CN113416119B - Method for synthesizing 4, 4' -dihydroxybiphenyl by adopting loop reactor - Google Patents
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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 42
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 110
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 50
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012046 mixed solvent Substances 0.000 claims abstract description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000001953 recrystallisation Methods 0.000 claims abstract description 5
- 238000005092 sublimation method Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 28
- -1 -tert-butyl biphenyl diphenol Chemical compound 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000011968 lewis acid catalyst Substances 0.000 claims description 7
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- WNFSFUSCVXIYGN-UHFFFAOYSA-N phenylaluminum Chemical compound [Al]C1=CC=CC=C1 WNFSFUSCVXIYGN-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- ZYTJPPRBIGGXRO-UHFFFAOYSA-N propan-2-ylalumane Chemical compound C(C)(C)[AlH2] ZYTJPPRBIGGXRO-UHFFFAOYSA-N 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical group CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000002841 Lewis acid Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 150000007517 lewis acids Chemical class 0.000 abstract 1
- 239000012043 crude product Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000006900 dealkylation reaction Methods 0.000 description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 description 4
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000020335 dealkylation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- ABSXMLODUTXQDJ-UHFFFAOYSA-N 4-(4-sulfophenyl)benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C1=CC=C(S(O)(=O)=O)C=C1 ABSXMLODUTXQDJ-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
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- 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
-
- 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
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
-
- 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
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 4,4 '-dihydroxybiphenyl by adopting a loop reactor, and relates to the field of synthetic methods of 4, 4' -dihydroxybiphenyl. The invention aims to solve the problems of low yield, low reaction efficiency and environmental pollution of 4, 4' -dihydroxybiphenyl synthesized by the existing method. The method comprises the following steps: cheap and easily available phenol is used as a raw material, the phenol and isobutene are added to generate di-tert-butylphenol under the catalysis of Lewis acid, then the di-tert-butylphenol is dissolved in an organic solvent under the alkaline condition and is subjected to oxidative coupling to generate tetra-tert-butylbiphenyl diphenol, finally strong acid is added into a mixed solvent to be catalyzed and removed, the isobutene is recovered, and the high-purity 4, 4' -dihydroxybiphenyl is obtained through a recrystallization method or a sublimation method. The method has the advantages of total yield of over 90 percent, simple operation, high conversion rate, low cost, less three wastes, high product purity and the like. The method is used for preparing the 4, 4' -dihydroxybiphenyl.
Description
Technical Field
The invention relates to the field of a synthetic method of 4, 4' -dihydroxybiphenyl.
Background
4, 4' -dihydroxy biphenyl is widely used for preparing engineering composite materials, polyester, polyurethane, polyphenylsulfone, epoxy resin, dye intermediates, photosensitive materials and the like with excellent performance in the chemical industry because of good heat resistance, no pollution, oxidation resistance and anti-aging effect. The high-purity 4, 4' -dihydroxybiphenyl is mainly applied to thermotropic liquid crystal polymer engineering plastics, and the annual demand of the thermotropic liquid crystal polymer engineering plastics serving as the production center of world electronic products in China accounts for half of the global demand, but the thermotropic liquid crystal polymer engineering plastics can only be imported basically. 4, 4' -dihydroxybiphenyl is used as a basic raw material of thermotropic liquid crystal polymer engineering plastics, has huge domestic market, and the market scale must keep higher acceleration along with the upgrading and updating of the domestic communication electronic industry.
