CN111533646A - Industrial preparation method of 4,4 '-dibromodiphenyl ether and 4,4' -dihydroxydiphenyl ether - Google Patents
Industrial preparation method of 4,4 '-dibromodiphenyl ether and 4,4' -dihydroxydiphenyl ether Download PDFInfo
- Publication number
- CN111533646A CN111533646A CN202010450102.9A CN202010450102A CN111533646A CN 111533646 A CN111533646 A CN 111533646A CN 202010450102 A CN202010450102 A CN 202010450102A CN 111533646 A CN111533646 A CN 111533646A
- Authority
- CN
- China
- Prior art keywords
- ether
- bromine
- reaction
- dibromodiphenyl
- dibromodiphenyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- YAWIAFUBXXPJMQ-UHFFFAOYSA-N 1-bromo-4-(4-bromophenoxy)benzene Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1 YAWIAFUBXXPJMQ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 48
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 48
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 14
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000010521 absorption reaction Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 36
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 35
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005893 bromination reaction Methods 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 5
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011265 semifinished product Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 210000003298 dental enamel Anatomy 0.000 claims description 3
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- JTYRXXKXOULVAP-UHFFFAOYSA-N 1,2-dibromo-3-phenoxybenzene Chemical compound BrC1=CC=CC(OC=2C=CC=CC=2)=C1Br JTYRXXKXOULVAP-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 239000007868 Raney catalyst Substances 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 22
- OKTLIOWWGVGPKG-PMACEKPBSA-N (2s)-2-[2-[[(s)-carboxy-(2-hydroxyphenyl)methyl]-(carboxymethyl)amino]ethyl-(carboxymethyl)amino]-2-(2-hydroxyphenyl)acetic acid Chemical compound C1([C@@H](C(O)=O)N(CC(O)=O)CCN(CC(=O)O)[C@H](C(O)=O)C=2C(=CC=CC=2)O)=CC=CC=C1O OKTLIOWWGVGPKG-PMACEKPBSA-N 0.000 description 13
- 108010021819 N,N'-bis(hydroxycarbonylmethyl)-N,N'-bis(alpha-hydroxycarbonyl-2-hydroxytolyl)diaminoethane Proteins 0.000 description 13
- 230000007062 hydrolysis Effects 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RJQLQJZMLISKRJ-UHFFFAOYSA-N 1-bromo-2-(4-bromophenoxy)benzene Chemical compound C1=CC(Br)=CC=C1OC1=CC=CC=C1Br RJQLQJZMLISKRJ-UHFFFAOYSA-N 0.000 description 1
- URUJZHZLCCIILC-UHFFFAOYSA-N 1-chloro-4-(4-chlorophenoxy)benzene Chemical compound C1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1 URUJZHZLCCIILC-UHFFFAOYSA-N 0.000 description 1
- -1 1-trichloroethane Chemical compound 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 241001585533 Callitris endlicheri Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 102000018997 Growth Hormone Human genes 0.000 description 1
- 108010051696 Growth Hormone Proteins 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000000122 growth hormone Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000008635 plant growth Effects 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
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/093—Hydrogen bromide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/10—Bromides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an industrial preparation method of 4,4 '-dibromodiphenyl ether and 4,4' -dihydroxydiphenyl ether, belonging to the technical field of organic synthesis. Heating diphenyl ether and a catalyst in a reaction kettle to 20-100 ℃, stirring and dropwise adding bromine, and gradually increasing the temperature along with the addition of the bromine to prepare a crude product of 4,4' -dibromodiphenyl ether; brominating hydrogen produced in the reaction process is absorbed by three-stage water to prepare hydrobromic acid, and the reaction is carried out under the condition of micro negative pressure; recrystallizing the obtained crude 4,4 '-dibromodiphenyl ether by using an organic solvent to obtain the 4,4' -dibromodiphenyl ether. Sodium hydroxide, a catalyst and deionized water are further added, and after hydrolysis reaction, post-treatment is carried out to prepare the 4,4' -dihydroxy diphenyl ether. The invention can effectively reduce the consumption of energy and raw materials, and has high product efficiency, good quality and low cost. The invention adopts effective environmental protection measures in the production process, is provided with a tail gas absorption device and a sewage treatment facility, and effectively controls and treats the three wastes so as to ensure that the three wastes meet the emission standard.
Description
Technical Field
The invention relates to an industrial preparation method of 4,4 '-dibromodiphenyl ether (DBDE) and 4,4' -dihydroxydiphenyl ether (DHDE), in particular to a method for preparing intermediate 4,4 '-dibromodiphenyl ether firstly and then preparing 4,4' -dihydroxydiphenyl ether, belonging to the technical field of organic synthesis.
