CN114736367A - Green and safe polyarylether gas-liquid heterogeneous synthesis method - Google Patents
Green and safe polyarylether gas-liquid heterogeneous synthesis method Download PDFInfo
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- CN114736367A CN114736367A CN202210433659.0A CN202210433659A CN114736367A CN 114736367 A CN114736367 A CN 114736367A CN 202210433659 A CN202210433659 A CN 202210433659A CN 114736367 A CN114736367 A CN 114736367A
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- polyarylether
- gas
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- green
- microchannel reactor
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- 229920000090 poly(aryl ether) Polymers 0.000 title claims abstract description 31
- 239000007788 liquid Substances 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000007864 aqueous solution Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 30
- 150000002989 phenols Chemical class 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 claims description 5
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims description 4
- CIRRFAQIWQFQSS-UHFFFAOYSA-N 6-ethyl-o-cresol Chemical compound CCC1=CC=CC(C)=C1O CIRRFAQIWQFQSS-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000001844 chromium Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 claims description 2
- NAILKKRDWBJCNH-UHFFFAOYSA-N 2,6-dipropylphenol Chemical compound CCCC1=CC=CC(CCC)=C1O NAILKKRDWBJCNH-UHFFFAOYSA-N 0.000 claims description 2
- MTUHNOQQFRNDBN-UHFFFAOYSA-N 2-(2,6-dimethylphenyl)phenol Chemical compound CC1=CC=CC(C)=C1C1=CC=CC=C1O MTUHNOQQFRNDBN-UHFFFAOYSA-N 0.000 claims description 2
- KTIRRDOBTNZKNL-UHFFFAOYSA-N 2-bromo-6-ethylphenol Chemical compound CCC1=CC=CC(Br)=C1O KTIRRDOBTNZKNL-UHFFFAOYSA-N 0.000 claims description 2
- YXZPTVOCJLCMRO-UHFFFAOYSA-N 2-bromo-6-methylphenol Chemical compound CC1=CC=CC(Br)=C1O YXZPTVOCJLCMRO-UHFFFAOYSA-N 0.000 claims description 2
- XNJCFOQHSHYSLG-UHFFFAOYSA-N 2-chloro-6-ethylphenol Chemical compound CCC1=CC=CC(Cl)=C1O XNJCFOQHSHYSLG-UHFFFAOYSA-N 0.000 claims description 2
- TVOICAOPKRBXDY-UHFFFAOYSA-N 2-methyl-6-(2-methylphenyl)phenol Chemical compound CC1=CC=CC(C=2C(=CC=CC=2)C)=C1O TVOICAOPKRBXDY-UHFFFAOYSA-N 0.000 claims description 2
- NXSQQKKFGJHACS-UHFFFAOYSA-N 2-methyl-6-propylphenol Chemical compound CCCC1=CC=CC(C)=C1O NXSQQKKFGJHACS-UHFFFAOYSA-N 0.000 claims description 2
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 2
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 claims description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010981 drying operation Methods 0.000 claims description 2
- ZYZHMSJNPCYUTB-UHFFFAOYSA-N n-benzyl-1-phenylethanamine Chemical compound C=1C=CC=CC=1C(C)NCC1=CC=CC=C1 ZYZHMSJNPCYUTB-UHFFFAOYSA-N 0.000 claims description 2
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 claims description 2
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 claims description 2
- XHFGWHUWQXTGAT-UHFFFAOYSA-N n-methylpropan-2-amine Chemical compound CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 16
- 229920001955 polyphenylene ether Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 10
- ZJJKYZDLXJABCP-UHFFFAOYSA-M CC(C=CC=C1C)=C1O.[OH-].[Na+] Chemical compound CC(C=CC=C1C)=C1O.[OH-].[Na+] ZJJKYZDLXJABCP-UHFFFAOYSA-M 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 5
- TXRXQYAWKZOYLW-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;copper Chemical compound [Cu].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O TXRXQYAWKZOYLW-UHFFFAOYSA-N 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000012673 precipitation polymerization Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- -1 copper halide Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- C08G65/38—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
- C08G65/44—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 by oxidation of phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of polymer synthesis, and particularly relates to a green and safe polyarylether gas-liquid heterogeneous synthesis method. The method comprises the steps of taking an alkaline aqueous solution of a phenol derivative and a high-oxygen-containing gas as raw materials, taking a metal salt-amine complex as a catalyst, introducing the phenol derivative and the catalyst into a straight-flow type microchannel reactor by using a metering pump for preheating, then injecting the preheated catalyst into a reaction module formed by connecting a plurality of enhanced mixed type continuous flow microchannel reactors in series, simultaneously introducing the oxygen-containing gas into each enhanced mixed type continuous flow microchannel reactor synchronously for reaction, then obtaining a polyarylether dispersion liquid, and obtaining a final product polyarylether through filtering, washing and drying. The method utilizes the continuous flow microchannel reactor to synthesize the polyarylether, uses no organic solvent in the whole process, has simple operation, safe, controllable and green polymerization process, high yield, narrow molecular weight distribution and high production efficiency, and can realize continuous industrial batch production.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a green and safe polyarylether gas-liquid heterogeneous synthesis method.
