CN105968344B - A kind of synthetic method of brominated polyphenylether - Google Patents
A kind of synthetic method of brominated polyphenylether Download PDFInfo
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- CN105968344B CN105968344B CN201610538255.2A CN201610538255A CN105968344B CN 105968344 B CN105968344 B CN 105968344B CN 201610538255 A CN201610538255 A CN 201610538255A CN 105968344 B CN105968344 B CN 105968344B
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- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 33
- 238000010189 synthetic method Methods 0.000 title claims abstract description 28
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- 238000005893 bromination reaction Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 18
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000009413 insulation Methods 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- -1 sodium alkoxide Chemical class 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 9
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 8
- 239000012044 organic layer Substances 0.000 claims abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000000638 solvent extraction Methods 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 14
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical group BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 14
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 235000014121 butter Nutrition 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000001119 stannous chloride Substances 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- 238000010792 warming Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- ZNACBVKYBDCOKF-UHFFFAOYSA-N [Na].BrC1=C(C=CC=C1)O Chemical compound [Na].BrC1=C(C=CC=C1)O ZNACBVKYBDCOKF-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical class Br* 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- JTYRXXKXOULVAP-UHFFFAOYSA-N 1,2-dibromo-3-phenoxybenzene Chemical compound BrC1=CC=CC(OC=2C=CC=CC=2)=C1Br JTYRXXKXOULVAP-UHFFFAOYSA-N 0.000 description 1
- HEAUGIUDKRRLPJ-UHFFFAOYSA-N 1-bromodibenzo-p-dioxin Chemical class O1C2=CC=CC=C2OC2=C1C=CC=C2Br HEAUGIUDKRRLPJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 206010016275 Fear Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LZCORJASKQWUDL-UHFFFAOYSA-N bromobenzene phenol Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.BrC1=CC=CC=C1 LZCORJASKQWUDL-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a kind of synthetic method of brominated polyphenylether, includes the following steps：P bromophenol is melted, the alcoholic solution of sodium alkoxide is added, p bromophenol sodium is obtained by the reaction, adds organic solvent and catalyst, steams alcohol, heating carries out insulation reaction；Chlorobenzene is added and continues insulation reaction, organic solvent is evaporated off after reaction, washes, with solvent extraction, distillation organic solvent obtains polyphenylene oxide intermediate；Organic solvent and composite catalyst is added in polyphenylene oxide intermediate, bromating agent is added dropwise, carries out bromination reaction；By above-mentioned organic layer product after sodium sulfite is except bromine decoloration, water and emulsifier is added, organic solvent is distilled out, through washing, being dried to obtain brominated polyphenylene ether product.The present invention is using p bromophenol as starting material, brominated polyphenylether is made after aggregated in the reaction system, sealing end, bromination reaction, simplify traditional handicraft, reaction yield reaches as high as 90% or more, at low cost, product quality is high, reaction condition is mild, easily controllable.
Description
Technical field
The present invention relates to technical field of organic synthesis, more particularly to a kind of synthetic method of brominated polyphenylether.
Background technology
Brominated polyphenylether be a kind of novel, wide spectrum, efficiently, the additive flame retardant of environmental protection, thermal cracking or burning when not
Toxic more bromo dibenzo dioxanes (PBDO) and polybrominated dibenzofurans (PBDF) are generated, it is complete with its fire-retardant material
Meet requirement of the Europe about dioxin regulations, does not cause damages to environment.Its bromine content is high, and thermal stability is good, uvioresistant
Excellent performance is exudative low compared with other bromide fire retardants；Especially suitable for production computer, facsimile machine, telephone set, duplicator, family
The high-grade material of electricity etc. it is fire-retardant.Brominated polyphenylether will not generate any teratogenesis, to aquatic organism without any toxicity to biology
Such as fish is without side-effects, it may be said that meets the requirement of environmental protection.Its heat resistance, light resistance and it is not easy the features such as leaching better than ten
Dibromodiphenyl ether, the two anti-flammability is almost the same, but it is fire-retardant when not will produce more bromines two that fears are entertained that and peck English problem, be ten bromines two
The excellent substitute of phenylate.Brominated polyphenylether is suitable for the gluings such as polystyrene, high-phenylethylene, ABS, epoxy resin, elastomer
Agent and sealant.
Invention content
The present invention provides a kind of synthetic method of brominated polyphenylether, and can substitute deca-BDE becomes the resistance of high-grade material
Fire agent.