Background
4,4' -dibromodiphenyl ether is abbreviated as DBDE, and the DBDE is used as an important intermediate for synthesizing various functional polymers and requires high purity, otherwise, the use value is not large. The synthetic process route of DHDE generally includes the following international reports:
1.4, 4' -diaminodiphenyl ether is subjected to diazotization and hydrolysis to synthesize DHDE, the yield is about 50%, and the purity of crude DHDE is about 47%;
2. the DHDE is obtained by hydrolyzing 4,4' -dichlorodiphenyl ether at high temperature, the yield is about 40 percent, and the purity of the crude DHDE is about 38 percent;
3. the DHDE is obtained by dehydration condensation of hydroquinone, the yield is about 50 percent, and the purity of crude DHDE is about 38 percent;
4. the yield of DHDE obtained by hydrolyzing 4,4' -dibromodiphenyl ether is only 50 percent, and the purity of crude DHDE is approximately 47 percent.
The above methods all have the disadvantages of more side reactions, low yield and high cost, so that the DHDE has wide application, but the market popularization is limited due to high production cost and high product price.
CN01121644A discloses a method for preparing 4,4' -dihydroxy diphenyl ether and its intermediate 4,4' -dibromodiphenyl ether in 2008, 2.13.2, 4' -dibromodiphenyl ether is prepared by reacting diphenyl ether with bromine, and purified by recrystallization. However, the method generates a large amount of HBr in the preparation process, which does not meet the environmental protection requirement, needs high-cost environmental protection treatment and is not beneficial to industrial application and production.
Internationally, countries in which 4,4' -dibromodiphenyl ether is industrially produced include japan and the uk. Among them, the product purity of a certain company in Japan is 87%, and the product purity of a certain company in England is 85%.
4,4' -dihydroxy diphenyl ether can be further produced on the basis of 4,4' -dibromo diphenyl ether, and-OH groups at two ends of 4,4' -dihydroxy diphenyl ether molecules are relatively active functional groups and can react with various organic molecules to synthesize a novel polymer material with high insulating property, high impact strength, high modulus, high temperature resistance and various special properties. For example, various functional polymer materials such as epoxy resin, polycarbonate, polyester resin, liquid crystal polymer, optoelectronic information material, and plant growth hormone with special functions are widely used. Is widely used for manufacturing special materials and medicine synthesis in the fields of aerospace and electronic and electrical industry.
4,4 '-dihydroxy diphenyl ether is a new product filling up the blank in China, the domestic market is only purchased in small batches by research units such as the chemical institute of Chinese academy of sciences, the university of east China's science, the university of Nanjing industry, the university of major research, the university of Sichuan and the like, and the new product is developed, and the achievements of the new product are not industrialized yet.
The foreign market is mainly the japanese market, and the demand is increasing from the first several hundred kilograms to the fixed demand of 5-10 tons/year in the later period in the aspects of developing high-efficiency liquid crystals, electronic packaging materials and the like. For the downstream user in japan, the developed product itself is also a new product at first, and it is developed to a market demand which is relatively large and fixed at present, and it is seen that the market development speed and the industrialization process are still fast. Due to the fact that the industrial device cannot be produced and cannot be supplied in stock recently, the Japan client is very urgent, the manufacturer for producing the product cannot be found internationally, the tin-free state is reached by a few times of special journey, and the negotiation is very easy, the production is expected to be recovered and expanded as soon as possible, if the China cannot reproduce in a short time, the product can be produced in cooperation with the Japan, and preliminary ideas and schemes are proposed. Therefore, the DHDE product is also a new product for filling the international blank.
On the basis of the patent number ZL 200910147473.3 lab scale invention patent, an industrial device which produces 10 tons every year is built in 2010, industrial production and technical development research of nearly ten years are carried out, and the product is subjected to market trial sale and development. Japanese customers also develop new customers and new products from the earlier small batch orders of around 200 kg/year using the prior art 4,4' -dihydroxydiphenyl ether (DHDE) to the later fixed demand of 5-10 tons/year. In the process, the Japanese customers continuously put forward new requirements on the quality indexes of the products, and the Japanese customers continuously improve the requirements on the aspects of environmental protection, safety and the like of chemical products according to the national requirements, so that a plurality of technical breakthrough progresses are obtained, and basic data for amplifying industrial scale design are accumulated.
Disclosure of Invention
The invention aims to overcome the defects and provide the industrial preparation method of the 4,4' -dibromodiphenyl ether, which can recycle generated HBr, has low production cost, intrinsically safe and environment-friendly process and no emission of waste gas and waste water.
