CN116891402A - Preparation method of methyl octabromoether - Google Patents
Preparation method of methyl octabromoether Download PDFInfo
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- CN116891402A CN116891402A CN202311159754.7A CN202311159754A CN116891402A CN 116891402 A CN116891402 A CN 116891402A CN 202311159754 A CN202311159754 A CN 202311159754A CN 116891402 A CN116891402 A CN 116891402A
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 126
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 50
- 238000006266 etherification reaction Methods 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 39
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000005893 bromination reaction Methods 0.000 claims abstract description 13
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000004005 microsphere Substances 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 24
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 24
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 239000002808 molecular sieve Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 235000010265 sodium sulphite Nutrition 0.000 claims description 12
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 12
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 11
- 229920000858 Cyclodextrin Polymers 0.000 claims description 11
- 239000001116 FEMA 4028 Substances 0.000 claims description 11
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 11
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 11
- 229960004853 betadex Drugs 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 10
- 229920002643 polyglutamic acid Polymers 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 9
- 229940057995 liquid paraffin Drugs 0.000 claims description 9
- 239000001587 sorbitan monostearate Substances 0.000 claims description 9
- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 9
- 229940035048 sorbitan monostearate Drugs 0.000 claims description 9
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004153 Potassium bromate Substances 0.000 claims description 8
- 229940094037 potassium bromate Drugs 0.000 claims description 8
- 235000019396 potassium bromate Nutrition 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 15
- 230000035484 reaction time Effects 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- 238000005406 washing Methods 0.000 description 16
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- 238000004811 liquid chromatography Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 5
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011895 specific detection Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- SCZZNWQQCGSWSZ-UHFFFAOYSA-N 1-prop-2-enoxy-4-[2-(4-prop-2-enoxyphenyl)propan-2-yl]benzene Chemical compound C=1C=C(OCC=C)C=CC=1C(C)(C)C1=CC=C(OCC=C)C=C1 SCZZNWQQCGSWSZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GRTULCMYXWUUEK-UHFFFAOYSA-N 2,3-dibromo-1-(2,3-dibromobutoxy)butane Chemical compound BrC(COCC(C(Br)C)Br)C(C)Br GRTULCMYXWUUEK-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- DSDHFHLZEFQSFM-UHFFFAOYSA-N 2-chlorobut-2-ene Chemical compound CC=C(C)Cl DSDHFHLZEFQSFM-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and meanwhile Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with 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
- C07C41/18—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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of methyl octabromoether, which belongs to the technical field of methyl octabromoether, and comprises the following steps: etherification reaction, bromination reaction and post-treatment; adding tetrabromobisphenol A and methallyl chloride into a reactor, controlling the temperature of the reactor to 45-55 ℃, stirring for 10-15min, adding sodium hydroxide aqueous solution to adjust the pH to 9-10, adding a composite phase transfer catalyst, continuously stirring for 4-5h, stopping stirring, and cooling to obtain an intermediate methyl tetrabromoether; the method can reduce the catalyst consumption in the etherification reaction, shorten the etherification reaction time, improve the purity and yield of the prepared methyl octabromoether, reduce the recovery difficulty of the catalyst in the etherification reaction, and still achieve higher catalytic activity after the catalyst in the etherification reaction is used for a plurality of times.
Description
Technical Field
The invention relates to the technical field of methyl octabromoether, in particular to a preparation method of methyl octabromoether.
Background
Methyl octabromoether, also known as tetrabromobisphenol A-bis (2, 3-dibromo (methyl) propyl) ether, is an important species in brominated flame retardants, and is a high molecular organic flame retardant with aromatic bromine and aliphatic bromine. The methyl octabromoether is white crystal powder in appearance, can be dissolved in organic solvents such as acetone and ester, has a flame retardant effect higher than that of a brominated aromatic flame retardant, has excellent heat stability, and can ensure safer processing equipment and more excellent product performance.
At present, the preparation method of the methyl octabromoether mainly comprises three steps of etherification, bromination and washing, specifically, tetrabromobisphenol A and an etherifying agent are subjected to etherification reaction under an alkaline condition to obtain an intermediate, a catalyst which is usually used in the etherification reaction is a phase transfer catalyst, the intermediate is subjected to bromination reaction to obtain a crude product, and then the crude product is washed to obtain the methyl octabromoether; however, the above method has two problems: firstly, the use amount of the phase transfer catalyst is large, the recovery is difficult, the etherification reaction time is long, and secondly, the purity and the yield of the prepared product methyl octabromoether are low. Although the phase transfer catalyst can be recovered by loading the phase transfer catalyst, the recovery rate of the loaded phase transfer catalyst is low, and the catalytic efficiency is greatly reduced after multiple uses.
Chinese patent CN112830868B provides a method for preparing high purity methyl octabromoether, comprising the steps of: adding tetrabromobisphenol A and caustic soda flakes into a solvent A, stirring until the tetrabromobisphenol A and caustic soda flakes are completely dissolved, adding an efficient catalyst A, dropwise adding methyl chloropropene for reaction, and filtering after the reaction is finished to obtain an intermediate product methyl tetrabromoether; adding an intermediate product methyl tetrabromoether into the solvent B, stirring and dissolving, washing and separating water after all materials are dissolved, adding the high-efficiency catalyst B, and dropwise adding bromine to obtain a solution containing methyl octabromoether; neutralizing a solution containing methyl octabromoether with a sodium sulfite solution, washing with water to separate water, distilling for crystallization, filtering and drying to obtain methyl octabromoether; the purity of the methyl octabromoether prepared by the patent can reach more than 98 percent, but the use amount of the phase transfer catalyst is large, the recovery is difficult, the etherification reaction time is long, and the yield is low.