In order to solve the above technical problems, the technical scheme is that：
A kind of synthetic method of brominated polyphenylether, includes the following steps：
The first step melts p bromophenol at 45-60 DEG C, and the alcoholic solution of sodium alkoxide is added in a reservoir, is obtained by the reaction pair
Organic solvent and catalyst is added in bromophenol sodium later, steams alcohol, and heating carries out insulation reaction；Chlorobenzene is added and continues heat preservation instead
It answers, organic solvent is evaporated off after reaction, wash crude product, with solvent extraction, distillation organic solvent obtains polyphenylene oxide intermediate；
Polyphenylene oxide intermediate is added organic solvent and composite catalyst, bromating agent is added dropwise, continues bromination by second step
Reaction；By above-mentioned organic layer product after sodium sulfite is except bromine decoloration, water is added and emulsifier distills out organic solvent, through water
It washes, be dried to obtain brominated polyphenylene ether product.
Wherein it is preferred to which the alcoholic solution of sodium alkoxide described in the first step is the methanol solution of sodium methoxide and/or the second of sodium ethoxide
Alcoholic solution, addition are that the molar ratio of sodium alkoxide and p bromophenol is 1-1.5：1.
Wherein it is preferred to organic solvent described in the first step be dimethyl sulfoxide (DMSO), in DMF, DMAC any one or it is several
Kind.
Wherein it is preferred to which catalyst described in the first step is any one in copper nitrate, copper powder, stannous chloride, copper chloride
Kind is several, and the catalyst amount is the 0.5%-10% of p bromophenol quality.
Wherein it is preferred to which the reaction temperature of insulation reaction described in the first step is 160 DEG C -220 DEG C.
Wherein it is preferred to which the addition of chlorobenzene described in the first step and the molar ratio of p bromophenol are 0.1-2：1.
Wherein it is preferred to which it is dichloroethanes or chloroform to extract solvent used described in the first step；Extraction solvent used
Dosage is 2-3 times of p bromophenol amount.
Wherein it is preferred to which organic solvent described in second step is in dichloromethane, dichloroethanes, chloroform, carbon tetrachloride
Any one is several, and the composite catalyst is butter of tin and titanium tetrachloride, and the dosage of the composite catalyst is pair
The 2%-4% of bromophenol quality.
Wherein it is preferred to bromating agent described in second step is bromine chloride, the bromine chloride and p bromophenol molar ratio 2~3:
1, bromination reaction temperature is 0-5 DEG C, and the bromination reaction time is 2-8h.
Wherein it is preferred to which emulsifier described in second step is dodecyl sodium sulfate, OP-10, fatty alcohol ether phosphate, phenol
In ether phosphate any one or it is several, the emulsifier be water 2-5%, vapo(u)rizing temperature be 90-100 DEG C.
Beneficial effects of the present invention：
The present invention proposes a kind of synthetic method of brominated polyphenylether, using p bromophenol as starting material, in reaction system
In aggregated, sealing end, brominated polyphenylether is made after bromination reaction, simplify the operating procedure of traditional handicraft, reaction yield highest
It is at low cost, product quality is high, reaction condition is mild, easily controllable up to 90% or more.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
A kind of synthetic method of brominated polyphenylether, includes the following steps：
The first step melts p bromophenol at 45-60 DEG C, and the alcoholic solution of sodium alkoxide is added in a reservoir, is obtained by the reaction pair
Organic solvent and catalyst is added in bromophenol sodium later, steams alcohol, and heating carries out insulation reaction；Chlorobenzene is added and continues heat preservation instead
It answers, organic solvent is evaporated off after reaction, wash crude product, with solvent extraction, distillation organic solvent obtains polyphenylene oxide intermediate；
Polyphenylene oxide intermediate is added organic solvent and composite catalyst, bromating agent is added dropwise, continues bromination by second step
Reaction；By above-mentioned organic layer product after sodium sulfite is except bromine decoloration, water is added and emulsifier distills out organic solvent, through water
It washes, be dried to obtain brominated polyphenylene ether product.