The technical scheme of the invention is that the industrial preparation method of 4,4 '-dibromodiphenyl ether comprises the steps of heating diphenyl ether and a catalyst in a reaction kettle to 20-100 ℃, stirring and dripping bromine, and controlling the temperature to gradually increase along with the addition of the bromine to prepare a crude product of the 4,4' -dibromodiphenyl ether; brominating hydrogen produced in the reaction process is absorbed by three-stage water to prepare hydrobromic acid, and the reaction is carried out under the condition of micro negative pressure; recrystallizing the obtained crude 4,4 '-dibromodiphenyl ether by using an organic solvent to obtain the 4,4' -dibromodiphenyl ether.
The chemical reaction equation of the invention is as follows:
further, the steps are as follows: pressing bromine in a bromine storage tank into a bromine high-level metering tank by using compressed air for later use; heating and melting diphenyl ether at 30-50 ℃, pumping the diphenyl ether into a reaction kettle, and adding a catalyst; dropwise adding bromine into a reaction kettle, starting bromination reaction, controlling the reaction temperature at 28-100 ℃, and blowing air to drive out hydrogen bromide and residual bromine in the reaction kettle to prepare a crude product of the 4,4' -dibromodiphenyl ether.
Further, the molar weight of the bromine is 2-2.5 times of that of the diphenyl ether; the adding amount of the catalyst is 0.1-1.0 percent of the weight of the diphenyl ether.
Further, when bromine is dropwise added, the reaction temperature is strictly controlled, the reaction temperature is gradually increased from 20 ℃ to 55 ℃ from the beginning of the dropwise adding of the bromine until the addition of a certain amount of bromine is completed for 10 hours in total; the heating rate is in direct proportion to the bromine dripping rate and is controlled at 3.5 ℃/h; after the bromine is added dropwise, the reaction temperature is controlled to be gradually increased from 55 ℃ to 80 ℃ for 3 hours, and the temperature rising speed is 8 ℃/h, so that the reaction is fully carried out; after the reaction is finished, the temperature is raised to 100 ℃, and hydrogen bromide and residual bromine in the reaction kettle are driven out by blowing.
Further, after the reaction is finished, 0.5-0.7 percent of sodium hydroxide and 0.05-0.07 percent of urea are added into the reaction kettle according to the mass of bromine, and hydrogen bromide and residual bromine in the product are fully removed.
Further, the catalyst is one or more of titanium chloride, tin chloride and zinc chloride.
Further, the organic solvent used for recrystallization is one or more of organic chlorine solvent, methanol, acetone and toluene.
Further, the obtained 4,4' -dibromodiphenyl ether can be further recrystallized and purified by adopting an organic chlorine solvent; the organic chlorine solvent is specifically two or more of chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, dichloromethane, dichloroethane, trichloroethane, 1-trichloroethane and 2-chloropropane.
Further, the hydrogen bromide gas generated by the reaction is processed by first-stage 5M3Second order 3M3Third order 3M3The absorption is carried out by an enamel kettle, and the process is ensured to be carried out under the condition of micro negative pressure.
Furthermore, 57% hydrobromic acid is obtained after primary water absorption of the hydrogen bromide gas, the secondary concentration is 15%, and the tertiary concentration is less than 1%.
The 4,4 '-dibromodiphenyl ether produced by the process is further used for producing 4,4' -dihydroxy diphenyl ether, and the reaction equation is as follows:
taking 4,4 '-dibromodiphenyl ether DBDE as a raw material, adding sodium hydroxide, a catalyst and deionized water into a reaction kettle, filtering to remove the catalyst after the hydrolysis reaction is finished, neutralizing the obtained mother liquor with hydrobromic acid, and filtering to obtain a crude product of the 4,4' -dihydroxy diphenyl ether; extracting with water to obtain 4,4' -dihydroxy diphenyl ether semi-finished product; and further recrystallizing the obtained semi-finished product, and cooling, filtering, elutriating, filtering and drying to obtain a finished product of the 4,4' -dihydroxy diphenyl ether.
The DBDE to sodium hydroxide molar ratio is 1: 1-5, the adding amount of the catalyst is 0.1-5.0% of the DBDE weight; the adding amount of the deionized water is 1-5 times of the weight of the DBDE; the reaction temperature is 100 ℃ and 200 ℃, and the reaction pressure is 0.5-2.5 MPa.
The catalyst is specifically one or a combination of more of titanium chloride, tin chloride, copper chloride, zinc chloride, cuprous chloride, copper oxide and Raney nickel;
the solvent used in the recrystallization is a mixture of any two or more of carbon tetrachloride, chloroform, trichloroethane, dichloroethane, methyl chloride, toluene, o-dichlorobenzene, m-dichlorobenzene, acetone, ethanol and water.