Chinese patent CN105622362B discloses a method for preparing methyl octabromoether flame retardant, which comprises etherifying bisphenol a with etherifying agent to obtain bisphenol a bis allyl ether intermediate; then, hydrobromic acid and hydrogen peroxide are taken as brominating agents to carry out bromination reaction with bisphenol A bis allyl ether intermediate to prepare methyl octabromoether or octabromoether; the yield of the methyl octabromoether or octabromoether prepared by the patent is up to 98 percent, and the purity is up to 98.5 percent; however, the amount of the phase transfer catalyst used is large, the recovery is difficult, and the etherification reaction time is long.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the preparation method of the methyl octabromoether, which can reduce the catalyst dosage in the etherification reaction, shorten the etherification reaction time, improve the purity and the yield of the prepared methyl octabromoether, reduce the recovery difficulty of the catalyst in the etherification reaction, and can still achieve higher catalytic activity after the catalyst in the etherification reaction is used for a plurality of times.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the methyl octabromoether comprises the following steps: etherification reaction, bromination reaction and post-treatment;
adding tetrabromobisphenol A and methallyl chloride into a reactor, controlling the temperature of the reactor to 45-55 ℃, stirring for 10-15min, adding sodium hydroxide aqueous solution to adjust the pH to 9-10, adding a composite phase transfer catalyst, continuously stirring for 4-5h, stopping stirring, and cooling to obtain an intermediate methyl tetrabromoether;
in the etherification reaction, the mass ratio of tetrabromobisphenol A to methallyl chloride to the composite phase transfer catalyst is 54-55:21-23:0.11-0.12;
the mass fraction of the sodium hydroxide aqueous solution is 10-15%;
the preparation method of the composite phase transfer catalyst comprises the following steps: preparing microspheres, preparing chloridized microspheres and loading;
the preparation method comprises the steps of (1) adding polyvinyl alcohol 2488, beta-cyclodextrin, polyvinyl amine, glutaraldehyde aqueous solution and deionized water into a reactor, controlling the temperature of the reactor to 40-50 ℃, stirring for 10-20min, adding gamma-polyglutamic acid and sorbitan monostearate, and continuously stirring for 30-40min to obtain a mixed solution; adding liquid paraffin into a reactor, controlling the temperature of the reactor to 60-70 ℃, dropwise adding the mixed solution into the reactor while stirring, continuously stirring for 40-50min after the dropwise adding is finished, filtering, cleaning and drying filter residues to obtain microspheres;
in the preparation of the microsphere, the mass ratio of polyvinyl alcohol 2488, beta-cyclodextrin, polyvinyl amine, glutaraldehyde aqueous solution, deionized water, gamma-polyglutamic acid, sorbitan monostearate and liquid paraffin is 6-7:5-6:1.5-2:18-20:20-25:0.3-0.4:0.2-0.3:150-200;
the mass fraction of the glutaraldehyde aqueous solution is 50%;
the dropping speed of the mixed solution is 4-5g/min;
adding microspheres, epichlorohydrin and hydrochloric acid aqueous solution into a reactor, controlling the temperature of the reactor to 60-70 ℃, stirring for 50-60min, filtering, cleaning and drying filter residues to obtain the chloridized microspheres;
in the preparation of the chloridized microsphere, the mass ratio of the microsphere, the epichlorohydrin to the hydrochloric acid aqueous solution is 2-2.2:5-5.5:70-75;
the mass fraction of the hydrochloric acid aqueous solution is 10-12%;
adding chloridized microspheres, tetrabutylammonium bromide, tetrabutylammonium chloride and sodium hydroxide aqueous solution into a reactor, controlling the temperature of the reactor to 60-70 ℃, stirring for 10-15min, adding ZSM-5 molecular sieve, stirring for 30-40min, adding ethylenediamine, continuously stirring for 4-5h, filtering, cleaning and drying filter residues to obtain a composite phase transfer catalyst;
in the load, the mass ratio of the chloridized microspheres to the tetrabutylammonium bromide to the tetrabutylammonium chloride to the sodium hydroxide aqueous solution to the ZSM-5 molecular sieve to the ethylenediamine is 2-2.2:1-1.2:1-1.2:15-16:8-9:25-30;
silicon-aluminum molar ratio SiO of ZSM-5 molecular sieve 2 /Al 2 O 3 35-70;
adding aqueous hydrochloric acid solution into a reactor filled with intermediate methyl tetrabromoether to adjust the pH to 7-7.5, then adding deionized water, controlling the temperature of the reactor to 25-30 ℃, stirring for 10-15min, adding hydrobromic acid and potassium bromate, continuously stirring for 10-20min, dropwise adding hydrogen peroxide, and continuously stirring for 3.5-4h after the dropwise adding is finished to obtain a reaction solution;
the mass ratio of tetrabromobisphenol A in the etherification reaction to deionized water, hydrobromic acid, potassium bromate and hydrogen peroxide in the bromination reaction is 54-55:300-330:210-230:2-2.5:65-70;
the mass fraction of hydrobromic acid is 38-40%;
the mass fraction of the hydrogen peroxide is 28-30%;
the dropping speed of the hydrogen peroxide is 5-6g/min;
the mass fraction of the hydrochloric acid aqueous solution is 4-5%;
the post-treatment is carried out, the reaction liquid is filtered, a sodium sulfite aqueous solution is used for cleaning a filter cake, deionized water is used for cleaning the filter cake, methylene dichloride is added after cleaning, stirring and filtering are carried out, filter residues are dried and used as a recovered composite phase transfer catalyst for recycling, filtrate is desolventized, and methyl octabromoether is obtained after the solvent is completely removed;