Background
The continuous flow micro-channel reactor is a small reaction system, the size of the pipeline of the continuous flow micro-channel reactor is far smaller than that of a conventional reactor, the miniaturization of a reaction channel can obviously increase the contact area between the channel and a heat exchange medium, and the heat exchange efficiency is improved.
Wherein, the extremely strong turbulent flow process in the microchannel can lead the mass transfer effect to have exponential increase, and particularly for heterogeneous reaction, the mass transfer enhancement effect is more obvious. In addition, the continuous flow microchannel reactor can realize operations such as multi-step continuous reaction, step-by-step addition of raw materials and the like, can directly realize mass production by amplification without pilot plant test, and has the advantages of high safety, controllable production process, high reaction selectivity and the like.
At present, the continuous flow microchannel reactor is mainly applied to synthesis of small molecules and industrial production thereof, and compared with the prior art, many researches and reports are not available in the field of industrial synthesis and modification of polymers, and most of the continuous flow microchannel reactor only stays in a laboratory stage.
Nagaki et al, 2004, reported cationic polymerization of vinyl butyl ether in microreactors for the first time (J.S.Chem., 2004, 126(45): 14702-. In 2005, Iwasaki et al prepared polybutyl acrylate (macromolecules, 2005, 38(4): 1159-1163.) with Mn =20800 and PDI =3.16 by free radical polymerization in a microreactor. By 2008, Nagaki et al have also achieved anionic polymerization of styrene in microreactors (macromolecules, 2008, 41(17): 6322-6330.).
Further, the polycondensation reaction can also be carried out in a microreaction system, for example, Kuboyama et al, in which the polycondensation reaction between diaminodiphenyl ether and isophthaloyl dichloride is carried out (society of chemical Engineers, 2005:132 d.).
On the other hand, polyphenylene ether, which is a representative of polyarylene ether, has now become one of the most consumed resins among five major engineering plastics. Polyphenylene oxide has excellent electrical insulation, dimensional stability, mechanical properties, high and low temperature resistance and extremely low dielectric loss, and is widely applied to the fields of automobile industry, electronic and electrical industry, communication industry, mechanical industry and the like.
Since the first commercial production of polyphenylene ether by GE company in the united states in 1965, various synthetic methods such as bulk polymerization, solution polymerization, precipitation polymerization and all-aqueous medium polymerization have been developed.
Among them, the bulk polymerization method was first introduced by GE corporation, and although the method avoids the use of a solvent, it has a long reaction time, a difficult control of the polymerization process, and a difficult separation, and finally, it has not been possible to realize industrial production. In the solution polymerization method, toluene and xylene are usually used as solvents, and after the reaction is completed, the product polyphenylene ether is completely dissolved in the solvents, and then a poor solvent for polyphenylene ether such as methanol is injected to precipitate polyphenylene ether. In the precipitation polymerization method, the organic solvent is a mixed solution of a good solvent and a poor solvent of the polyphenylene ether, and the polyphenylene ether automatically precipitates and precipitates from a polymerization solution along with the progress of the polymerization reaction when the molecular weight of the polyphenylene ether is increased to a certain degree.
Nowadays, Sabic, xu Kasei and Mitsubishi gas all adopt a solution polymerization method, and China's Lanxing chemical industry adopts a precipitation polymerization method. The subsequent processes of the solution polymerization method and the precipitation polymerization method both consume a large amount of energy, and treat and recover various organic solvents such as toluene, methanol and the like through complex operation procedures, so that the production cost is high, the environmental pollution is serious, the risk coefficient is high, people are forced to develop a green synthesis method of polyphenyl ether by taking water as a single solvent, and certain achievements are achieved. Saito et al, Japan, prepared polyphenylene ether having a molecular weight of 1.3 ten thousand in an all-aqueous medium using sodium hydroxide as a pH adjuster, sodium dodecyl sulfate as a surfactant, and potassium ferricyanate as a catalyst (German applied Chemicals, 2004, 43(6): 730-. The molecular weight of polyphenylene oxide prepared by an all-aqueous medium polymerization method is further improved to 3.7 ten thousand by taking a magnetic load type metal ion-polyamide amine complex as a catalyst (Chinese patent CN 200910096196).
In essence, the synthesis of polyphenylene ether is achieved by oxidative condensation polymerization of 2, 6-dimethylphenol. The conventional polyarylether synthesis processes described above usually employ a kettle reactor, which is initiated by blowing an oxygen-containing gas into a phenol derivative solution to initiate oxidative condensation polymerization. However, because the exothermic amount of the polymerization process is large, only gas with oxygen content lower than 25v/v% is generally selected, and especially in the initial stage of the polymerization reaction, the reaction must be controlled at a lower temperature, and oxygen-containing gas is slowly introduced to prevent the danger caused by implosion, so that the whole reaction period is longer and the energy consumption is higher. The research work of preparing polyphenyl ether or polyarylether by oxidizing oxygen in an all-aqueous medium by using a continuous flow microchannel reactor is not reported so far, and the industrial large-scale production of the all-aqueous medium method is not realized.
