CN105968344A - Synthetic method of bromide polyphenylene oxide - Google Patents
Synthetic method of bromide polyphenylene oxide Download PDFInfo
- Publication number
- CN105968344A CN105968344A CN201610538255.2A CN201610538255A CN105968344A CN 105968344 A CN105968344 A CN 105968344A CN 201610538255 A CN201610538255 A CN 201610538255A CN 105968344 A CN105968344 A CN 105968344A
- Authority
- CN
- China
- Prior art keywords
- bromophenol
- synthetic method
- reaction
- organic solvent
- polyphenylene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000010189 synthetic method Methods 0.000 title claims abstract description 30
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 22
- 229920006380 polyphenylene oxide Polymers 0.000 title claims abstract description 22
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 title abstract description 6
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000003960 organic solvent Substances 0.000 claims abstract description 34
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005893 bromination reaction Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000009413 insulation Methods 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 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 16
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000012044 organic layer Substances 0.000 claims abstract description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 9
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 31
- 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 13
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 11
- -1 sodium alkoxide Chemical class 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 235000014121 butter Nutrition 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 229920001955 polyphenylene ether Polymers 0.000 claims description 7
- 230000035484 reaction time Effects 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
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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 compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 238000000638 solvent extraction Methods 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 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 abstract description 3
- WYMJZZIWGKJZJD-UHFFFAOYSA-N 4-bromophenol;sodium Chemical compound [Na].OC1=CC=C(Br)C=C1 WYMJZZIWGKJZJD-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000284 extract Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 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 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010016275 Fear Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
Abstract
The invention discloses a synthetic method of bromide polyphenylene oxide. The synthetic method comprises the following steps of melting p-bromophenol, adding an alcohol solution of sodium alcoholate, and reacting to obtain p-bromophenol sodium; then adding an organic solvent and a catalyst, distilling to obtain alcohol, raising the temperature and performing a thermal insulation reaction; adding chlorobenzene and continuing the thermal insulation reaction; after the reaction is ended, distilling to remove the organic solvent, washing with water, extracting with a solvent, and distilling the organic solvent to obtain a polyphenylene oxide intermediate; adding the polyphenylene oxide intermediate into the organic solvent and a composite catalyst, and dropwise adding a brominating agent and performing a bromination reaction; performing bromide removal and decoloring on an organic layer product through sodium sulfite, then adding water and an emulsifier, distilling to obtain an organic solvent, and washing and drying to obtain a bromide polyphenylene oxide product. According to the synthetic method disclosed by the invention, the p-bromophenol is used as a starting material and is subjected to polymerizing, terminating and bromination reaction in a reaction system, thereby obtaining the bromide polyphenylene oxide. A traditional process is simplified, and the reaction yield can maximally reach 90 percent or higher; the product is low in cost and high in quality; reaction conditions are mild and easy to control.
Description
Technical field
The present invention relates to technical field of organic synthesis, particularly to the synthetic method of a kind of brominated polyphenylether.
Background technology
Brominated polyphenylether be a kind of novel, wide spectrum, efficiently, the additive flame retardant of environmental protection, its thermal cracking or
Poisonous many bromos dibenzo dioxanes (PBDO) and PBDF is not produced during burning
(PBDF), comply fully with the Europe requirement about dioxin regulations with its fire-retardant material, environment is not made
Become harm.Its bromine content is high, Heat stability is good, and anti-ultraviolet property is good, oozing of relatively other bromide fire retardants
Going out property is low；It is particularly well-suited to produce the high-grade material of computer, facsimile machine, telephone set, photocopier, household electrical appliances etc.
Fire-retardant.Brominated polyphenylether, without any toxicity, also will not produce any teratogenecity to biology, to aquatic organism such as
Fishes etc. have no side effect, it may be said that meet the requirement of environmental protection.Its thermostability, light resistance and be difficult to the spies such as leaching
Point better than deca-BDE, the two anti-flammability is basically identical, but it is many to produce time fire-retardant that fears are entertained that
Bromine two pecks English problem, is the excellent succedaneum of deca-BDE.Brominated polyphenylether is applicable to polystyrene, height
Adhesive and the sealants such as styrene, ABS, epoxy resin, elastomer.
Summary of the invention
The present invention provides the synthetic method of a kind of brominated polyphenylether, and can substitute deca-BDE becomes high-grade material
The fire retardant of material.