in the post-treatment, the mass fraction of the sodium sulfite aqueous solution is 8-10%;
the mass ratio of tetrabromobisphenol A in the etherification reaction to methylene dichloride in the post-treatment is 54-55:280-300.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of methyl octabromoether can reduce the dosage of the catalyst in etherification reaction, and the mass ratio of the composite phase transfer catalyst to tetrabromobisphenol A is 0.11-0.12:54-55;
(2) The preparation method of methyl octabromoether can shorten the etherification reaction time to 250-315min;
(3) According to the preparation method of the methyl octabromoether, the purity of the prepared methyl octabromoether can reach 97.94-98.64%, and the yield can reach 97.82-98.45%;
(4) The preparation method of methyl octabromoether can reduce the recovery difficulty of the catalyst in etherification reaction, and can realize the recovery of the composite phase transfer catalyst in the recrystallization step;
(5) According to the preparation method of the methyl octabromoether, after the catalyst in the etherification reaction is used for 20 times, the purity of the prepared methyl octabromoether can still reach 97.82-98.56%, and the yield can still reach 92.06-93.54%.
Drawings
FIG. 1 is a liquid chromatogram of methyl octabromoether prepared in example 1;
FIG. 2 is a liquid chromatogram of methyl octabromoether prepared in example 2;
FIG. 3 is a liquid chromatogram of methyl octabromoether prepared in example 3;
FIG. 4 is a liquid chromatogram of methyl octabromoether prepared in example 4.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
The preparation method of the methyl octabromoether specifically comprises the following steps:
1. etherification reaction: adding 54g of tetrabromobisphenol A and 21g of methallyl chloride into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 45 ℃, controlling the stirring rotation speed to 300rpm, stirring for 10min, adding 10% sodium hydroxide aqueous solution by mass fraction to adjust the pH value to 9, adding 0.11g of composite phase transfer catalyst, continuously stirring for 4h, stopping stirring, and naturally cooling to room temperature to obtain an intermediate methyl tetrabromoether;
the preparation method of the composite phase transfer catalyst comprises the following steps: adding 6g of polyvinyl alcohol 2488, 5g of beta-cyclodextrin, 1.5g of polyvinyl amine, 18g of glutaraldehyde water solution with the mass fraction of 50% and 20g of deionized water into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 40 ℃, controlling the stirring speed to 100rpm, stirring for 10min, adding 0.3g of gamma-polyglutamic acid and 0.2g of sorbitan monostearate, and continuing stirring for 30min to obtain a mixed solution; 150g of liquid paraffin is added into a four-mouth bottle, the temperature of the four-mouth bottle is controlled to be 60 ℃, the stirring speed is controlled to be 100rpm, then mixed liquid is dripped into the four-mouth bottle, the dripping speed of the mixed liquid is controlled to be 4g/min, stirring is continued for 40min after dripping is finished, filtering is carried out, deionized water is used for cleaning filter residues for 2 times, and the filter residues are dried at 110 ℃ to obtain microspheres; adding 2g of microspheres, 5g of epichlorohydrin and 70g of hydrochloric acid aqueous solution with the mass fraction of 10% into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 60 ℃, controlling the stirring speed to 200rpm, stirring for 50min, filtering, cleaning filter residues with deionized water for 2 times, and drying the filter residues at 110 ℃ to obtain chlorinated microspheres; adding 2g of chloridized microspheres, 1g of tetrabutylammonium bromide, 1g of tetrabutylammonium chloride and 15g of sodium hydroxide aqueous solution with the mass fraction of 4% into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 60 ℃, controlling the stirring speed to 200rpm, stirring for 10min, adding 8g of ZSM-5 molecular sieve, stirring for 30min, adding 25g of ethylenediamine, continuously stirring for 4h, filtering, cleaning filter residues with deionized water for 2 times, and drying the filter residues at 110 ℃ to obtain a composite phase transfer catalyst;
silicon-aluminum molar ratio SiO of ZSM-5 molecular sieve 2 /Al 2 O 3 35;
2. bromination reaction: adding 4% hydrochloric acid aqueous solution into a four-mouth bottle filled with intermediate methyl tetrabromoether to adjust the pH to 7, then adding 300g of deionized water, controlling the temperature of the four-mouth bottle to 25 ℃, controlling the stirring rotation speed to 200rpm, stirring for 10-15min, adding 210g of 38% hydrobromic acid and 2g of potassium bromate, continuously stirring for 10min, dropwise adding 65g of 28% hydrogen peroxide, controlling the dropwise adding speed to be 5g/min, and continuously stirring for 3.5h after the dropwise adding is finished to obtain a reaction solution;
3. post-treatment: the reaction solution is filtered, the filter cake is washed for 2 times by using sodium sulfite aqueous solution with the mass fraction of 8%, the dosage of the sodium sulfite aqueous solution is 200g during each washing, then the filter cake is washed for 3 times by using deionized water, the dosage of the deionized water during each washing is 200g, 280g of methylene dichloride is added after the washing is finished, the mixture is stirred for 20min at the stirring speed of 100rpm at the temperature of 30 ℃, the mixture is filtered, filter residues are dried and used as a recovered composite phase transfer catalyst for recycling, the filtrate is placed at the temperature of 45 ℃ for desolventizing, and 96.23g of methyl octabromoether is obtained after the solvent is totally desolventized.