The invention has the beneficial effects that: the method for preparing the 4,4' -dibromodiphenyl ether has the advantages of high efficiency, high purity (not less than 99 percent), simple preparation process, low production cost, intrinsically safe process, environmental protection, no waste gas and waste water discharge, clean production according with various indexes of occupational health, and provision of technical support for realizing industrial large-scale production.
The invention further prepares the 4,4 '-dihydroxy diphenyl ether by the 4,4' -dibromo diphenyl ether, the technical process is carried out under the closed condition, the whole technical process has no release of toxic and harmful substances, the environmental and labor protection conditions are good, and the invention is environment-friendly and safe; the advanced automatic control technology is adopted to perform centralized control on parameters such as temperature, pressure, quality, liquid level and the like in the production process, and the automatic control system has the advantages of high automation degree, stable and reliable technology and good safety performance.
The invention can effectively reduce the consumption of energy and raw materials, and has high product efficiency, good quality and low cost. The invention adopts effective environmental protection measures in the production process, is provided with a tail gas absorption device and a sewage treatment facility, and effectively controls and treats the three wastes so as to ensure that the three wastes meet the emission standard.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a gas-mass diagram of the crude product prepared by the present invention.
FIG. 3 is a chromatogram of crude product from preparation of 200710131773.3.
FIG. 4 is a chromatogram of a sample obtained by purifying 4,4' -dibromodiphenyl ether crystals prepared by a company of UK.
FIG. 5 is a chromatogram of a sample of 4,4' -dibromodiphenyl ether prepared by Nippon Tekken Co.
FIG. 6 is a flow chart of a process for producing 4,4' -dihydroxydiphenyl ether.
Detailed Description
EXAMPLE 14 preparation of 4,4' -Dibromodiphenyl ether
The preparation is carried out according to the process flow chart shown in figure 1, and the specific steps are as follows:
7500kg bromine in the bromine storage tank is pressed into a bromine high-level metering tank by compressed air for standby. Heating 3750kg of diphenyl ether to melt (30-50 deg.C), pumping into 5m3And adding a catalyst into the reaction kettle. Bromine is added into the reaction kettle dropwise to start bromination reaction. Diphenyl ether and bromine are added into the reaction kettle according to the molar ratio of 2.0-2.5. The addition amount of the catalyst is 0.1-1.0 percent of the weight of the diphenyl ether, and the catalyst is titanium chloride, tin chloride and chlorineOne or a combination of zinc compounds.
The bromination reaction temperature should be strictly controlled, the bromine is added dropwise for 10 hours, and the quantitative bromine is added for 10 hours, and the temperature is gradually increased to 55 ℃ from 20 ℃. The temperature rise rate is in direct proportion to the bromine addition rate and rises by 3.5 ℃ per hour. After the bromine is dripped, the temperature is gradually increased from 55 ℃ to 80 ℃ over 3h, and the temperature rising speed is 8 ℃/h, so that the reaction is fully carried out. After the reaction is finished, the temperature is raised and air is blown to drive out the hydrogen bromide and the residual bromine in the reaction kettle. The temperature was raised from 80 ℃ to 100 ℃ for 1 h.
50kg of sodium hydroxide and 5kg of urea are added into a reaction kettle, and hydrogen bromide and residual bromine in the product are sufficiently removed, so that a crude product of the 4,4' -dibromodiphenyl ether is obtained.
GCMS detection is carried out on the crude 4,4' -dibromodiphenyl ether, and the detection result is shown in figure 2. In fig. 2, peak No. 1 is 4-monobromodiphenyl ether (1.64%), peak No. 2 is an isomer of 4,4' -dibromodiphenyl ether, peak No. 3 is an isomer of 4,4' -dibromodiphenyl ether, and peak No. 4 is 4,4' -dibromodiphenyl ether (96.67%).
Comparative examples
1. According to the step of 200710131773.3 patent specification [ 0032 ], controlling the reaction temperature at 50-60 ℃ to obtain a liquid phase map of the crude 4,4' -dibromodiphenyl ether product, wherein the purity is 70.16 percent, and the specific detection result is shown in figure 3.
2. The result of examining the recrystallized and purified 4,4' -dibromodiphenyl ether from a company of UK, supplied by Mitsubishi corporation in 2019, in 3 months is shown in FIG. 4, and the purity is 98.01%.
3. The liquid phase spectrum detection result of the recrystallized and purified 4,4' -dibromodiphenyl ether sample provided by Nippon Nigri iron company in 2019, 1 month is shown in FIG. 5, and the purity is only 88.55%.
The purity of the crude 4,4' -dibromodiphenyl ether obtained by the steps of the invention reaches 97 percent, and the yield greatly exceeds that of ZL 200710131773.3 patent and products in British and Japan. The purity of the product after recrystallization in British and Japan is less than 90 percent, so the total yield is less than 90 percent.