Embodiment 1
This implementation provides a kind of synthetic method of brominated polyphenylether, includes the following steps：
The first step melts p bromophenol at 45-60 DEG C, and the methanol solution of 20% sodium methoxide is added in a reservoir,
The molar ratio of sodium alkoxide and p bromophenol is 1.2：1, when measuring pH=9, p bromophenol sodium is obtained by the reaction, it is sub- that dimethyl is added later
Sulfone and copper nitrate, copper nitrate dosage are the 5% of p bromophenol quality, are warming up to 200 DEG C of progress insulation reactions, are steamed in temperature-rise period
Go out methanol, after reaction, chlorobenzene is added and continues insulation reaction, the addition of chlorobenzene and the molar ratio of p bromophenol are 1：1, instead
Dimethyl sulfoxide (DMSO) is evaporated off after answering, washes crude product, is extracted with dichloroethanes, dichloroethanes dosage is the 2.5 of p bromophenol amount
Times, distillation organic solvent obtains polyphenylene oxide intermediate；
Second step, it is 1 that dichloromethane and mass ratio, which is added, in polyphenylene oxide intermediate：1 butter of tin and titanium tetrachloride, it is multiple
The dosage for closing catalyst is the 3% of p bromophenol quality, and bromine chloride, bromine chloride and p bromophenol molar ratio 2.5 is added dropwise:1, continue
Bromination reaction is carried out, bromination reaction temperature is 3 DEG C, and the bromination reaction time is 5h, and above-mentioned organic layer product is removed through sodium sulfite
After bromine decoloration, be added water and dodecyl sodium sulfate, dodecyl sodium sulfate dosage is the 4% of water, 95 DEG C distill out it is organic
Solvent, through washing, being dried to obtain brominated polyphenylene ether product.
The present embodiment synthetic method yield 97.2%, the content 99.48% through gas chromatographic detection brominated polyphenylether.
Embodiment 2
This implementation provides a kind of synthetic method of brominated polyphenylether, includes the following steps：
The first step melts p bromophenol at 45-60 DEG C, and the ethanol solution of 20% sodium ethoxide is added in a reservoir,
The molar ratio of sodium ethoxide and p bromophenol is 1：1, when measuring pH=9, p bromophenol sodium is obtained by the reaction, DMF and copper are added later
Powder, copper powder dosage are the 0.5% of p bromophenol quality, are warming up to 160 DEG C of progress insulation reactions, ethyl alcohol is steamed in temperature-rise period,
After reaction, chlorobenzene is added and continues insulation reaction, the addition of chlorobenzene and the molar ratio of p bromophenol are 1.5：1, reaction knot
DMF is evaporated off after beam, washes crude product, is extracted with chloroform, chloroform dosage is 2.7 times of p bromophenol amount, and distillation organic solvent obtains
Polyphenylene oxide intermediate；
Second step, it is 2 that dichloroethanes and mass ratio, which is added, in polyphenylene oxide intermediate：1 butter of tin and titanium tetrachloride, it is multiple
The dosage for closing catalyst is the 2% of p bromophenol quality, and bromine chloride, bromine chloride and p bromophenol molar ratio 2 is added dropwise:1, continue into
Row bromination reaction, bromination reaction temperature are 0 DEG C, and the bromination reaction time is 8h, and above-mentioned organic layer product is removed bromine through sodium sulfite
After decoloration, the dosage that water and OP-10, OP-10 is added is the 2% of water, and 90 DEG C distill out organic solvent, through washing, drying
To brominated polyphenylene ether product.
The present embodiment synthetic method yield 96.9%, the content 99.56% through gas chromatographic detection brominated polyphenylether.
Embodiment 3
This implementation provides a kind of synthetic method of brominated polyphenylether, includes the following steps：
The first step melts p bromophenol at 45-60 DEG C, and the methanol solution of 20% sodium methoxide is added in a reservoir,
The molar ratio of sodium methoxide and p bromophenol is 1.5：1, when measuring pH=9, p bromophenol sodium is obtained by the reaction, dimethyl is added later
Sulfoxide and stannous chloride, stannous chloride dosage are the 10% of p bromophenol quality, are warming up to 220 DEG C of progress insulation reactions, chlorobenzene
Addition and p bromophenol molar ratio be 0.1：1, methanol is steamed in temperature-rise period, after reaction, chlorobenzene is added and continues
Dimethyl sulfoxide (DMSO) is evaporated off in insulation reaction after reaction, washes crude product, is extracted with dichloroethanes, and dichloroethanes dosage is to bromine
2 times of phenol amount, distillation organic solvent obtain polyphenylene oxide intermediate；
Second step, it is 1 that chloroform and mass ratio, which is added, in polyphenylene oxide intermediate：1 butter of tin and titanium tetrachloride, it is compound to urge
The dosage of agent is the 4% of p bromophenol quality, and bromine chloride, bromine chloride and p bromophenol molar ratio 3 is added dropwise:1, continue bromine
Change reaction, bromination reaction temperature is 5 DEG C, and the bromination reaction time is 2h, by above-mentioned organic layer product through sodium sulfite except bromine decolourizes
Afterwards, be added water and fatty alcohol ether phosphate, the dosage of fatty alcohol ether phosphate is the 5% of water, 100 DEG C distill out it is organic molten
Agent, through washing, being dried to obtain brominated polyphenylene ether product.