The prepared methyl octabromoether is subjected to liquid chromatography, and the specific detection method comprises the following steps:
adopting Zhejiang Fuli LC5090 liquid chromatography and a sun-C18 column, wherein the column length is 150mm, the inner diameter is 4.6mm, the particle size is 3.5 μm, the column temperature is 40 ℃, the mobile phase consists of acetonitrile and water, and the acetonitrile is controlled: water=95:5, flow rate 1mL/min, detection wavelength 220nm, stop time 25min, time locking 3min, maximum drift 150, sample introduction amount 10 μl, liquid chromatogram obtained is shown in fig. 1, purity of the prepared methyl octabromoether is 98.25%, and molar yield of the methyl octabromoether is 98.00% calculated according to purity of the methyl octabromoether.
Example 2
The preparation method of the methyl octabromoether specifically comprises the following steps:
1. etherification reaction: adding 54.5g of tetrabromobisphenol A and 22g of methallyl chloride into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 48 ℃, controlling the stirring rotation speed to 320rpm, stirring for 12min, adding 12% sodium hydroxide aqueous solution by mass fraction to adjust the pH value to 9.5, adding 0.12g of composite phase transfer catalyst, continuing stirring for 4.5h, stopping stirring, and naturally cooling to room temperature to obtain intermediate methyl tetrabromoether;
the preparation method of the composite phase transfer catalyst comprises the following steps: adding 6.2g of polyvinyl alcohol 2488, 5.2g of beta-cyclodextrin, 1.6g of polyvinyl amine, 19g of glutaraldehyde water solution with the mass fraction of 50% and 21g of deionized water into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 42 ℃, controlling the stirring speed to 120rpm, stirring for 12min, adding 0.3g of gamma-polyglutamic acid and 0.23g of sorbitan monostearate, and continuously stirring for 34min to obtain a mixed solution; 160g of liquid paraffin is added into a four-mouth bottle, the temperature of the four-mouth bottle is controlled to 62 ℃, the stirring speed is controlled to 120rpm, then the mixed solution is dripped into the four-mouth bottle, the dripping speed of the mixed solution is controlled to be 4.2g/min, stirring is continued for 42min after the dripping is finished, filtering is carried out, the filter residue is washed 3 times by deionized water, and then the filter residue is dried at 115 ℃ to obtain microspheres; adding 2.1g of microspheres, 5.2g of epichlorohydrin and 72g of hydrochloric acid aqueous solution with the mass fraction of 10.5% into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 62 ℃, controlling the stirring speed to 220rpm, stirring for 52min, filtering, cleaning filter residues with deionized water for 2 times, and drying the filter residues at 112 ℃ to obtain chlorinated microspheres; adding 2.1g of chloridized microspheres, 1.1g of tetrabutylammonium bromide, 1.1g of tetrabutylammonium chloride and 15.2g of sodium hydroxide aqueous solution with the mass fraction of 4.2% into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 62 ℃, controlling the stirring speed to 220rpm, stirring for 12min, adding 8.2g of ZSM-5 molecular sieve, stirring for 32min, adding 26g of ethylenediamine, continuously stirring for 4.2h, filtering, washing filter residues for 2 times by using deionized water, and drying the filter residues at 115 ℃ to obtain the composite phase transfer catalyst;
silicon-aluminum molar ratio SiO of ZSM-5 molecular sieve 2 /Al 2 O 3 45;
2. bromination reaction: adding 4.5% hydrochloric acid aqueous solution into a four-mouth bottle filled with intermediate methyl tetrabromoether to adjust the pH to 7.2, then adding 310g of deionized water, controlling the temperature of the four-mouth bottle to 26 ℃, controlling the stirring rotation speed to 220rpm, stirring for 11min, adding 220g of hydrobromic acid with the mass fraction of 38.5% and 2.5g of potassium bromate, continuously stirring for 12min, dropwise adding 66g of hydrogen peroxide with the mass fraction of 29%, controlling the dropwise adding speed to 6g/min, and continuously stirring for 4h after the dropwise adding is finished to obtain a reaction solution;
3. post-treatment: the reaction solution is filtered, a filter cake is washed for 2 times by using sodium sulfite aqueous solution with the mass fraction of 8.5%, the dosage of the sodium sulfite aqueous solution is 210g during each washing, then the filter cake is washed for 3 times by using deionized water, the dosage of the deionized water during each washing is 220g, 285g of methylene dichloride is added after the washing is finished, the mixture is stirred for 24 minutes at the stirring speed of 150rpm at the temperature of 32 ℃, the mixture is filtered, filter residues are dried and used as a recovered composite phase transfer catalyst for recycling, the filtrate is placed at the temperature of 46 ℃ for desolventizing, and 97.18g of methyl octabromoether is obtained after the solvent is completely desolventized.