The crude product with the purity of 97 percent prepared by the invention meets the index requirement of continuously preparing the 4,4' -dihydroxy diphenyl ether and can be directly used. And 4,4' -dibromodiphenyl ether supplied to the market needs to be recrystallized and purified, so that the purity reaches the product quality index of not less than 99 percent.
The recrystallization solvent used is chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, dichloromethane, dichloroethane, trichloroethane, 1-trichloroethane, 2-chloropropane, and a combination of two or more of them.
And (4) feeding the filtrate separated in the filtering step into a distillation kettle to evaporate the solvent for reuse. The residual substance in the reactor mainly comprises 4-monobromodiphenyl ether, and the residual substance returns to the bromination reaction kettle to continuously add bromine to produce 4,4' -dibromodiphenyl ether.
The yield of the invention can reach more than 99 percent, and greatly exceeds other background technical levels.
Hydrogen bromide gas generated in the bromination reaction is absorbed by three stages of water to prepare 57% hydrobromic acid for standby or sale.
Hydrogen bromide gas first 5M3Second order 3M3Third order 3M3Absorption in an enamel kettle at the first level of 5M3Hydrobromic acid with the concentration of 57 percent can be obtained in the kettle, the second-level concentration is 15 percent, and the third-level concentration is less than 1 percent. Therefore, the whole process is carried out under the condition of micro negative pressure, and the method achieves the purposes of intrinsic safety, environmental protection, zero emission, clean production and occupational health standard.
EXAMPLE 24 preparation of 4,4' -dihydroxydiphenyl ether
4,4' -dibromodiphenyl ether, NaOH and a catalyst are added into a 5000L hydrolysis kettle according to the proportion to carry out hydrolysis reaction; after the reaction is finished, neutralizing the mother liquor by hydrobromic acid; after the product is separated out, filtering to obtain a crude product; concentrating the filtrate to obtain sodium bromide crystal; and filtering and drying the sodium bromide crystal to obtain a finished product of sodium bromide for sale. Recycling the filtrate; recrystallizing and purifying the crude product by using a mixed solvent to obtain a finished product with the purity of more than 99.5 percent; filtering and drying the sodium bromide crystal, and packaging for sale; evaporating the recrystallization filtrate for reuse; washing the residue with hot water to obtain useful product, and recovering the washing water.
The waste residue component is 4,4' -dihydroxy diphenyl ether self-polymer, the appearance is like black cypress oily solid, and the solid waste incineration center is incinerated after the waste residue component is packaged. Since the black asphalt-like solid is a self-polymer and contains only carbon, hydrogen and oxygen atoms, the carbon black asphalt-like solid is CO2 and H2O after incineration, and does not affect the environment.
In the bromination step in the above reaction process, 310 tons of diphenyl ether and 600 tons of bromine were charged in a year to produce 598 tons of 4,4' -dibromodiphenyl ether [ 95% ]and300 tons of hydrogen bromide, and 600 tons of hydrobromic acid [ 50% ] was absorbed by water for self use.
In the above reaction process, 598 tons of dibromodiphenyl ether (95%), 388 tons of solid caustic soda, 600 tons of self-made hydrobromic acid (50%) and 353 tons of hydrobromic acid (50%) are put into the hydrolysis process every year. 368 tons of [ 81% ] crude 4,4' -dihydroxydiphenyl ether and [ 20% ] sodium bromide solution 6437.5 tons are produced.
368 tons of [ 82% ] dihydroxy diphenyl ether crude product is put into the recrystallization process in the reaction process; recrystallizing with mixed solvent of water, dichloroethane and ethanol. 300 tons of 4,4 '-dihydroxy diphenyl ether with the purity of 99.5 percent is produced, 68 tons of waste residue is produced, and the main components are hydrocarbons such as self-polymer and isomer of the 4,4' -dihydroxy diphenyl ether, and the like, and the hydrocarbons are sent to a solid waste treatment center for incineration. Two tons of solvent ethanol and two tons of dichloroethane are consumed annually.
The preparation process of sodium bromide in the reaction process comprises the following steps: 6437.7 tons/year of 20 percent sodium bromide solution generated in the hydrolysis procedure is concentrated, crystallized, filtered and dried to obtain 1000 tons/year of finished sodium bromide for sale. The steam condensate water is supplied for supplementing water in the hydrolysis process.
The item material table is specifically shown in table 1.
TABLE 1
Compared with ZL 200910147473.3 patent, the invention has the following aspects to make breakthroughs
In terms of product quality, in the process of trial sale for 10 years, Japanese customers continuously put forward a requirement for improving the quality, mainly 1, and the purity index is improved from 99% to 99.5%. 2, the color value is increased to 2 from the original value of ≦ 6. 3, the chloride ion content of the product is increased to less than or equal to 0.2PPM from the original less than or equal to 100 PPM.