For solving above-mentioned technical problem, the technical scheme is that
The synthetic method of a kind of brominated polyphenylether, comprises the following steps:
The first step, melts p bromophenol at 45-60 DEG C, adds the alcoholic solution of sodium alkoxide in a reservoir, reaction
Obtain p bromophenol sodium, add organic solvent and catalyst afterwards, steam alcohol, heat up and carry out insulation reaction；
Adding chlorobenzene and continue insulation reaction, reaction is evaporated off organic solvent after terminating, and washes crude product, with solvent extraction,
Distillation organic solvent obtains polyphenylene oxide intermediate；
Second step, adds organic solvent and composite catalyst by polyphenylene oxide intermediate, drips bromating agent, continues
Carry out bromination reaction；By above-mentioned organic layer product after sodium sulfite decolours except bromine, add water and emulsifying agent steams
Distillate organic solvent, through washing, be dried to obtain brominated polyphenylene ether product.
Wherein it is preferred to, the alcoholic solution of sodium alkoxide described in the first step is methanol solution and/or the ethanol of Feldalat NM
The ethanol solution of sodium, addition is sodium alkoxide and the mol ratio of p bromophenol is 1-1.5:1.
Wherein it is preferred to organic solvent described in the first step is any in dimethyl sulfoxide, DMF, DMAC
One or more.
Wherein it is preferred to catalyst described in the first step is in copper nitrate, copper powder, Cu-lyt., copper chloride
Any one or several, described catalyst amount is the 0.5%-10% of p bromophenol quality.
Wherein it is preferred to the reaction temperature of insulation reaction described in the first step is 160 DEG C-220 DEG C.
Wherein it is preferred to the mol ratio of the addition of chlorobenzene described in the first step and p bromophenol is 0.1-2:1.
Wherein it is preferred to extracting solvent used described in the first step is dichloroethanes or chloroform；Extraction is used
2-3 times that solvent load is p bromophenol amount.
Wherein it is preferred to organic solvent described in second step is dichloromethane, dichloroethanes, chloroform, tetrachloro
Change in carbon any one or several, described composite catalyst is butter of tin and titanium tetrachloride, described multiple
Close the 2%-4% that consumption is p bromophenol quality of catalyst.
Wherein it is preferred to bromating agent described in second step is bromine chloride, described bromine chloride and p bromophenol mole
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 emulsifying agent described in second step is dodecyl sodium sulfate, OP-10, fatty alcohol ether phosphorus
In acid esters, 2, 2-Oxydiphenol phosphate ester any one or several, described emulsifier is the 2-5% of the water yield, steam
Evaporate temperature and be 90-100 DEG C.
Beneficial effects of the present invention:
The present invention proposes the synthetic method of a kind of brominated polyphenylether, with p bromophenol as initiation material, instead
Answer aggregated in system, end-blocking, prepare brominated polyphenylether after bromination reaction, simplify the operation of traditional handicraft
Step, reaction yield reaches as high as more than 90%, and low cost, product quality are high, reaction condition is gentle, easily
In control.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described
Embodiment be only a part of embodiment of the present invention rather than whole embodiments.Based in the present invention
Embodiment, it is every other that those of ordinary skill in the art are obtained under not making creative work premise
Embodiment, broadly falls into the scope of protection of the invention.
The synthetic method of a kind of brominated polyphenylether, comprises the following steps:
The first step, melts p bromophenol at 45-60 DEG C, adds the alcoholic solution of sodium alkoxide in a reservoir, reaction
Obtain p bromophenol sodium, add organic solvent and catalyst afterwards, steam alcohol, heat up and carry out insulation reaction；
Adding chlorobenzene and continue insulation reaction, reaction is evaporated off organic solvent after terminating, and washes crude product, with solvent extraction,
Distillation organic solvent obtains polyphenylene oxide intermediate；
Second step, adds organic solvent and composite catalyst by polyphenylene oxide intermediate, drips bromating agent, continues
Carry out bromination reaction；By above-mentioned organic layer product after sodium sulfite decolours except bromine, add water and emulsifying agent steams
Distillate organic solvent, through washing, be dried to obtain brominated polyphenylene ether product.