The present embodiment synthetic method yield 97.0%, the content 99.53% through gas chromatographic detection brominated polyphenylether.
Embodiment 4
This implementation provides a kind of synthetic method of brominated polyphenylether, includes the following steps：
The first step melts p bromophenol at 45-60 DEG C, and the ethanol solution of 20% sodium ethoxide is added in a reservoir,
The molar ratio of sodium ethoxide and p bromophenol is 1.3：1, measure pH=9 when, p bromophenol sodium is obtained by the reaction, later be added DMAC and
The mass ratio of copper powder, stannous chloride, copper powder and stannous chloride is 1：1, catalyst amount is the 8% of p bromophenol quality, heating
Insulation reactions are carried out to 180 DEG C, ethyl alcohol is steamed in temperature-rise period, after reaction, chlorobenzene is added and continues insulation reaction, chlorobenzene
Addition and the molar ratio of p bromophenol are 2：1, DMAC is evaporated off after reaction, washes crude product, is extracted with chloroform, chloroform dosage
It it is 2.2 times of p bromophenol amount, distillation organic solvent obtains polyphenylene oxide intermediate；
Second step, it is 1 that carbon tetrachloride and mass ratio, which is added, in polyphenylene oxide intermediate：1 butter of tin and titanium tetrachloride, it is multiple
The dosage for closing catalyst is the 3% of p bromophenol quality, and bromine chloride, bromine chloride and p bromophenol molar ratio 2.2 is added dropwise:1, continue
Bromination reaction is carried out, bromination reaction temperature is 4 DEG C, and the bromination reaction time is 4h, and above-mentioned organic layer product is removed through sodium sulfite
After bromine decoloration, water and phenolic ether phosphate is added, the dosage of phenolic ether phosphate is the 4% of water, and 96 DEG C distill out organic solvent, warp
It washes, be dried to obtain brominated polyphenylene ether product.
The present embodiment synthetic method yield 96.2%, the content 99.67% through gas chromatographic detection brominated polyphenylether.
Embodiment 5
This implementation provides a kind of synthetic method of brominated polyphenylether, includes the following steps：
The first step melts p bromophenol at 45-60 DEG C, and the methanol solution of 20% sodium methoxide is added in a reservoir,
The molar ratio of sodium methoxide and p bromophenol is 1.4：1, when measuring pH=9, p bromophenol sodium is obtained by the reaction, volume ratio is added later
It is 1：1 dimethyl sulfoxide (DMSO), DMF and copper chloride, copper chloride dosage are the 3% of p bromophenol quality, are warming up to 210 DEG C and are protected
Temperature reaction, steams ethyl alcohol in temperature-rise period, after reaction, chlorobenzene is added and continues insulation reaction, the addition of chlorobenzene with to bromine
The molar ratio of phenol is 0.6：1, dimethyl sulfoxide (DMSO) and DMF are evaporated off after reaction, washes crude product, is extracted with dichloroethanes, two
Chloroethanes dosage is 3 times of p bromophenol amount, and distillation organic solvent obtains polyphenylene oxide intermediate；
Second step, it is 1 that volume ratio, which is added, in polyphenylene oxide intermediate：1 chloroform and carbon tetrachloride and mass ratio are 1：1 tetrachloro
Change tin and titanium tetrachloride, the dosage of composite catalyst is the 3% of p bromophenol quality, is added dropwise bromine chloride, bromine chloride with to bromobenzene
Phenol molar ratio 2.8:1, continue bromination reaction, bromination reaction temperature is 4 DEG C, and the bromination reaction time is 6h, will be above-mentioned organic
For layer product after sodium sulfite is except bromine decoloration, it is 1 that water and mass ratio, which is added,：1 dodecyl sodium sulfate, OP-10, dodecyl
Sodium sulfonate and OP-10 dosages are 4 times of p bromophenol amount, and 98 DEG C distill out organic solvent, through washing, being dried to obtain brominated polyphenylene
Ether product.
