CN108409959A - A kind of bromomethylation polyphenylene oxide and preparation method thereof - Google Patents
A kind of bromomethylation polyphenylene oxide and preparation method thereof Download PDFInfo
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- CN108409959A CN108409959A CN201810312742.6A CN201810312742A CN108409959A CN 108409959 A CN108409959 A CN 108409959A CN 201810312742 A CN201810312742 A CN 201810312742A CN 108409959 A CN108409959 A CN 108409959A
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- Prior art keywords
- polyphenylene oxide
- bromomethylation
- methylene
- source reagent
- preparation
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 43
- 229920006380 polyphenylene oxide Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 36
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000005997 bromomethyl group Chemical group 0.000 claims abstract description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 4
- 238000005893 bromination reaction Methods 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002841 Lewis acid Substances 0.000 abstract description 3
- -1 benzyl halogen Chemical class 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 150000007517 lewis acids Chemical class 0.000 abstract description 3
- 230000029936 alkylation Effects 0.000 abstract description 2
- 238000005804 alkylation reaction Methods 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 239000007848 Bronsted acid Substances 0.000 abstract 1
- 239000012456 homogeneous solution Substances 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000003011 anion exchange membrane Substances 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 4
- 229920001955 polyphenylene ether Polymers 0.000 description 4
- 238000007265 chloromethylation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000005002 aryl methyl group Chemical group 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical group 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The present invention provides a kind of bromomethylation polyphenylene oxide and preparation method thereof, belong to filed of functional, polyphenylene oxide is dissolved in organic solvent by the present invention forms homogeneous solution, then methylene-group source reagent, bromine source reagent are added in reactor, it is stirred to react at 20 ~ 80 DEG C 1 ~ 24 hour, then reaction solution is slowly dropped into precipitating reagent and is washed to pH close to neutrality with precipitating reagent, collect precipitation and drying to obtain bromomethylation polyphenylene oxide.The bromomethylation degree of the obtained bromomethylation polyphenylene oxide of the present invention can reach very high, hydrogen can even be reached on 200% i.e. polyphenylene oxide phenyl ring all by Bromomethyl Substituted, far above the method for existing bromomethylation, and relative to existing polyphenylene oxide halomethylation method, the invention avoids the use of lewis acid or strong bronsted acid catalyst during usual halomethylation, the further Fu Shi alkylations of the benzyl halogen caused by these catalyst are avoided and the cross-linking reaction that is formed.
Description
Technical field
The invention belongs to filed of functional, and in particular to a kind of bromomethylation polyphenylene oxide and preparation method thereof.
Background technology
Polyphenylene oxide is a kind of excellent thermoplastic engineering plastic, have good mechanical performance, hot property and electrical property and
It is cheap.In order to improve the performance of polyphenylene oxide, expand its application field, the functionalization and modification of people's polyphenylene ether expands extensively
General research.The polyphenylene oxide that wherein halomethylation is modified is to prepare anion-exchange membrane, phosphorated cation based on polyphenylene oxide
The important intermediate of the functional high molecule materials such as exchange membrane, flame-resistant polyphenylether containing phosphine.For example, Xu Tongwen
(JournalofMembraneScience, 2001,190:159-166) etc. the arylmethyl in first polyphenylene ether carries out bromomethyl
Change, is then reacted again with three-level ammonium and convert benzyl bromide to quaternary ammonium group, anion-exchange membrane is finally prepared.Shandong at present
The DF120 anion-exchange membranes of Tian Wei companies are this anion-exchange membrane.But the bromine used during bromomethylation
Element is noxious material, and since reaction carries out at a higher temperature, needs to use higher boiling toxic solvent chlorobenzene.
NanwenLi (Energy&EnvironmentalScience, 2012,5:7888-7892) etc. then use N- bromo maleimides
Arylmethyl in amine polyphenylene ether carries out bromomethylation, N- bromos maleimide higher price used;ShuangGu
(ChemSusChem, 2012,5:843-848) etc. using in paraformaldehyde, trim,ethylchlorosilane and lewis acid elder generation polyphenylene ether
Phenyl ring carry out chloromethylation, then prepare anion-exchange membrane, but the process has the shortcomings that usual chloromethylation process
Such as the chloromethane etherifying reagent that chloromethylation degree is not high, easy crosslinking, reaction time are long, directly uses or generates in situ in reaction process
With carcinogenicity etc..