At present, the synthesis process of 4, 4' -dihydroxybiphenyl at home and abroad mainly comprises the following steps: (1) biphenyl sulfonation alkali fusion method. Reacting biphenyl serving as a raw material with concentrated sulfuric acid to obtain biphenyl disulfonic acid, adding sodium hydroxide into solid separated out after cooling to react at 200-300 ℃, and finally neutralizing with sulfuric acid to obtain the product. The method has low cost, and is adopted by some domestic manufacturers, but the obtained product has low purity, cannot meet the requirements of polymer-grade production, needs a large amount of acid and alkali, and has serious environmental pollution. (2) Di-tert-butyl phenol oxidation coupling dealkylation method. The compound formed by the transition metal salt and the organic amine is used for catalyzing and oxidizing the di-tert-butylphenol, and then the product is obtained by acid catalytic dealkylation, the total yield is only 70 percent, and the industrial economy is not enough. (3) A continuous reaction method for oxidative coupling dealkylation of di-tert-butylphenol. And (3) using a continuous reaction device, carrying out air continuous oxidative coupling on the di-tert-butylphenol to obtain tetra-tert-butyl diphenol, and continuously dealkylating in 4-tert-butylphenol to obtain a product. The continuous reaction has high efficiency and is suitable for popularization in industrial production, but the dealkylation reaction has the temperature of more than 220 ℃, and tar byproducts are easy to generate in the reaction.
Disclosure of Invention
The invention provides a method for synthesizing 4,4 '-dihydroxybiphenyl, which has the advantages of high efficiency, high yield and low tar byproduct, and aims to solve the problems of low yield, low reaction efficiency and environmental pollution of the existing method for synthesizing 4, 4' -dihydroxybiphenyl.
A method for synthesizing 4, 4' -dihydroxybiphenyl using a loop reactor, the method comprising the steps of:
firstly, adding phenol into a reaction kettle provided with a loop reaction system;
secondly, introducing nitrogen for evacuation, adding a Lewis acid catalyst, introducing isobutene, reacting by using a reaction kettle provided with a loop reaction system at the temperature of 90-120 ℃ for 4-8 hours to obtain di-tert-butylphenol;
dissolving di-tert-butylphenol in an organic solvent, sequentially adding an alkali catalyst and an oxidant, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 50-100 ℃, reacting for 2-4 h, then heating to 180-200 ℃, reacting for 3-5 h, cooling, and filtering to obtain tetra-tert-butyl biphenol;
dissolving tetra-tert-butyl biphenyl diphenol in a mixed solvent, adding a strong acid catalyst, controlling the temperature to be 120-160 ℃ for reaction, then obtaining 4, 4' -dihydroxy biphenyl by adopting a recrystallization method or a sublimation method, cooling and recovering isobutene generated by the reaction, and completing the process;
step two, the structural formula of the di-tert-butylphenol is as follows:
step three, the structural formula of the tetra-tert-butyl biphenyl diphenol is as follows:
fourthly, the structural formula of the 4, 4' -dihydroxybiphenyl is as follows:
the reaction scheme equation is as follows:
among the above-mentioned technical scheme, the reation kettle who disposes return circuit reaction system includes reation kettle and return circuit reaction system, and return circuit reaction system includes venturi ejector, return circuit circulating pump and heat exchanger. Under the action of the loop circulating pump, the fluid in the kettle is continuously sprayed out through the nozzle of the venturi ejector, and at the nozzle, gas is continuously sucked due to low pressure, and reaction liquid and reaction gas are continuously mixed in the venturi ejector, so that the reaction efficiency is accelerated, the mass transfer ratio (the volume ratio of the gas to the liquid) of the reaction is 0.5-2, and the mass transfer ratio of the common stirring reaction is 0.15-0.35, and the reaction efficiency is greatly improved by a loop reaction system under the comparison.
Optionally, under the condition that the circulating pump is not started, only stirring is started to carry out the reaction, and the rotating speed is 30-60 r/min.
In the above technical scheme, the strong acid catalyst and the mixed solvent in the step four can be recycled for further use.
In the technical scheme, the isobutene generated by the reaction in the fourth step can be recovered by refrigeration and used for the reaction of the second step and phenol to synthesize the di-tert-butylphenol.
