 4-diphenyl diphenol is obtained, and the following reaction is ready for use.
3, 5-tetra-tert-butyl-4, 4-biphenol (3832 g,0.93 mol) is added into a 1L high-temperature reaction kettle with a condensation receiving device, the temperature is increased to 280-330 ℃ for reaction, isobutene which is a byproduct generated by evaporation during the reaction is cooled and collected until the reaction is completed, and 165g of 4,4' -dihydroxybiphenyl product is obtained by vacuum distillation and purification of the product. (total molar yield 88%, purity 99.5%)
Comparative example 1
Methanol (800 g), a common oxidative coupling catalyst (mainly a derivative of copper salt) (20 g), 2, 6-di-tert-butylphenol (206 g,1 mol) were added to a 1L reaction flask, the mixture was stirred and dissolved, the temperature was raised to 40-45 ℃, and air was introduced at 40-45 ℃. Continuously introducing air for 10-15 hours, removing methanol after the sample feeding detection raw material 2, 6-di-tert-butylphenol is converted, adding chloroform dissolution products, filtering the catalyst, washing the chloroform solution with water, and removing chloroform to obtain 360g of 3, 5-tetra-tert-butyl-4, 4-biphenyl quinone intermediate.
3, 5-tetra-tert-butyl-4, 4-diphenyl quinone (360 g,0.88 mol) is added into an autoclave, methylene dichloride solution (600 g) is added, methanol (600 g) is added, modified Raney nickel catalyst RAN1300 (41 g) is added, nitrogen is replaced three times, hydrogen is replaced three times, the reaction is carried out under the pressure of 0.1-0.3 Mpa at 40-45 ℃, after the conversion of raw materials is finished, the reaction is stopped, the catalyst is filtered out under the nitrogen atmosphere, the solvent is removed under reduced pressure, and 371g of 3, 5-tetra-tert-butyl-4, 4-diphenyl diphenol is obtained, and the following reaction is carried out for standby.
3, 5-tetra-tert-butyl-4, 4-biphenol (361 g,0.88 mol) is added into a 1L high-temperature reaction kettle with a condensation receiving device, the temperature is increased to 280-330 ℃ for reaction, isobutene which is a byproduct generated by evaporation during the reaction is cooled and collected until the reaction is completed, and 165g of 4,4' -dihydroxybiphenyl product is obtained by vacuum distillation and purification of the product. (total molar yield 84.5%, purity 98.5%)
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (9)
1. A preparation process of 4,4' -dihydroxybiphenyl is characterized in that the reaction route is as follows:
the method comprises the following specific steps:
a) Adding 2, 6-di-tert-butylphenol, a catalyst I and a first solvent into a reaction kettle, heating and continuously introducing air, carrying out heat preservation reaction until the reaction is finished, and purifying to obtain an intermediate product I;
b) Adding the intermediate product I, the catalyst II, the cosolvent and the second solvent obtained in the step a) into a reactor, sequentially carrying out nitrogen and hydrogen replacement, then carrying out reaction, and purifying to obtain an intermediate product II;
c) And c), heating the intermediate product II obtained in the step b) to react, collecting a byproduct isobutene until the reaction is completed, and distilling under reduced pressure to obtain the 4,4' -dihydroxybiphenyl.
2. The process for preparing 4,4' -dihydroxybiphenyl according to claim 1, wherein the reaction kettle used in the step (a) is a reaction kettle with a circulating filter device, and comprises a reaction kettle body, a filter and a circulating pump, wherein a ventilation pipeline is arranged at the top end of the reaction kettle body, an inlet at the top end of the reaction kettle body is communicated with an outlet at the bottom of the filter, an outlet at the bottom of the reaction kettle body is communicated with an inlet at the top end of the filter through a pipeline, the circulating pump is arranged on the pipeline, and a stirring paddle is arranged in the reaction kettle body.
3. The process for preparing 4,4' -dihydroxybiphenyl according to claim 1, wherein in step a), the catalyst I is a self-made catalyst; the mass ratio of the catalyst I to the 2, 6-di-tert-butylphenol is 5: 100-10: 100; the first solvent is selected from at least one of methanol, ethanol, isopropanol or n-butanol; the mass ratio of the first solvent to the 2, 6-di-tert-butylphenol is 4:1 to 10:1, a step of; the temperature of the reaction is 40-45 ℃; and when brown intermediate is precipitated in the reaction kettle, starting a circulating filtering device of the reaction kettle and continuing until the reaction is finished.
4. The process for preparing 4,4' -dihydroxybiphenyl according to claim 3, wherein the self-made catalyst comprises the following steps: copper chloride, tetramethyl ethylenediamine and methanol are mixed according to the mass ratio of 13.4:11.6: (100-150), heating to 60 ℃, stirring for 2 hours, filtering insoluble substances, and obtaining the self-made catalyst methanol solution.
5. The process for preparing 4,4' -dihydroxybiphenyl according to claim 1, wherein in step a), the temperature is reduced to 20-25 ℃ before purification; the purification step comprises pulping and washing the obtained product with methanol at 0-10 ℃, carrying out centrifugal filtration and airing to obtain an intermediate I.
6. The process for preparing 4,4' -dihydroxybiphenyl according to claim 1, wherein in step b), the catalyst II is at least one selected from the group consisting of modified raney nickel catalysts RAN1000 and RAN 1300; the usage amount of the catalyst II is 10% -15% of the weight of the intermediate product I; the second solvent is selected from at least one of methanol, ethanol or isopropanol; the use amount of the second solvent is 1.5-2 times of the weight of the intermediate product I; the cosolvent is selected from at least one of dichloromethane, dichloroethane and tetrahydrofuran; the amount of the cosolvent is 1 time of the weight of the second solvent.
7. The process for preparing 4,4' -dihydroxybiphenyl according to claim 1, wherein in step b), the reaction is started under a hydrogen pressure of 0.1 to 0.3MPa after hydrogen substitution, and the reaction temperature is 40 to 45 ℃.
8. The process for preparing 4,4' -dihydroxybiphenyl according to claim 1, wherein in step b), the purification step is: and filtering to remove the catalyst II under nitrogen atmosphere, and removing the solvent to obtain an intermediate II.
9. The process for preparing 4,4' -dihydroxybiphenyl according to claim 1, wherein in step c), the reaction is carried out in a high-temperature reaction kettle with a condensation receiving device, and the temperature of the reaction is 280-330 ℃; the pressure of the reduced pressure distillation is 50 Pa to 300Pa; the temperature of the reduced pressure distillation is 60-120 ℃.
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