Embodiment 1
This enforcement provides the synthetic method of a kind of brominated polyphenylether, comprises the following steps:
The first step, melts p bromophenol at 45-60 DEG C, adds the methanol of the Feldalat NM of 20% in a reservoir
Solution, sodium alkoxide is 1.2:1 with the mol ratio of p bromophenol, and when measuring pH=9, reaction obtains p bromophenol sodium,
Adding dimethyl sulfoxide and copper nitrate afterwards, copper nitrate consumption is the 5% of p bromophenol quality, is warmed up to 200 DEG C
Carry out insulation reaction, temperature-rise period steam methanol, after reaction terminates, add chlorobenzene and continue insulation reaction,
The addition of chlorobenzene and the mol ratio of p bromophenol are 1:1, and reaction is evaporated off dimethyl sulfoxide after terminating, washing
Crude product, extracts with dichloroethanes, and dichloroethanes consumption is 2.5 times of p bromophenol amount, and distillation organic solvent obtains
To polyphenylene oxide intermediate；
Second step, adds dichloromethane and butter of tin that mass ratio is 1:1 and tetrachloro by polyphenylene oxide intermediate
Change titanium, the consumption of composite catalyst is the 3% of p bromophenol quality, drip bromine chloride, bromine chloride with to bromobenzene
Phenol mol ratio 2.5:1, proceeds bromination reaction, and bromination reaction temperature is 3 DEG C, and the bromination reaction time is 5h,
By above-mentioned organic layer product after sodium sulfite decolours except bromine, add water and dodecyl sodium sulfate, dodecane
Base sodium sulfonate consumption is the 4% of the water yield, and 95 DEG C distill out organic solvent, through washing, is dried to obtain brominated polyphenylene
Ether product.
The present embodiment synthetic method yield 97.2%, through the content 99.48% of gas chromatographic detection brominated polyphenylether.
Embodiment 2
This enforcement provides the synthetic method of a kind of brominated polyphenylether, comprises the following steps:
The first step, melts p bromophenol at 45-60 DEG C, adds the ethanol of the Sodium ethylate of 20% in a reservoir
Solution, Sodium ethylate is 1:1 with the mol ratio of p bromophenol, and when measuring pH=9, reaction obtains p bromophenol
Sodium, adds DMF and copper powder afterwards, and copper powder consumption is the 0.5% of p bromophenol quality, is warmed up to 160 DEG C and enters
Row insulation reaction, steams ethanol in temperature-rise period, after reaction terminates, add chlorobenzene and continue insulation reaction, chlorine
The addition of benzene and the mol ratio of p bromophenol are 1.5:1, and reaction is evaporated off DMF after terminating, wash crude product,
Extracting with chloroform, chloroform consumption is 2.7 times of p bromophenol amount, and distillation organic solvent obtains polyphenylene oxide intermediate；
Second step, adds dichloroethanes and butter of tin that mass ratio is 2:1 and tetrachloro by polyphenylene oxide intermediate
Change titanium, the consumption of composite catalyst is the 2% of p bromophenol quality, drip bromine chloride, bromine chloride with to bromobenzene
Phenol mol ratio 2:1, proceeds bromination reaction, and bromination reaction temperature is 0 DEG C, and the bromination reaction time is 8h,
By above-mentioned organic layer product after sodium sulfite decolours except bromine, the consumption adding water and OP-10, OP-10 is water
The 2% of amount, 90 DEG C distill out organic solvent, through washing, are dried to obtain brominated polyphenylene ether product.
The present embodiment synthetic method yield 96.9%, through the content 99.56% of gas chromatographic detection brominated polyphenylether.
Embodiment 3
This enforcement provides the synthetic method of a kind of brominated polyphenylether, comprises the following steps:
The first step, melts p bromophenol at 45-60 DEG C, adds the methanol of the Feldalat NM of 20% in a reservoir
Solution, Feldalat NM is 1.5:1 with the mol ratio of p bromophenol, and when measuring pH=9, reaction obtains p bromophenol
Sodium, adds dimethyl sulfoxide and Cu-lyt. afterwards, and Cu-lyt. consumption is the 10% of p bromophenol quality,
Being warmed up to 220 DEG C and carry out insulation reaction, the addition of chlorobenzene and the mol ratio of p bromophenol are 0.1:1, heat up
During steam methanol, after reaction terminates, add chlorobenzene and continue insulation reaction, reaction is evaporated off diformazan after terminating
Base sulfoxide, washes crude product, extracts with dichloroethanes, and dichloroethanes consumption is 2 times of p bromophenol amount, steams
Evaporate organic solvent and obtain polyphenylene oxide intermediate；
Second step, adds chloroform and butter of tin that mass ratio is 1:1 and titanium tetrachloride by polyphenylene oxide intermediate,
The consumption of composite catalyst is the 4% of p bromophenol quality, drips bromine chloride, bromine chloride and p bromophenol mole
Ratio 3:1, proceeds bromination reaction, and bromination reaction temperature is 5 DEG C, and the bromination reaction time is 2h, by above-mentioned
Organic layer product, after sodium sulfite decolours except bromine, adds water and fatty alcohol ether phosphate ester, fatty alcohol ether phosphoric acid
The consumption of ester is the 5% of the water yield, and 100 DEG C distill out organic solvent, through washing, is dried to obtain brominated polyphenylether
Product.