The invention has the beneficial effects that:
(1) the invention provides a method for synthesizing 4, 4' -dihydroxybiphenyl by adopting a loop reactor, wherein a reaction device is provided with a loop reaction system, so that the mass transfer rate of gas-liquid phase reaction can be greatly improved, the reaction efficiency is improved, the reaction time can be shortened by 60 percent, the energy consumption of the reaction is correspondingly reduced, and the production cost is reduced. Meanwhile, the external heat exchanger can take away part of reaction heat release, reduce reaction risk and improve the safety coefficient of the reaction.
(2) According to the invention, the mixed solvent of alkane and aromatic ring is used in the tetra-tert-butyl diphenol dealkylation reaction, the reaction temperature is low (120-160 ℃), the byproduct tar is avoided being generated under the high temperature (200 ℃), and meanwhile, the self-polymerization of isobutene molecules generated by the reaction can be avoided and isobutene can be recycled for the reaction with phenol, so that the product economy is improved. After the 4, 4' -dihydroxybiphenyl product prepared by the method is refined in a recrystallization or sublimation mode, the product purity is more than 99.5 percent, and the requirements of polymer-grade industrial products are met.
In the invention, the used strong acid catalyst has a generally higher price, and can be recovered by adding water to dissolve the catalyst after the reaction is finished and the temperature is reduced, so that the method accords with the concept of green chemistry and can also reduce the production cost.
The verification proves that the total yield of the method is more than 90 percent, and the purity of the high-purity 4, 4' -dihydroxybiphenyl prepared by the method reaches more than 99.5 percent.
The method is used for preparing the 4, 4' -dihydroxybiphenyl.
Drawings
FIG. 1 is a schematic view of a reactor equipped with a loop reaction system according to one embodiment;
FIG. 2 is a liquid chromatogram of the product of the first example.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the embodiment relates to a method for synthesizing 4, 4' -dihydroxybiphenyl by adopting a loop reactor, which comprises the following steps:
firstly, adding phenol into a reaction kettle provided with a loop reaction system;
secondly, introducing nitrogen for evacuation, adding a Lewis acid catalyst, introducing isobutene, reacting by using a reaction kettle provided with a loop reaction system at the temperature of 90-120 ℃ for 4-8 hours to obtain di-tert-butylphenol;
dissolving di-tert-butylphenol in an organic solvent, sequentially adding an alkali catalyst and an oxidant, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 50-100 ℃, reacting for 2-4 h, then heating to 180-200 ℃, reacting for 3-5 h, cooling, and filtering to obtain tetra-tert-butyl biphenol;
dissolving tetra-tert-butyl biphenyl diphenol in a mixed solvent, adding a strong acid catalyst, controlling the temperature to be 120-160 ℃ for reaction, then obtaining 4, 4' -dihydroxy biphenyl by adopting a recrystallization method or a sublimation method, cooling and recovering isobutene generated by the reaction, and completing the process;
step two, the structural formula of the di-tert-butylphenol is as follows:
step three, the structural formula of the tetra-tert-butyl biphenyl diphenol is as follows:
fourthly, the structural formula of the 4, 4' -dihydroxybiphenyl is as follows:
the second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: step one, a reaction kettle for configuring a loop reaction system comprises a reaction kettle 1 and the loop reaction system, wherein the loop reaction system comprises a Venturi ejector 3, a loop circulating pump 4 and a heat exchanger 2; the venturi ejector 3 is arranged at the top end of the reaction kettle 1, an inlet of the venturi ejector 3 is communicated with an outlet of the heat exchanger 2, an outlet at the bottom of the reaction kettle 1 is communicated with an inlet at the bottom of the heat exchanger 2, and a loop circulating pump 4 is arranged on a pipeline communicated with the outlet at the bottom of the reaction kettle 1 and the inlet at the bottom of the heat exchanger 2. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: and step two, the Lewis acid catalyst is one or a mixture of more of ferric chloride, aluminum chloride, zinc chloride, isopropyl aluminum and phenyl aluminum, and the dosage of the Lewis acid catalyst is 0.1-10% of the mass of the phenol. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: and in the second step, the mass ratio of the isobutene to the phenol is 1: 1.2-1.7. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and step three, the organic solvent is ethanol, isopropanol, butanol, isobutanol, amyl alcohol, octanol, ethyl acetate, toluene, xylene, p-methyl phenol or m-methyl phenol, and the dosage of the organic solvent is 200-450% of the mass of the di-tert-butyl phenol. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and step three, the oxidant is oxygen-containing mixed gas or oxygen, and the oxygen-containing mixed gas is nitrogen and oxygen mixed gas or air. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and step three, the alkali catalyst is one or a mixture of more of sodium methoxide, sodium ethoxide, sodium tert-butoxide, sodium hydroxide, potassium carbonate, sodium carbonate, diisopropylamine, triethylamine, tetramethylethylenediamine and diethylenetriamine, and the amount of the alkali catalyst is 0.5-5% of the mass of the di-tert-butylphenol. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the mixed solvent is the mixture of a benzene solvent and an alkane solvent, wherein the mass ratio of the benzene solvent to the alkane solvent is 1: 3-6; the benzene solvent is benzene, toluene or xylene, and the alkane solvent is octane, nonane, decane or undecane. The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and fourthly, the mass ratio of the tetra-tert-butyl biphenyl diphenol solution to the mixed solvent is 1 to (2-5.5). The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and step four, the strong acid catalyst is one or a mixture of more of concentrated sulfuric acid, benzenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid and phosphoric acid, and the dosage of the strong acid catalyst is 0.2-20% of the mass of the tetra-tert-butyl diphenol. The other is the same as one of the first to ninth embodiments.
The concrete implementation mode eleven: the present embodiment differs from one of the first to tenth embodiments in that: the purity of the 4, 4' -dihydroxybiphenyl obtained in the fourth step is more than 99.5%. The rest is the same as one of the first to tenth embodiments.
The following examples and comparative experiments were used to verify the beneficial effects of the present invention:
example 1:
this example is a process for the synthesis of 4, 4' -dihydroxybiphenyl using a loop reactor, comprising the steps of:
firstly, adding 500kg of phenol into a reaction kettle provided with a loop reaction system;
secondly, introducing nitrogen for evacuation, adding 10kg of aluminum chloride, introducing isobutene, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 100-120 ℃, and reacting for 6 hours to obtain di-tert-butylphenol;
dissolving di-tert-butylphenol in 2500kg of isobutanol, adding 44kg of sodium hydroxide, continuously introducing oxygen, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 70-80 ℃, reacting for 2 hours, introducing nitrogen to exhaust oxygen, heating to 180-200 ℃, reacting for 3.5 hours, cooling to room temperature, and filtering to obtain tetra-tert-butyl diphenol;
dissolving tetra-tert-butyl biphenyl diphenol in a mixed solvent of toluene and nonane, wherein the mass ratio of toluene to nonane in the mixed solvent is 1: 5; then slowly adding 165kg of concentrated sulfuric acid, controlling the temperature to be 120-135 ℃, reacting for 5 hours, cooling to room temperature, carrying out centrifugal filtration to obtain a crude product, recovering the mixed solvent, recrystallizing the crude product by using ethanol to obtain 416kg of high-purity white crystals of 4, 4' -dihydroxybiphenyl, wherein the purity is 99.8%, and the yield is 84%; freezing and recovering isobutene generated in the reaction.