The prepared methyl octabromoether is subjected to liquid chromatography, and the specific detection method comprises the following steps:
adopting Zhejiang Fuli LC5090 liquid chromatography and a sun-C18 column, wherein the column length is 150mm, the inner diameter is 4.6mm, the particle size is 3.5 μm, the column temperature is 40 ℃, the mobile phase consists of acetonitrile and water, and the acetonitrile is controlled: water=95:5, flow rate 1mL/min, detection wavelength 220nm, stop time 25min, time locking 3min, maximum drift 150, sample injection amount 10 μl, liquid chromatogram obtained is shown in fig. 2, purity of the prepared methyl octabromoether is 98.64%, and molar yield of the methyl octabromoether is 98.45% calculated according to purity of the methyl octabromoether.
Example 3
The preparation method of the methyl octabromoether specifically comprises the following steps:
1. etherification reaction: adding 54.7g of tetrabromobisphenol A and 22g of methallyl chloride into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 52 ℃, controlling the stirring rotation speed to 380rpm, stirring for 14min, adding 14% sodium hydroxide aqueous solution by mass fraction to adjust the pH value to 9.5, adding 0.12g of composite phase transfer catalyst, continuing stirring for 4.8h, stopping stirring, and naturally cooling to room temperature to obtain intermediate methyl tetrabromoether;
the preparation method of the composite phase transfer catalyst comprises the following steps: adding 6.8g of polyvinyl alcohol 2488, 5.8g of beta-cyclodextrin, 1.8g of polyvinyl amine, 19g of glutaraldehyde water solution with the mass fraction of 50% and 24g of deionized water into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 48 ℃, controlling the stirring speed to 180rpm, stirring for 18min, adding 0.4g of gamma-polyglutamic acid and 0.25g of sorbitan monostearate, and continuously stirring for 38min to obtain a mixed solution; adding 190g of liquid paraffin into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 68 ℃, controlling the stirring speed to 170rpm, then dripping mixed liquid into the four-mouth bottle, controlling the dripping speed of the mixed liquid to be 4.8g/min, continuing stirring for 48min after dripping, filtering, cleaning filter residues with deionized water for 3 times, and drying the filter residues at 118 ℃ to obtain microspheres; adding 2.1g of microspheres, 5.4g of epichlorohydrin and 74g of 11.5% hydrochloric acid aqueous solution into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 68 ℃, controlling the stirring speed to 270rpm, stirring for 58min, filtering, cleaning filter residues with deionized water for 3 times, and drying the filter residues at 120 ℃ to obtain chlorinated microspheres; adding 2.1g of chloridized microspheres, 1.1g of tetrabutylammonium bromide, 1.1g of tetrabutylammonium chloride and 15.8g of sodium hydroxide aqueous solution with the mass fraction of 4.8% into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 67 ℃, controlling the stirring speed to 280rpm, stirring for 14min, adding 8.8g of ZSM-5 molecular sieve, stirring for 38min, adding 28g of ethylenediamine, continuously stirring for 4.8h, filtering, cleaning filter residues for 3 times by using deionized water, and drying the filter residues at 118 ℃ to obtain the composite phase transfer catalyst;
silicon-aluminum molar ratio SiO of ZSM-5 molecular sieve 2 /Al 2 O 3 60;
2. bromination reaction: adding 4.8% hydrochloric acid aqueous solution into a four-mouth bottle filled with intermediate methyl tetrabromoether to adjust the pH to 7.4, then adding 320g of deionized water, controlling the temperature of the four-mouth bottle to 27 ℃, controlling the stirring rotation speed to 280rpm, stirring for 14min, adding 225g of hydrobromic acid with the mass fraction of 39.5% and 2.2g of potassium bromate, continuously stirring for 18min, dropwise adding 68g of hydrogen peroxide with the mass fraction of 29%, controlling the dropwise adding speed to be 5.5g/min, and continuously stirring for 3.5h after the dropwise adding is finished to obtain a reaction solution;
3. post-treatment: the reaction solution is filtered, the filter cake is washed 3 times by using sodium sulfite aqueous solution with the mass fraction of 9.5%, the dosage of the sodium sulfite aqueous solution is 240g during each washing, then the filter cake is washed 4 times by using deionized water, the dosage of the deionized water during each washing is 290g, 295g of methylene dichloride is added after the washing is finished, the mixture is stirred for 28min at the stirring speed of 180rpm at 38 ℃, the mixture is filtered, filter residues are dried and used as a recovered composite phase transfer catalyst for recycling, the filtrate is placed at 48 ℃ for desolventizing, and 97.64g of methyl octabromoether is obtained after the solvent is completely removed.