In the aspect of yield, the yield is improved to 90 percent from 60 percent of the original small-scale invention technology.
Hydrochloric acid is used in the original hydrolysis neutralization process, so that a large amount of wastewater containing NaCl and NaBr is generated. The industrial scale experiment adopts hydrobromic acid for neutralization, so that only NaBr is contained in the wastewater separated in the process, the concentration and recovery of the sodium bromide product meeting the pharmaceutical grade standard are facilitated, the wastewater discharge is eliminated, and no waste gas is discharged.
In the aspect of safety, toluene is used as a solvent in the recrystallization process, so that the danger level of a production workshop is class A. At present, the mixed solvent of the class C solvent and the deionized water is used instead, so that the danger level of a production workshop is reduced to class C, and the production process and equipment are intrinsically safe.
In the aspect of occupational health, all production process flows are produced under the micro-negative pressure closed condition, and the automation level is improved, so that the production process reaches the occupational health standard.
Claims (10)
- The industrial preparation method of the 4,4' -dibromodiphenyl ether is characterized by comprising the following steps: heating diphenyl ether and a catalyst in a reaction kettle to 20-100 ℃, stirring and dropwise adding bromine, and gradually increasing the temperature along with the addition of the bromine to prepare a crude product of 4,4' -dibromodiphenyl ether; brominating hydrogen produced in the reaction process is absorbed by three-stage water to prepare hydrobromic acid, and the reaction is carried out under the condition of micro negative pressure; recrystallizing the obtained crude 4,4 '-dibromodiphenyl ether by using an organic solvent to obtain the 4,4' -dibromodiphenyl ether.
- 2. The process for industrially preparing 4,4 '-dibromodiphenyl ether as claimed in claim 1, wherein the crude 4,4' -dibromodiphenyl ether is prepared by the following steps: pressing bromine in a bromine storage tank into a bromine high-level metering tank by using compressed air for later use; heating and melting diphenyl ether at 30-50 ℃, pumping the diphenyl ether into a reaction kettle, and adding a catalyst; dropwise adding bromine into a reaction kettle, starting bromination reaction, controlling the reaction temperature at 28-100 ℃, and blowing air to drive out hydrogen bromide and residual bromine in the reaction kettle to prepare a crude product of the 4,4' -dibromodiphenyl ether.
- 3. The process for industrially preparing 4,4' -dibromodiphenyl ether as claimed in claim 2, which is characterized in that: the molar weight of the bromine is 2-2.5 times of that of the diphenyl ether; the adding amount of the catalyst is 0.1-1.0 percent of the weight of the diphenyl ether;when bromine is dropwise added, the reaction temperature is strictly controlled, the reaction temperature is gradually increased from 20 ℃ to 55 ℃ after 10 hours in total from the beginning of the dropwise adding of the bromine until the addition of a certain amount of bromine is completed; the heating rate is in direct proportion to the bromine dripping rate and is controlled at 3.5 ℃/h; after the bromine is added dropwise, the reaction temperature is controlled to be gradually increased from 55 ℃ to 80 ℃ for 3 hours, and the temperature rising speed is 8 ℃/h, so that the reaction is fully carried out; after the reaction is finished, raising the temperature to 100 ℃, and blowing air to drive out the hydrogen bromide and residual bromine in the reaction kettle;after the reaction is finished, 0.5-0.7 percent of sodium hydroxide and 0.05-0.07 percent of urea are added into the reaction kettle according to the mass of bromine, and hydrogen bromide and residual bromine in the product are fully removed.
- 4. The process for industrially preparing 4,4' -dibromodiphenyl ether as claimed in claim 2, which is characterized in that: the catalyst is specifically one or more of titanium chloride, tin chloride and zinc chloride;the organic solvent used for recrystallization is one or more of organic chlorine solvent, methanol, acetone and toluene.
- 5. The industrial process for preparing 4,4' -dibromodiphenyl ether as claimed in claim 1, which is characterized in that: the obtained 4,4' -dibromodiphenyl ether can be further recrystallized and purified by adopting an organic chlorine solvent; the organic chlorine solvent is specifically two or more of chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, dichloromethane, dichloroethane, trichloroethane, 1-trichloroethane and 2-chloropropane.
- 6. The process for industrially preparing 4,4' -dibromodiphenyl ether according to claim 1, wherein the dibromodiphenyl ether is prepared from a mixture of a diphenyl ether and a sulfur-containing compoundThe method comprises the following steps: the hydrogen bromide gas generated by the reaction is processed by first-grade 5M3Second order 3M3Third order 3M3The absorption is carried out by an enamel kettle, and the process is ensured to be carried out under the condition of micro negative pressure.