The liquid chromatogram of the product prepared in this example is shown in FIG. 2, which is obtained by testing Shimadzu LC-20AT apparatus, Lichrospher C18 column (4.6 mm. times.250 mm, 5 μm), mobile phase methanol: 1:1 for water, the sample volume tested was 20 μ L, the detector wavelength was 230nm, as can be seen, there were three characteristic peaks in total, as specified in table 1 below,
TABLE 1
Example 2:
this example is a process for the synthesis of 4, 4' -dihydroxybiphenyl using a loop reactor, comprising the steps of:
firstly, adding 800kg of phenol into a reaction kettle provided with a loop reaction system;
secondly, introducing nitrogen for evacuation, adding 2kg of isopropyl aluminum, introducing isobutene, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 90-110 ℃, and reacting for 4.5 hours to obtain di-tert-butylphenol;
dissolving di-tert-butylphenol in 4500kg of amyl alcohol, adding 85kg of potassium carbonate, continuously introducing oxygen, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 70-80 ℃, reacting for 3.5 hours, introducing nitrogen to exhaust oxygen, heating to 185-200 ℃, reacting for 4.5 hours, cooling to room temperature, and filtering to obtain tetra-tert-butyl diphenol;
dissolving tetra-tert-butyl biphenyl diphenol in a mixed solvent of toluene and undecane, wherein the mass ratio of toluene to undecane in the mixed solvent is 1: 3; slowly adding 17kg of methanesulfonic acid, controlling the temperature to be 130-160 ℃, reacting for 3.5h, cooling to room temperature, performing centrifugal filtration to obtain a crude product, recovering the mixed solvent, recrystallizing the crude product by using ethyl acetate to obtain 720kg of high-purity white crystal 4, 4' -dihydroxybiphenyl, wherein the purity is 99.6%, and the yield is 91%; freezing and recovering isobutene generated in the reaction.
Example 3:
this example is a process for the synthesis of 4, 4' -dihydroxybiphenyl using a loop reactor, comprising the steps of:
firstly, adding 600kg of phenol into a reaction kettle provided with a loop reaction system;
secondly, introducing nitrogen for evacuation, adding 6kg of aluminum chloride and 7kg of phenyl aluminum, introducing isobutene, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 90-110 ℃, and reacting for 4 hours to obtain di-tert-butylphenol;
dissolving di-tert-butylphenol in 4500kg of octanol, adding 10kg of sodium methoxide, continuously introducing oxygen, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 70-90 ℃, reacting for 2.5 hours, then introducing nitrogen to exhaust oxygen, heating to 185-200 ℃, reacting for 4 hours, cooling to room temperature, and filtering to obtain tetra-tert-butyl diphenol;
dissolving tetra-tert-butyl biphenyl diphenol in a mixed solvent of xylene and undecane, wherein the mass ratio of the xylene to the undecane in the mixed solvent is 1: 3; then slowly adding a mixture of 26kg of benzenesulfonic acid and 26kg of p-toluenesulfonic acid, controlling the temperature to be 140-160 ℃, reacting for 3.5h, cooling to room temperature, adding 100kg of water, carrying out centrifugal filtration to obtain a crude product, recovering a water-containing mixed solvent, and recrystallizing the crude product with methanol to obtain 540kg of high-purity white crystal 4, 4' -dihydroxybiphenyl with the purity of 99.7% and the yield of 90%; freezing and recovering isobutene generated in the reaction.
Example 4:
this example is a process for the synthesis of 4, 4' -dihydroxybiphenyl using a loop reactor, comprising the steps of:
firstly, adding 600kg of phenol into a reaction kettle provided with a loop reaction system;
secondly, introducing nitrogen for evacuation, adding 6kg of aluminum chloride and 7kg of phenyl aluminum, introducing isobutene, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 90-110 ℃, and reacting for 4 hours to obtain di-tert-butylphenol;
dissolving di-tert-butylphenol in 4500kg of octanol, adding 10kg of sodium methoxide, continuously introducing oxygen, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 70-90 ℃, reacting for 2.5 hours, then introducing nitrogen to exhaust oxygen, heating to 185-200 ℃, reacting for 4 hours, cooling to room temperature, and filtering to obtain tetra-tert-butyl diphenol;
fourthly, dissolving the tetra-tert-butyl biphenyl diphenol in the water-containing mixed solvent recovered in the third embodiment, and distilling off water at the temperature of 120 ℃; then slowly adding a mixture of 26kg of benzenesulfonic acid and 26kg of p-toluenesulfonic acid, controlling the temperature to be 140-160 ℃, reacting for 4 hours, cooling to room temperature, adding 100kg of water, carrying out centrifugal filtration to obtain a crude product, recovering a mixed solvent, recrystallizing the crude product by using methanol to obtain 540kg of high-purity white crystal 4, 4' -dihydroxybiphenyl, wherein the purity is 99.6%, and the yield is 89.3%; freezing and recovering isobutene generated in the reaction.