The prepared methyl octabromoether is subjected to liquid chromatography, and the specific detection method comprises the following steps:
adopting Zhejiang Fuli LC5090 liquid chromatography and a sun-C18 column, wherein the column length is 150mm, the inner diameter is 4.6mm, the particle size is 3.5 μm, the column temperature is 40 ℃, the mobile phase consists of acetonitrile and water, and the acetonitrile is controlled: water=95:5, flow rate 1mL/min, detection wavelength 220nm, stop time 25min, time locking 3min, maximum drift 150, sample injection amount 10 μl, liquid chromatogram obtained is shown in fig. 3, purity of the prepared methyl octabromoether is 98.22%, and molar yield of the methyl octabromoether is 98.13% calculated according to purity of the methyl octabromoether as can be seen from fig. 3.
Example 4
The preparation method of the methyl octabromoether specifically comprises the following steps:
1. etherification reaction: adding 55g of tetrabromobisphenol A and 23g of methallyl chloride into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 55 ℃, controlling the stirring rotation speed to 400rpm, stirring for 15min, adding 15% sodium hydroxide aqueous solution by mass fraction to adjust the pH value to 10, adding 0.11g of composite phase transfer catalyst, continuously stirring for 5h, stopping stirring, and naturally cooling to room temperature to obtain an intermediate methyl tetrabromoether;
the preparation method of the composite phase transfer catalyst comprises the following steps: adding 7g of polyvinyl alcohol 2488, 6g of beta-cyclodextrin, 2g of polyvinyl amine, 20g of glutaraldehyde water solution with the mass fraction of 50% and 25g of deionized water into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 50 ℃, controlling the stirring speed to 200rpm, stirring for 20min, adding 0.4g of gamma-polyglutamic acid and 0.3g of sorbitan monostearate, and continuing stirring for 40min to obtain a mixed solution; adding 200g of liquid paraffin into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 70 ℃, controlling the stirring speed to 200rpm, then dripping mixed liquid into the four-mouth bottle, controlling the dripping speed of the mixed liquid to be 5g/min, continuing stirring for 50min after dripping, filtering, cleaning filter residues with deionized water for 3 times, and drying the filter residues at 120 ℃ to obtain microspheres; adding 2.2g of microspheres, 5.5g of epichlorohydrin and 75g of 12% hydrochloric acid aqueous solution into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 70 ℃, controlling the stirring speed to 300rpm, stirring for 60min, filtering, cleaning filter residues with deionized water for 3 times, and drying the filter residues at 120 ℃ to obtain chlorinated microspheres; adding 2.2g of chloridized microspheres, 1.2g of tetrabutylammonium bromide, 1.2g of tetrabutylammonium chloride and 16g of sodium hydroxide aqueous solution with mass fraction of 5% into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 70 ℃, controlling the stirring speed to 300rpm, stirring for 15min, adding 9g of ZSM-5 molecular sieve, stirring for 40min, adding 30g of ethylenediamine, continuously stirring for 5h, filtering, cleaning filter residues with deionized water for 3 times, and then drying the filter residues at 120 ℃ to obtain a composite phase transfer catalyst;
silicon-aluminum molar ratio SiO of ZSM-5 molecular sieve 2 /Al 2 O 3 70;
2. bromination reaction: adding 5% hydrochloric acid aqueous solution into a four-mouth bottle filled with intermediate methyl tetrabromoether to adjust the pH to 7.5, then adding 330g of deionized water, controlling the temperature of the four-mouth bottle to 30 ℃, controlling the stirring rotation speed to 300rpm, stirring for 15min, adding 230g of hydrobromic acid with the mass fraction of 40% and 2.5g of potassium bromate, continuously stirring for 20min, dropwise adding 70g of 30% hydrogen peroxide with the mass fraction of 30%, controlling the dropwise adding speed to be 5.5g/min, and continuously stirring for 4h after the dropwise adding is finished to obtain a reaction solution;
3. post-treatment: the reaction solution is filtered, a filter cake is washed 3 times by using 10% sodium sulfite aqueous solution with the dosage of 250g during each washing, then the filter cake is washed 4 times by using deionized water with the dosage of 300g during each washing, 300g of methylene dichloride is added after the washing is finished, the mixture is stirred at the stirring speed of 200rpm for 30min at the temperature of 40 ℃, the mixture is filtered, filter residues are dried and recycled as a recovered composite phase transfer catalyst, the filtrate is placed at the temperature of 50 ℃ for desolventizing, and 98.14g of methyl octabromoether is obtained after the solvent is totally desolventized.
The prepared methyl octabromoether is subjected to liquid chromatography, and the specific detection method comprises the following steps:
adopting Zhejiang Fuli LC5090 liquid chromatography and a sun-C18 column, wherein the column length is 150mm, the inner diameter is 4.6mm, the particle size is 3.5 μm, the column temperature is 40 ℃, the mobile phase consists of acetonitrile and water, and the acetonitrile is controlled: water=95:5, flow rate 1mL/min, detection wavelength 220nm, stop time 25min, time locking 3min, maximum drift 150, sample introduction amount 10 μl, liquid chromatogram obtained is shown in fig. 4, purity of the prepared methyl octabromoether is 97.94%, and molar yield of the methyl octabromoether is 97.82% calculated according to purity of the methyl octabromoether.