- 7. The process for industrially preparing 4,4' -dibromodiphenyl ether according to claim 6, which is characterized in that: 57% hydrobromic acid is obtained after primary water absorption of the hydrogen bromide gas, the secondary concentration is 15%, and the tertiary concentration is less than 1%.
- The industrial preparation method of 4,4' -dihydroxy diphenyl ether is characterized by comprising the following steps: taking 4,4 '-dibromodiphenyl ether DBDE as a raw material, adding sodium hydroxide, a catalyst and deionized water into a reaction kettle, filtering to remove the catalyst after the hydrolysis reaction is finished, neutralizing the obtained mother liquor with hydrobromic acid, and filtering to obtain a crude product of the 4,4' -dihydroxy diphenyl ether; extracting with water to obtain 4,4' -dihydroxy diphenyl ether semi-finished product; and further recrystallizing the obtained semi-finished product, and cooling, filtering, elutriating, filtering and drying to obtain a finished product of the 4,4' -dihydroxy diphenyl ether.
- 9. The process for the industrial preparation of 4,4' -dihydroxydiphenyl ether according to claim 8, wherein: the DBDE to sodium hydroxide molar ratio is 1: 1-5, the adding amount of the catalyst is 0.1-5.0% of the DBDE weight; the adding amount of the deionized water is 1-5 times of the weight of the DBDE; the reaction temperature is 100 ℃ and 200 ℃, and the reaction pressure is 0.5-2.5 MPa.
- 10. The process for the industrial preparation of 4,4' -dihydroxydiphenyl ether according to claim 8, wherein: the catalyst is specifically one or a combination of more of titanium chloride, tin chloride, copper chloride, zinc chloride, cuprous chloride, copper oxide and Raney nickel;the solvent used in the recrystallization is a mixture of any two or more of carbon tetrachloride, chloroform, trichloroethane, dichloroethane, methyl chloride, toluene, o-dichlorobenzene, m-dichlorobenzene, acetone, ethanol and water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010450102.9A CN111533646A (en) | 2020-05-25 | 2020-05-25 | Industrial preparation method of 4,4 '-dibromodiphenyl ether and 4,4' -dihydroxydiphenyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010450102.9A CN111533646A (en) | 2020-05-25 | 2020-05-25 | Industrial preparation method of 4,4 '-dibromodiphenyl ether and 4,4' -dihydroxydiphenyl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111533646A true CN111533646A (en) | 2020-08-14 |
Family
ID=71978076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010450102.9A Pending CN111533646A (en) | 2020-05-25 | 2020-05-25 | Industrial preparation method of 4,4 '-dibromodiphenyl ether and 4,4' -dihydroxydiphenyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111533646A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896619A (en) * | 2021-11-01 | 2022-01-07 | 白银图微新材料科技有限公司 | Preparation method of 4,4' -dibromodiphenyl ether |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3518316A (en) * | 1968-07-08 | 1970-06-30 | Du Pont | Bromination process |
| US4835322A (en) * | 1987-10-19 | 1989-05-30 | Great Lakes Chemical Corporation | Process for producing 4,4'-dibromodiphenyl ether |
| EP0429975A1 (en) * | 1989-11-27 | 1991-06-05 | Bromine Compounds Ltd. | Process for the preparation of 4,4'-dibromodiphenylether |
| CN101121644A (en) * | 2007-08-29 | 2008-02-13 | 徐浩清 | Method for preparing 4,4'-dihydroxydiphenyl ether and intermediate 4,4'-dibromodiphenyl ether thereof |
| CN101575271A (en) * | 2007-08-29 | 2009-11-11 | 徐浩清 | Method for utilizing 4,4'- dibromodiphenyl ether to prepare 4,4'-dihydroxy diphenyl ether |
| JP2011057652A (en) * | 2009-09-14 | 2011-03-24 | Agro Kanesho Co Ltd | Method for producing 4,4'-dihydroxydiphenyl ether |
| CN103724169A (en) * | 2012-10-12 | 2014-04-16 | 苏州四同医药科技有限公司 | Preparation method of 4,4'-dihydroxydiphenyl ether |
| CN105492498A (en) * | 2013-09-03 | 2016-04-13 | Dic株式会社 | Polyarylene sulfide resin and manufacturing method therefor, poly(arylene sulfonium salt) and manufacturing method therefor, and sulfoxide |
| CN106146807A (en) * | 2016-06-27 | 2016-11-23 | 华南理工大学 | One class main chain polyfluorene base polymer containing non-conjugated units and preparation method and application |