Example 5:
the present embodiment is different from the third embodiment in that: and step four, sublimating the crude product by using a sublimation device, controlling the temperature to be 220-320 ℃, and sublimating to obtain 510kg of high-purity white crystal 4, 4' -dihydroxybiphenyl, wherein the purity is 99.8 percent, and the total yield is 85.9 percent.
Example 6:
this example is a process for the synthesis of 4, 4' -dihydroxybiphenyl using a loop reactor, comprising the steps of:
firstly, adding 500kg of phenol into a reaction kettle provided with a loop reaction system;
secondly, introducing nitrogen for evacuation, adding 5kg of zinc chloride and 6kg of phenyl aluminum, introducing isobutene, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 90-110 ℃, and reacting for 4 hours to obtain di-tert-butylphenol;
dissolving di-tert-butylphenol in 200kg of p-methylphenol, adding 33kg of potassium hydroxide, continuously introducing air, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 70-90 ℃, reacting for 4 hours, introducing nitrogen to exhaust oxygen, heating to 185-200 ℃, reacting for 5 hours, cooling to room temperature, and filtering to obtain tetra-tert-butyl diphenol;
dissolving tetra-tert-butyl biphenyl diphenol in a mixed solvent of benzene and decane, wherein the mass ratio of the benzene to the decane in the mixed solvent is 1: 5; then slowly adding a mixture of 32kg of chlorosulfonic acid and 32kg of p-toluenesulfonic acid, controlling the temperature to be 135-160 ℃, reacting for 6.5h, cooling to room temperature, adding 80kg of water, carrying out centrifugal filtration to obtain a crude product, recovering a water-containing mixed solvent, and recrystallizing the crude product with ethyl acetate to obtain 440kg of high-purity white crystal 4, 4' -dihydroxybiphenyl with the purity of 99.5% and the yield of 88.9%; freezing and recovering isobutene generated in the reaction.
Control experiment
Firstly, adding 800kg of phenol into a common reaction kettle;
secondly, introducing nitrogen for evacuation, adding 2kg of isopropyl aluminum, introducing isobutene, controlling the temperature to be 90-110 ℃, and reacting for 9 hours to obtain di-tert-butylphenol;
dissolving di-tert-butylphenol in 4500kg of amyl alcohol, adding 85kg of potassium carbonate, continuously introducing oxygen, controlling the temperature to be 70-80 ℃, reacting for 3.5 hours, then introducing nitrogen to exhaust oxygen, heating to 185-200 ℃, reacting for 6 hours, cooling to room temperature, and filtering to obtain tetra-tert-butyl biphenyl diphenol;
dissolving tetra-tert-butyl biphenyl diphenol in a mixed solvent of toluene and undecane, wherein the mass ratio of toluene to undecane in the mixed solvent is 1: 5; slowly adding 17kg of methanesulfonic acid, controlling the temperature to be 130-160 ℃, reacting for 9 hours, cooling to room temperature, performing centrifugal filtration to obtain a crude product, recovering the mixed solvent, recrystallizing the crude product by using ethyl acetate to obtain 630kg of high-purity white crystal 4, 4' -dihydroxybiphenyl, wherein the purity is 98.9%, and the yield is 79.6%; freezing and recovering isobutene generated in the reaction.
In the second and third steps of the experiment, the reaction is carried out by only starting stirring under the condition of not starting a circulating pump, and the rotating speed is controlled to be 30-60 r/min.