Comparative example 1
The same method for preparing methyl octabromoether as in example 2 was employed, except that: in the etherification step 1, 0.06g of tetrabutylammonium bromide and 0.06g of tetrabutylammonium chloride were used in place of 0.12g of the composite phase transfer catalyst;
78.02g of methyl octabromoether were obtained with a purity of 97.24% and a molar yield of 77.92%.
Comparative example 2
The same method for preparing methyl octabromoether as in example 2 was employed, except that: in the step 1 etherification reaction, 0.06g of a mixture of tetrabutylammonium bromide and 0.06g of tetrabutylammonium chloride is used to replace 0.12g of the composite phase transfer catalyst, and the stirring time of the step 1 etherification reaction is prolonged from 4.5h to 6.5 h;
96.71g of methyl octabromoether were obtained with a purity of 98.07% and a molar yield of 97.41%.
Comparative example 3
The same method for preparing methyl octabromoether as in example 2 was employed, except that: in the etherification step 1, 0.12g of a mixture of 0.12g of tetrabutylammonium bromide and 0.12g of tetrabutylammonium chloride was used in place of 0.12g of the composite phase transfer catalyst;
94.78g of methyl octabromoether were obtained with a purity of 98.14% and a molar yield of 95.53%.
From the results of examples 1 to 3 and comparative examples 1 to 3, it can be seen that the composite phase transfer catalysts prepared in examples 1 to 3 can reduce the catalyst amount in the etherification reaction and shorten the etherification reaction time;
through further analysis, the composite phase transfer catalyst is characterized in that the phase transfer catalyst is firstly loaded in a molecular sieve, then the molecular sieve is compounded with the polyvinyl alcohol microsphere, the high specific surface areas of the microsphere and the molecular sieve can improve the transfer efficiency of the phase transfer catalyst, and meanwhile, beta-cyclodextrin in the polyvinyl alcohol microsphere can also play a role in transferring reactants, so that the catalyst dosage in etherification reaction is reduced, and the etherification reaction time is shortened.
Comparative example 4
The same method for preparing methyl octabromoether as in example 2 was employed, except that: the preparation method of the composite phase transfer catalyst in the etherification reaction of step 1 is changed into:
adding 6.2g of polyvinyl alcohol 2488, 19g of glutaraldehyde water solution with the mass fraction of 50% and 21g of deionized water into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 42 ℃, controlling the stirring speed to 120rpm, stirring for 12min, adding 0.23g of sorbitan monostearate, and continuing stirring for 34min to obtain a mixed solution; 160g of liquid paraffin is added into a four-mouth bottle, the temperature of the four-mouth bottle is controlled to 62 ℃, the stirring speed is controlled to 120rpm, then the mixed solution is dripped into the four-mouth bottle, the dripping speed of the mixed solution is controlled to be 4.2g/min, stirring is continued for 42min after the dripping is finished, filtering is carried out, the filter residue is washed 3 times by deionized water, and then the filter residue is dried at 115 ℃ to obtain microspheres; adding 2.1g of microspheres, 5.2g of epichlorohydrin and 72g of hydrochloric acid aqueous solution with the mass fraction of 10.5% into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 62 ℃, controlling the stirring speed to 220rpm, stirring for 52min, filtering, cleaning filter residues with deionized water for 2 times, and drying the filter residues at 112 ℃ to obtain chlorinated microspheres; adding 2.1g of chloridized microspheres, 1.1g of tetrabutylammonium bromide, 1.1g of tetrabutylammonium chloride and 15.2g of sodium hydroxide aqueous solution with the mass fraction of 4.2% into a four-mouth bottle, controlling the temperature of the four-mouth bottle to 62 ℃, controlling the stirring speed to 220rpm, stirring for 12min, adding 26g of ethylenediamine, continuously stirring for 4.2h, filtering, cleaning filter residues with deionized water for 2 times, and then drying the filter residues at 115 ℃ to obtain a composite phase transfer catalyst;
namely, the addition of beta-cyclodextrin, polyvinyl amine, gamma-polyglutamic acid and ZSM-5 molecular sieve is omitted in the preparation of the composite phase transfer catalyst;
95.04g of methyl octabromoether were obtained with a purity of 98.32% and a molar yield of 95.97%.