The present embodiment synthetic method yield 97.0%, through the content 99.53% of gas chromatographic detection brominated polyphenylether.
Embodiment 4
This enforcement provides the synthetic method of a kind of brominated polyphenylether, comprises the following steps:
The first step, melts p bromophenol at 45-60 DEG C, adds the ethanol of the Sodium ethylate of 20% in a reservoir
Solution, Sodium ethylate is 1.3:1 with the mol ratio of p bromophenol, and when measuring pH=9, reaction obtains p bromophenol
Sodium, the mass ratio adding DMAC and copper powder, Cu-lyt., copper powder and Cu-lyt. afterwards is 1:1, urges
Agent consumption is the 8% of p bromophenol quality, is warmed up to 180 DEG C and carries out insulation reaction, steams in temperature-rise period
Ethanol, after reaction terminates, adds chlorobenzene and continues insulation reaction, the addition of chlorobenzene and p bromophenol mole
Ratio is 2:1, and reaction is evaporated off DMAC after terminating, wash crude product, extracts with chloroform, and chloroform consumption is to bromine
2.2 times of phenol amount, distillation organic solvent obtains polyphenylene oxide intermediate；
Second step, adds carbon tetrachloride and butter of tin that mass ratio is 1:1 and tetrachloro by polyphenylene oxide intermediate
Change titanium, the consumption of composite catalyst is the 3% of p bromophenol quality, drip bromine chloride, bromine chloride with to bromobenzene
Phenol mol ratio 2.2:1, proceeds bromination reaction, and bromination reaction temperature is 4 DEG C, and the bromination reaction time is 4h,
By above-mentioned organic layer product after sodium sulfite decolours except bromine, add water and 2, 2-Oxydiphenol phosphate ester, 2, 2-Oxydiphenol phosphate ester
Consumption is the water yield 4%, 96 DEG C distill out organic solvent, through washing, be dried to obtain brominated polyphenylene ether product.
The present embodiment synthetic method yield 96.2%, through the content 99.67% of gas chromatographic detection brominated polyphenylether.
Embodiment 5
This enforcement provides the synthetic method of a kind of brominated polyphenylether, comprises the following steps:
The first step, melts p bromophenol at 45-60 DEG C, adds the methanol of the Feldalat NM of 20% in a reservoir
Solution, Feldalat NM is 1.4:1 with the mol ratio of p bromophenol, and when measuring pH=9, reaction obtains p bromophenol
Sodium, adding volume ratio afterwards is the dimethyl sulfoxide of 1:1, DMF and copper chloride, and copper chloride consumption is to bromine
The 3% of phenol quality, is warmed up to 210 DEG C and carries out insulation reaction, steam ethanol in temperature-rise period, and reaction terminates
After, adding chlorobenzene and continue insulation reaction, the addition of chlorobenzene and the mol ratio of p bromophenol are 0.6:1, instead
Dimethyl sulfoxide and DMF should be evaporated off after terminating, wash crude product, extract with dichloroethanes, dichloroethanes consumption
For 3 times of p bromophenol amount, distillation organic solvent obtains polyphenylene oxide intermediate；
Second step, is 1:1 chloroform and carbon tetrachloride by polyphenylene oxide intermediate addition volume ratio and mass ratio is 1:
The butter of tin of 1 and titanium tetrachloride, the consumption of composite catalyst is the 3% of p bromophenol quality, drips chlorination
Bromine, bromine chloride and p bromophenol mol ratio 2.8:1, proceed bromination reaction, and bromination reaction temperature is 4 DEG C,
The bromination reaction time is 6h, by above-mentioned organic layer product after sodium sulfite decolours except bromine, adds water and quality
Comparing is the dodecyl sodium sulfate of 1:1, OP-10, and dodecyl sodium sulfate and OP-10 consumption are to bromobenzene
4 times of phenol amount, 98 DEG C distill out organic solvent, through washing, are dried to obtain brominated polyphenylene ether product.