Claims (3)
1. A method for synthesizing 4, 4' -dihydroxybiphenyl by using a loop reactor, characterized in that the method comprises the following steps:
firstly, adding phenol into a reaction kettle provided with a loop reaction system;
secondly, introducing nitrogen for evacuation, adding a Lewis acid catalyst, introducing isobutene, reacting by using a reaction kettle provided with a loop reaction system at the temperature of 90-120 ℃ for 4-8 hours to obtain di-tert-butylphenol;
dissolving di-tert-butylphenol in an organic solvent, sequentially adding an alkali catalyst and an oxidant, reacting by using a reaction kettle provided with a loop reaction system, controlling the temperature to be 50-100 ℃, reacting for 2-4 h, then heating to 180-200 ℃, reacting for 3-5 h, cooling, and filtering to obtain tetra-tert-butyl biphenol;
dissolving tetra-tert-butyl biphenyl diphenol in a mixed solvent, adding a strong acid catalyst, controlling the temperature to be 120-160 ℃ for reaction, then obtaining 4, 4' -dihydroxy biphenyl by adopting a recrystallization method or a sublimation method, cooling and recovering isobutene generated by the reaction, and completing the process;
step two, the structural formula of the di-tert-butylphenol is as follows:
step three, the structural formula of the tetra-tert-butyl biphenyl diphenol is as follows:
fourthly, the structural formula of the 4, 4' -dihydroxybiphenyl is as follows:
step one, a reaction kettle of the configuration loop reaction system comprises a reaction kettle (1) and a loop reaction system, wherein the loop reaction system comprises a Venturi ejector (3), a loop circulating pump (4) and a heat exchanger (2); the Venturi ejector (3) is arranged at the top end of the reaction kettle (1), the inlet of the Venturi ejector (3) is communicated with the outlet of the heat exchanger (2), the outlet at the bottom of the reaction kettle (1) is communicated with the inlet at the bottom of the heat exchanger (2), and a loop circulating pump (4) is arranged on a pipeline for communicating the outlet at the bottom of the reaction kettle (1) with the inlet at the bottom of the heat exchanger (2);
secondly, the Lewis acid catalyst is one or a mixture of more of ferric chloride, aluminum chloride, zinc chloride, isopropyl aluminum and phenyl aluminum, and the dosage of the Lewis acid catalyst is 0.1-10% of the mass of the phenol;
in the second step, the mass ratio of the isobutene to the phenol is 1: 1.2-1.7;
step three, the oxidant is oxygen-containing mixed gas or oxygen, and the oxygen-containing mixed gas is nitrogen and oxygen or air;
thirdly, the alkali catalyst is one or a mixture of more of sodium methoxide, sodium ethoxide, sodium tert-butoxide, sodium hydroxide, potassium carbonate, sodium carbonate, diisopropylamine, triethylamine, tetramethylethylenediamine and diethylenetriamine, and the amount of the alkali catalyst is 0.5-5% of the mass of the di-tert-butylphenol;
the mixed solvent is the mixture of a benzene solvent and an alkane solvent, wherein the mass ratio of the benzene solvent to the alkane solvent is 1: 3-6; the benzene solvent is benzene, toluene or xylene, and the alkane solvent is octane, nonane, decane or undecane;
and step four, the strong acid catalyst is one or a mixture of more of concentrated sulfuric acid, benzenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid and phosphoric acid, and the dosage of the strong acid catalyst is 0.2-20% of the mass of the tetra-tert-butyl diphenol.
2. The method for synthesizing 4, 4' -dihydroxybiphenyl by using loop reactor according to claim 1, characterized in that said organic solvent in step three is ethanol, isopropanol, butanol, isobutanol, pentanol, octanol, ethyl acetate, toluene, xylene, p-methyl phenol or m-methyl phenol, and the amount of organic solvent is 200% -450% of the mass of di-tert-butyl phenol.
3. The method for synthesizing 4, 4' -dihydroxybiphenyl by using a loop reactor as claimed in claim 1, wherein the mass ratio of the tetra-tert-butyldiphenol dissolved in step four to the mixed solvent is 1: 2-5.5.
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