Test examples
After the composite phase transfer catalyst was applied 20 times according to the preparation methods of methyl octabromoether of examples 1 to 3 and comparative example 4, respectively, the mass, purity and yield of the prepared methyl octabromoether were as follows at the 20 th application:
as shown by the results of the test examples, the beta-cyclodextrin, the polyvinyl amine, the gamma-polyglutamic acid and the ZSM-molecular sieve are added in the preparation of the composite phase transfer catalyst, namely, the phase transfer catalyst is firstly loaded on the molecular sieve, and then the molecular sieve is loaded on the polyvinyl alcohol microsphere, so that the dual loading of the phase transfer catalyst can be realized, the loss of the phase transfer catalyst can be reduced, and meanwhile, the polyvinyl alcohol microsphere can also play a role in promoting the phase transfer catalysis, so that the catalyst in etherification reaction can still reach higher catalytic activity after being applied for a plurality of times.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the methyl octabromoether is characterized by comprising the following steps of: etherification reaction, bromination reaction and post-treatment;
adding tetrabromobisphenol A and methallyl chloride into a reactor, controlling the temperature of the reactor to 45-55 ℃, stirring for 10-15min, adding sodium hydroxide aqueous solution to adjust the pH to 9-10, adding a composite phase transfer catalyst, continuously stirring for 4-5h, stopping stirring, and cooling to obtain an intermediate methyl tetrabromoether;
the preparation method of the composite phase transfer catalyst comprises the following steps: preparing microspheres, preparing chloridized microspheres and loading;
the preparation method comprises the steps of (1) adding polyvinyl alcohol 2488, beta-cyclodextrin, polyvinyl amine, glutaraldehyde aqueous solution and deionized water into a reactor, controlling the temperature of the reactor to 40-50 ℃, stirring for 10-20min, adding gamma-polyglutamic acid and sorbitan monostearate, and continuously stirring for 30-40min to obtain a mixed solution; adding liquid paraffin into a reactor, controlling the temperature of the reactor to 60-70 ℃, dropwise adding the mixed solution into the reactor while stirring, continuously stirring for 40-50min after the dropwise adding is finished, filtering, cleaning and drying filter residues to obtain microspheres;
adding microspheres, epichlorohydrin and hydrochloric acid aqueous solution into a reactor, controlling the temperature of the reactor to 60-70 ℃, stirring for 50-60min, filtering, cleaning and drying filter residues to obtain the chloridized microspheres;
adding chloridized microspheres, tetrabutylammonium bromide, tetrabutylammonium chloride and sodium hydroxide aqueous solution into a reactor, controlling the temperature of the reactor to 60-70 ℃, stirring for 10-15min, adding ZSM-5 molecular sieve, stirring for 30-40min, adding ethylenediamine, continuously stirring for 4-5h, filtering, cleaning and drying filter residues to obtain a composite phase transfer catalyst;
adding aqueous hydrochloric acid solution into a reactor filled with intermediate methyl tetrabromoether to adjust the pH to 7-7.5, then adding deionized water, controlling the temperature of the reactor to 25-30 ℃, stirring for 10-15min, adding hydrobromic acid and potassium bromate, continuously stirring for 10-20min, dropwise adding hydrogen peroxide, and continuously stirring for 3.5-4h after the dropwise adding is finished to obtain a reaction solution;
and (3) after-treatment, filtering the reaction liquid, cleaning a filter cake by using a sodium sulfite aqueous solution, cleaning the filter cake by using deionized water, adding methylene dichloride after cleaning, stirring, filtering, drying filter residues, recycling the filter residues as a recovered composite phase transfer catalyst, desolventizing the filtrate, and obtaining the methyl octabromoether after the solvent is completely removed.
2. The method for preparing methyl octabromoether according to claim 1, characterized in that in the etherification reaction, the mass ratio of tetrabromobisphenol a, methallyl chloride and a composite phase transfer catalyst is 54-55:21-23:0.11-0.12;
the mass fraction of the sodium hydroxide aqueous solution is 10-15%.
3. The method for preparing methyl octabromoether according to claim 1, wherein the mass ratio of polyvinyl alcohol 2488, beta-cyclodextrin, polyvinyl amine, glutaraldehyde aqueous solution, deionized water, gamma-polyglutamic acid, sorbitan monostearate and liquid paraffin in the preparation of microspheres is 6-7:5-6:1.5-2:18-20:20-25:0.3-0.4:0.2-0.3:150-200;
the mass fraction of the glutaraldehyde aqueous solution is 50%;
the dripping speed of the mixed solution is 4-5g/min.
4. The method for preparing methyl octabromoether according to claim 1, wherein the mass ratio of microspheres, epichlorohydrin and aqueous hydrochloric acid solution in the preparation of chlorinated microspheres is 2-2.2:5-5.5:70-75;
the mass fraction of the hydrochloric acid aqueous solution is 10-12%.
5. The method for preparing methyl octabromoether according to claim 1, wherein in the load, the mass ratio of the chloridized microsphere, tetrabutylammonium bromide, tetrabutylammonium chloride, sodium hydroxide aqueous solution, ZSM-5 molecular sieve and ethylenediamine is 2-2.2:1-1.2:1-1.2:15-16:8-9:25-30;
silicon-aluminum molar ratio SiO of ZSM-5 molecular sieve 2 /Al 2 O 3 35-70.
6. The method for preparing methyl octabromoether according to claim 1, wherein the mass ratio of tetrabromobisphenol a in the etherification reaction to deionized water, hydrobromic acid, potassium bromate and hydrogen peroxide in the bromination reaction is 54-55:300-330:210-230:2-2.5:65-70.
7. The method for producing methyl octabromoether according to claim 1, characterized in that the mass fraction of hydrobromic acid in the bromination reaction is 38-40%;
the mass fraction of the hydrogen peroxide is 28-30%;
the dropping speed of the hydrogen peroxide is 5-6g/min;
the mass fraction of the hydrochloric acid aqueous solution is 4-5%.
8. The method for producing methyl octabromoether according to claim 1, characterized in that in the post-treatment, the mass fraction of the aqueous sodium sulfite solution is 8-10%;
the mass ratio of tetrabromobisphenol A in the etherification reaction to methylene dichloride in the post-treatment is 54-55:280-300.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5998674A (en) * | 1997-08-22 | 1999-12-07 | Teijin Chemicals, Ltd. | Bromine compound production method |
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