The patent document of Publication No. CN106432744A disclose a kind of high alkali resistance polyphenylene oxide anion-exchange membrane and
Preparation method.Polyphenylene oxide is dissolved in solvent by the invention, obtains polyphenyl ethereal solution, and bromination is added into the polyphenyl ethereal solution
Bromomethylation polyphenyl ethereal solution is obtained by the reaction under logical condition of nitrogen gas in reagent, then drying obtains bromomethylation polyphenylene oxide.But
It is to use this method chlorobenzene for solvent, bromine is bromide reagent, and the bromomethylation degree of the bromomethylation polyphenylene oxide of preparation is not
It is high.
Invention content
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of bromomethylation polyphenylene oxide
And preparation method thereof.
In order to solve the above technical problems, the technical solution adopted by the present invention is:
A kind of bromomethylation polyphenylene oxide, chemical structure of general formula are:
Wherein, n represents the degree of polymerization of polyphenylene oxide, is 10~400 integer;X represents the number of the bromomethyl on average each phenyl ring
Mesh is 1%~200%.
Preferably, the preparation method of the bromomethylation polyphenylene oxide, comprises the steps of:
S1:Polyphenylene oxide, organic solvent are added in reactor, stirring and dissolving, obtained solution;
S2:Methylene-group source reagent, bromine source reagent are added in the solution obtained to step S1,1~24 is stirred to react at 20~80 DEG C
Hour, reaction solution is made;
S3:The obtained reaction solutions of step S2 are slowly dropped into precipitating reagent, are filtered, precipitating reagent is used in combination to wash to the close neutrality of pH,
Precipitation and drying are collected, bromomethylation polyphenylene oxide is obtained.
Preferably, in the step S1, organic solvent is chloroform or 1,2- dichloroethanes.
Preferably, in the step S2, bromine source reagent is bromination hydrogen, the acetum of hydrogen bromide or front three bromide silicon
Alkane;Methylene-group source reagent is paraformaldehyde or metaformaldehyde.
Preferably, the molar ratio of contained methylene and contained phenyl ring in polyphenylene oxide is 1 in the methylene-group source reagent:0.01
~2.5;The molar ratio of institute's bromine atom and contained methylene in the methylene-group source reagent is 1 in bromide source reagent:1~
1.5。
Preferably, in the step S3, precipitating reagent is the mixed solvent of ethyl alcohol, methanol, acetone or each ingredient and water.
The beneficial effects of the invention are as follows:Polyphenylene oxide is a kind of excellent thermoplastic engineering plastic, has good mechanicalness
Can, hot property and electrical property and cheap.The polyphenylene oxide that wherein halomethylation is modified is to prepare the anion based on polyphenylene oxide
The important intermediate of the functional high molecule materials such as exchange membrane, phosphorated cation-exchange membrane, flame-resistant polyphenylether containing phosphine.Institute of the present invention
The bromomethylation degree of obtained bromomethylation polyphenylene oxide can reach very high, increase with methylene-group source reagent additive amount, bromomethyl
Content increases, or even can reach hydrogen on 200% i.e. phenyl ring and be far above the side of existing bromomethylation all by Bromomethyl Substituted
Method, and high bromomethylation degree is all highly beneficial for further functionalization such as phosphine, quaternized etc..And relative to
Some polyphenylene oxide halomethylation methods, this method avoids lewis acid during usual halomethylation or by force Protic Acid Catalyzed
The use of agent, therefore the crosslinking for avoiding the further Fu Shi alkylations of the benzyl halogen caused by these catalyst and being formed is anti-
It answers;Relative to the method for methyl bromide on existing polyphenylene oxide, agents useful for same relative low price of the present invention, reaction temperature compared with
It is low.
First polyphenylene oxide, organic solvent are added in reactor by the present invention, stirring and dissolving, obtained solution;Add again into solution
Enter methylene-group source reagent, bromine source reagent, be stirred to react at 20~80 DEG C 1~24 hour, reaction solution is made;Then reaction solution is delayed
It in slow instillation precipitating reagent, filters, is used in combination precipitating reagent to wash to pH close to neutrality, collects precipitation and drying, it is poly- to obtain bromomethylation
Phenylate.The method of the present invention step is simple, simple process and low cost.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below to the skill of the embodiment of the present invention
Art scheme is clearly and completely described.Obviously, described embodiment is a part of the embodiment of the present invention, rather than complete
The embodiment in portion.Based on described the embodiment of the present invention, every other implementation that those of ordinary skill in the art are obtained
Example, shall fall within the protection scope of the present invention.