The present embodiment synthetic method yield 97.2%, the content 99.42% through gas chromatographic detection brominated polyphenylether.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of synthetic method of brominated polyphenylether, which is characterized in that include the following steps：
The first step melts p bromophenol at 45-60 DEG C, and the alcoholic solution of sodium alkoxide is added in a reservoir, is obtained by the reaction to bromobenzene
Organic solvent and catalyst is added in phenol sodium later, steams alcohol, and heating carries out insulation reaction；Chlorobenzene is added and continues insulation reaction, instead
Organic solvent is evaporated off after answering, washes crude product, with solvent extraction, distillation organic solvent obtains polyphenylene oxide intermediate；The alcohol
The alcoholic solution of sodium is the methanol solution of sodium methoxide and/or the ethanol solution of sodium ethoxide；The catalyst is copper nitrate, copper powder, chlorine
Change it is cuprous, in copper chloride any one or it is several；
Polyphenylene oxide intermediate is added organic solvent and composite catalyst, bromating agent is added dropwise, it is anti-to continue bromination by second step
It answers；By above-mentioned organic layer product after sodium sulfite is except bromine decoloration, water is added and emulsifier distills out organic solvent, through washing,
It is dried to obtain brominated polyphenylene ether product.
2. a kind of synthetic method of brominated polyphenylether according to claim 1, which is characterized in that sodium alkoxide described in the first step
Alcoholic solution addition be the molar ratio of sodium alkoxide and p bromophenol be 1-1.5: 1.
3. a kind of synthetic method of brominated polyphenylether according to claim 1, which is characterized in that organic described in the first step
Solvent is any one or a few in dimethyl sulfoxide (DMSO), DMF, DMAC.
4. a kind of synthetic method of brominated polyphenylether according to claim 1, which is characterized in that be catalyzed described in the first step
Agent dosage is the 0.5%-10% of p bromophenol quality.
5. a kind of synthetic method of brominated polyphenylether according to claim 1, which is characterized in that kept the temperature described in the first step
The reaction temperature of reaction is 160 DEG C -220 DEG C.
6. a kind of synthetic method of brominated polyphenylether according to claim 1, which is characterized in that chlorobenzene described in the first step
Addition and p bromophenol molar ratio be 0.1-2: 1.
7. a kind of synthetic method of brominated polyphenylether according to claim 1, which is characterized in that extracted described in the first step
Solvent used is dichloroethanes or chloroform；Extraction solvent dosage used is 2-3 times of p bromophenol amount.
8. a kind of synthetic method of brominated polyphenylether according to claim 1, which is characterized in that organic described in second step
Solvent be dichloromethane, dichloroethanes, chloroform, in carbon tetrachloride any one or it is several, the composite catalyst is four
Stannic chloride and titanium tetrachloride, the dosage of the composite catalyst are the 2%-4% of p bromophenol quality.
9. a kind of synthetic method of brominated polyphenylether according to claim 1, which is characterized in that bromination described in second step
Agent is bromine chloride, and the bromine chloride and p bromophenol molar ratio 2~3: 1, bromination reaction temperature are 0-5 DEG C, the bromination reaction time
For 2-8h.
10. a kind of synthetic method of brominated polyphenylether according to claim 1, which is characterized in that newborn described in second step
Agent be dodecyl sodium sulfate, OP-10, fatty alcohol ether phosphate, in phenolic ether phosphate any one or it is several, it is described
Emulsifier is the 2-5% of water, and vapo(u)rizing temperature is 90-100 DEG C.
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| GB1053638A (en) * | 1964-06-30 | 1967-01-04 | E.I. Du Pont De Nemours & Co. | Halogenated polyphenylene ethers |
| US4141880A (en) * | 1978-01-03 | 1979-02-27 | Velsicol Chemical Corporation | Flame retarded nylon composition |
| JPH07278290A (en) * | 1994-04-06 | 1995-10-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Preparation of brominated polyphenylene ether |
| CN101506269A (en) * | 2006-08-22 | 2009-08-12 | 科聚亚公司 | Brominated flame retardant |
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| GB1053638A (en) * | 1964-06-30 | 1967-01-04 | E.I. Du Pont De Nemours & Co. | Halogenated polyphenylene ethers |
| US4141880A (en) * | 1978-01-03 | 1979-02-27 | Velsicol Chemical Corporation | Flame retarded nylon composition |
| JPH07278290A (en) * | 1994-04-06 | 1995-10-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Preparation of brominated polyphenylene ether |
| CN101506269A (en) * | 2006-08-22 | 2009-08-12 | 科聚亚公司 | Brominated flame retardant |
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