| CN110590515A (en) * | 2019-09-23 | 2019-12-20 | 遵义医科大学 | Synthesis method of brominated hydroxydiphenyl ether compound |
-
2020
- 2020-05-25 CN CN202010450102.9A patent/CN111533646A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3518316A (en) * | 1968-07-08 | 1970-06-30 | Du Pont | Bromination process |
| US4835322A (en) * | 1987-10-19 | 1989-05-30 | Great Lakes Chemical Corporation | Process for producing 4,4'-dibromodiphenyl ether |
| EP0429975A1 (en) * | 1989-11-27 | 1991-06-05 | Bromine Compounds Ltd. | Process for the preparation of 4,4'-dibromodiphenylether |
| CN101121644A (en) * | 2007-08-29 | 2008-02-13 | 徐浩清 | Method for preparing 4,4'-dihydroxydiphenyl ether and intermediate 4,4'-dibromodiphenyl ether thereof |
| CN101575271A (en) * | 2007-08-29 | 2009-11-11 | 徐浩清 | Method for utilizing 4,4'- dibromodiphenyl ether to prepare 4,4'-dihydroxy diphenyl ether |
| JP2011057652A (en) * | 2009-09-14 | 2011-03-24 | Agro Kanesho Co Ltd | Method for producing 4,4'-dihydroxydiphenyl ether |
| CN103724169A (en) * | 2012-10-12 | 2014-04-16 | 苏州四同医药科技有限公司 | Preparation method of 4,4'-dihydroxydiphenyl ether |
| CN105492498A (en) * | 2013-09-03 | 2016-04-13 | Dic株式会社 | Polyarylene sulfide resin and manufacturing method therefor, poly(arylene sulfonium salt) and manufacturing method therefor, and sulfoxide |
| CN106146807A (en) * | 2016-06-27 | 2016-11-23 | 华南理工大学 | One class main chain polyfluorene base polymer containing non-conjugated units and preparation method and application |
| CN110590515A (en) * | 2019-09-23 | 2019-12-20 | 遵义医科大学 | Synthesis method of brominated hydroxydiphenyl ether compound |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896619A (en) * | 2021-11-01 | 2022-01-07 | 白银图微新材料科技有限公司 | Preparation method of 4,4' -dibromodiphenyl ether |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101823448B1 (en) | Reclaiming toluenediamine from tar waste residue discharged from synthesis of toluene diisocynate | |
| Duque‐Ingunza et al. | Process optimization for catalytic glycolysis of post‐consumer PET wastes | |
| CN110818543A (en) | Novel method for efficiently synthesizing dibenzoyl methane | |
| CN110372551B (en) | Preparation method of 3-mercaptopropionic acid | |
| CN110818886B (en) | Method for preparing regenerated food-grade PET polyester from waste PET polyester | |
| CN113117748B (en) | Bicyclic guanidine salt eutectic solvent catalyst and preparation method and application thereof | |
| CN102659590A (en) | Alcoholysis recovery method of waster polylactic acid in ionic liquid environment | |
| CN111533646A (en) | Industrial preparation method of 4,4 '-dibromodiphenyl ether and 4,4' -dihydroxydiphenyl ether | |
| Tabekh et al. | Chemical recycling of poly (ethylene terephthalate) using sulfuric acid | |
| CN100340538C (en) | Method for preparing bromopentoic acid | |
| CN101003466A (en) | Method for synthesizing bisphenol fluorine by catalysis of highly acidic cation exchange resin | |
| CN106220578A (en) | A kind of new benzoguanamine production method | |
| CN114276220A (en) | Preparation method of o-phenylphenoxyethanol | |
| CN114835569B (en) | Method for producing photoinitiator UV-184 by condensation method | |
| CN100343217C (en) | Method for oxidizing fluorene to 9-fluorenone | |
| CN114196002B (en) | Preparation method of transparent flame-retardant novel polycarbonate, polycarbonate and application thereof | |
| CN113735764B (en) | Method for recovering 2-cyano-3-chloro-5-trifluoromethylpyridine rectifying still residue | |
| CN111187138B (en) | Method for treating dichlorobenzene rectification residue | |
| CN115141363A (en) | Method for preparing regenerated cationic polyester by using waste polyester | |
| JP5529498B2 (en) | Process for producing dimethyl terephthalate from polyester | |
| CN114621088B (en) | Preparation method of diethyl terephthalamide | |
| CN102491951A (en) | Production process of triallyl cyanurate | |
| CN114751887B (en) | Synthesis method of ethylene carbonate | |
| CN116425620A (en) | Method for catalyzing controllable degradation of polyethylene terephthalate melt | |
| CN219518808U (en) | Green chlorine hydrogen internal consumption absorption system in foaming agent production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200814 |
|
| RJ01 | Rejection of invention patent application after publication |