Nuclear magnetic resonance spectroscopy uses deuterochloroform for solvent, and tetramethylsilane is internal standard.
Embodiment 1~13:
Dissolving is stirred at room temperature in the organic solvent of 1.2015 grams of polyphenylene oxide (phenyl containing 10mmol, commercially available), amL,
Then methylene-group source reagent (methylene containing bmmol) is added and bromine source reagent (bromine atom of the mmol containing c) is added equipped with condensation
In the round-bottomed flask of pipe and drying tube, it is stirred to react several hours at a certain temperature, reaction solution is then slowly dropped into ethyl alcohol
In, filtering, and wash to pH close to neutrality, it is drying to obtain a series of bromomethylation polyphenylene oxide of different bromomethyl contents.
Bromomethylation polyphenyl of amount, solvent type, reaction temperature and the time of specific each substance that component is added to gained
The influence of x is listed in table 1 in bromomethyl content (being obtained by corresponding nuclear magnetic spectrogram integral and calculating) i.e. formula 1 in ether.
Table 1
By embodiment 3 with 4 it can be seen that methylene-group source reagent is that paraformaldehyde or metaformaldehyde have not significant impact;
By embodiment 5,6 and 7 it can be seen that either selecting acetum, bromotrimethylsilane or the bromination hydrogen of hydrogen bromide
As bromine source reagent, the product that bromomethyl content is 100% can be obtained;By embodiment 4,10 and 11 it can be seen that with methylene
Base source reagent additive amount increases, and bromomethyl content increases, or even can reach on 200% i.e. phenyl ring hydrogen all by Bromomethyl Substituted,
Far above the method for existing bromomethylation.
Finally illustrate, the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, this field is common
Other modifications or equivalent replacement that technical staff makes technical scheme of the present invention, without departing from technical solution of the present invention
Spirit and scope, be intended to be within the scope of the claims of the invention.
Claims (6)
1. a kind of bromomethylation polyphenylene oxide, it is characterised in that:Its chemical structure of general formula is:
Wherein, n represents the degree of polymerization of polyphenylene oxide, is 10~400 integer;X represents the number of the bromomethyl on average each phenyl ring
Mesh is 1%~200%.
2. the preparation method of bromomethylation polyphenylene oxide as described in claim 1, it is characterised in that:It comprises the steps of:
S1:Polyphenylene oxide, organic solvent are added in reactor, stirring and dissolving, obtained solution;
S2:Methylene-group source reagent, bromine source reagent are added in the solution obtained to step S1,1~24 is stirred to react at 20~80 DEG C
Hour, reaction solution is made;
S3:The obtained reaction solutions of step S2 are slowly dropped into precipitating reagent, are filtered, precipitating reagent is used in combination to wash to the close neutrality of pH,
Precipitation and drying are collected, bromomethylation polyphenylene oxide is obtained.
3. the preparation method of bromomethylation polyphenylene oxide as claimed in claim 2, it is characterised in that:It is organic in the step S1
Solvent is chloroform or 1,2- dichloroethanes.
4. the preparation method of bromomethylation polyphenylene oxide as claimed in claim 2, it is characterised in that:In the step S2, bromine source
Reagent is the acetum or bromotrimethylsilane of bromination hydrogen, hydrogen bromide;Methylene-group source reagent is paraformaldehyde or trimerization
Formaldehyde.
5. the preparation method of bromomethylation polyphenylene oxide as claimed in claim 4, it is characterised in that:In the methylene-group source reagent
The molar ratio of contained methylene and contained phenyl ring in polyphenylene oxide is 1:0.01~2.5;In bromide source reagent institute's bromine atom with
The molar ratio of contained methylene is 1 in the methylene-group source reagent:1~1.5.
6. the preparation method of bromomethylation polyphenylene oxide as claimed in claim 2, it is characterised in that:In the step S3, precipitation
Agent is the mixed solvent of ethyl alcohol, methanol, acetone or each ingredient and water.
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DE3334068A1 (en) * | 1983-09-21 | 1985-04-11 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR BROMMETHYLATING POLYPHENYLENE ETHERS |
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CN107602848A (en) * | 2017-10-09 | 2018-01-19 | 山东日兴新材料股份有限公司 | A kind of preparation method of water process Noryl film |
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2018
- 2018-04-09 CN CN201810312742.6A patent/CN108409959B/en not_active Expired - Fee Related
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DE3334068A1 (en) * | 1983-09-21 | 1985-04-11 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR BROMMETHYLATING POLYPHENYLENE ETHERS |
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