The present embodiment synthetic method yield 97.2%, through the content 99.42% of gas chromatographic detection brominated polyphenylether.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Within bright spirit and principle, any modification, equivalent substitution and improvement etc. made, should be included in this
Within bright protection domain.
Claims (10)
1. the synthetic method of a brominated polyphenylether, it is characterised in that comprise the following steps:
The first step, melts p bromophenol at 45-60 DEG C, adds the alcoholic solution of sodium alkoxide in a reservoir, reaction
Obtain p bromophenol sodium, add organic solvent and catalyst afterwards, steam alcohol, heat up and carry out insulation reaction；
Adding chlorobenzene and continue insulation reaction, reaction is evaporated off organic solvent after terminating, and washes crude product, with solvent extraction,
Distillation organic solvent obtains polyphenylene oxide intermediate；
Second step, adds organic solvent and composite catalyst by polyphenylene oxide intermediate, drips bromating agent, continues
Carry out bromination reaction；By above-mentioned organic layer product after sodium sulfite decolours except bromine, add water and emulsifying agent steams
Distillate organic solvent, through washing, be dried to obtain brominated polyphenylene ether product.
The synthetic method of a kind of brominated polyphenylether the most according to claim 1, it is characterised in that first
The alcoholic solution of sodium alkoxide described in step is methanol solution and/or the ethanol solution of Sodium ethylate of Feldalat NM, and addition is
Sodium alkoxide is 1-1.5:1 with the mol ratio of p bromophenol.
The synthetic method of a kind of brominated polyphenylether the most according to claim 1, it is characterised in that first
Organic solvent described in step is any one or a few in dimethyl sulfoxide, DMF, DMAC.
The synthetic method of a kind of brominated polyphenylether the most according to claim 1, it is characterised in that first
Catalyst described in step be in copper nitrate, copper powder, Cu-lyt., copper chloride any one or several,
Described catalyst amount is the 0.5%-10% of p bromophenol quality.
The synthetic method of a kind of brominated polyphenylether the most according to claim 1, it is characterised in that first
The reaction temperature of insulation reaction described in step is 160 DEG C-220 DEG C.
The synthetic method of a kind of brominated polyphenylether the most according to claim 1, it is characterised in that first
The addition of chlorobenzene described in step and the mol ratio of p bromophenol are 0.1-2:1.
The synthetic method of a kind of brominated polyphenylether the most according to claim 1, it is characterised in that first
Extracting solvent used described in step is dichloroethanes or chloroform；Solvent load used by extraction is p bromophenol
2-3 times of amount.
The synthetic method of a kind of brominated polyphenylether the most according to claim 1, it is characterised in that second
Organic solvent described in step be in dichloromethane, dichloroethanes, chloroform, carbon tetrachloride any one or
Several, described composite catalyst is butter of tin and titanium tetrachloride, and the consumption of described composite catalyst is to bromine
The 2%-4% of phenol quality.
The synthetic method of a kind of brominated polyphenylether the most according to claim 1, it is characterised in that second
Bromating agent described in step is bromine chloride, described bromine chloride and p bromophenol mol ratio 2～3:1, bromination reaction temperature
For 0-5 DEG C, the bromination reaction time is 2-8h.
The synthetic method of a kind of brominated polyphenylether the most according to claim 1, it is characterised in that the
Emulsifying agent described in two steps is in dodecyl sodium sulfate, OP-10, fatty alcohol ether phosphate ester, 2, 2-Oxydiphenol phosphate ester
Any one or several, described emulsifier is the 2-5% of the water yield, and vapo(u)rizing temperature is 90-100 DEG C.
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| CN114759238A (en) * | 2022-03-14 | 2022-07-15 | 武汉轻工大学 | Star-shaped cross-linked alkaline polyelectrolyte and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107694346A (en) * | 2017-10-09 | 2018-02-16 | 山东日兴新材料股份有限公司 | A kind of preparation method of water process brominated polyphenylether anisotropic membrane |
| CN107694346B (en) * | 2017-10-09 | 2020-11-06 | 山东日兴新材料股份有限公司 | Preparation method of brominated polyphenylene oxide asymmetric membrane for water treatment |
| CN114759238A (en) * | 2022-03-14 | 2022-07-15 | 武汉轻工大学 | Star-shaped cross-linked alkaline polyelectrolyte and preparation method thereof |
| CN114759238B (en) * | 2022-03-14 | 2023-08-29 | 武汉轻工大学 | Star-shaped crosslinked alkaline polyelectrolyte and preparation method thereof |
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