Disclosure of Invention
The invention provides a green and safe polyarylether gas-liquid heterogeneous synthesis method, which can realize a green and safe synthesis process of polyphenylene oxide in a continuous flow microchannel reactor by firstly punching an enhanced mixed type continuous flow microchannel reactor, then preheating an alkaline aqueous solution of a phenol derivative, then injecting an oxygen-containing gas into a series module of the enhanced mixed type continuous flow microchannel reactor, and finally carrying out post-treatment on an oxidation condensation polymerization product.
The technical scheme adopted by the invention for solving the problems is as follows: a green and safe polyarylether gas-liquid heterogeneous synthesis method sequentially comprises the following steps:
s1, arranging a gas inlet on each reactor of the series module of the enhanced mixed continuous flow microchannel reactor;
s2, adding a phenol derivative alkaline aqueous solution into the straight-flow type microchannel reactor, and carrying out preheating operation to obtain a preheating solution;
s3, adding the preheating liquid into the series module of the enhanced mixed continuous flow microchannel reactor, injecting oxygen-containing gas at all the gas inlets, heating for reaction, and flowing out polyarylether dispersion liquid in the last reactor;
s4, sequentially carrying out standing, filtering, washing and drying operations on the polyarylether dispersion liquid to obtain a final polyarylether product.
In the present invention, the phenol derivative alkaline aqueous solution is fed to the flow-through type microchannel reactor by a metering pump.
The further preferred technical scheme is as follows: in S2, the material composition of the phenol derivative alkaline aqueous solution comprises a phenol derivative, a surfactant and a metal salt-amine complex catalyst, and the pH value of the phenol derivative alkaline aqueous solution is not less than 9.
In the present invention, sodium hydroxide is added for adjusting the pH of the phenol derivative alkaline aqueous solution.
The further preferred technical scheme is as follows: in S2, the phenol derivative is any one of 2, 6-dimethylphenol, 2, 6-diethylphenol, 2, 6-di-n-propylphenol, 2, 6-diphenylphenol, 2, 6-xylylphenol, 2,3, 6-trimethylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-tolylphenol, 2-methyl-6-bromophenol, and 2-ethyl-6-chlorophenol, and the concentration of the phenol derivative in the alkaline aqueous solution is 0.5 to 30 wt%.
In the present invention, the surfactant is a common anionic surfactant, and is used in an amount of 0.01 to 3wt% based on the phenol derivative alkaline aqueous solution.
The further preferred technical scheme is as follows: in S2, the metal salt in the metal salt-amine complex catalyst is any one or a mixture of copper salt, manganese salt and chromium salt, the amine is any one or a mixture of dimethylamine, diethylamine, dipropylamine, dibutylamine, dibenzylamine, dicyclohexylamine, diethanolamine, methylethylamine, N-methylisopropylamine, N-methylcyclohexylamine, N-ethylisopropylamine, N-benzylmethylamine, N-benzyl-1-phenylethylamine, N-dimethylbutylamine and any one or a mixture of N, N-dialkylethylenediamine and pyridine, and the concentration of the metal salt-amine complex catalyst in the phenol derivative alkaline aqueous solution is 0.1 to 45 wt%.
In the invention, the metal salt is any one or a mixture of more of copper halide, cuprous halide, copper sulfate, cuprous sulfate, cupric nitrate, cuprous nitrate, cupric acetate, cuprous acetate, cupric propionate, cuprous propionate, cupric dodecanoate, cupric hexadecanoate, cuprous benzoate and corresponding manganese salt and chromium salt.
The further preferred technical scheme is as follows: in S2, the preheating operation temperature is less than or equal to 60 ℃, the time is 5-300S, and the flow rate of the phenol derivative alkaline aqueous solution in the straight-flow type microchannel reactor is 0.3-40 mL/min.
In the invention, when the enhanced mixed continuous flow microchannel reactor and the direct flow microchannel reactor are used, the enhanced mixed continuous flow microchannel reactor and the direct flow microchannel reactor are required to be heated and are heated by an external heat exchanger, wherein a heating medium is any one of heat conduction oil, water, brine ice and ethanol.
The further preferred technical scheme is as follows: in S3, the oxygen concentration of the oxygen-containing gas is 80-100v/v%, and the molar ratio of the total amount of oxygen injected from all the gas inlets to the added amount of the phenol derivative is (0.8-1.3): 1.
The further preferred technical scheme is as follows: in S3, the amount of oxygen injected at the gas inlet of the first intensive mixing type continuous flow microchannel reactor is 50-100% of the total amount of oxygen, and the amount of oxygen injected at the gas inlet of the second intensive mixing type continuous flow microchannel reactor is 0-40% of the total amount of oxygen.
The further preferred technical scheme is as follows: in S3, the total reaction time of the preheating liquid in the series module of the enhanced mixed type continuous flow microchannel reactor is 30-2400S.
The further preferred technical scheme is as follows: in S1, the vertical cross-section of the channel of the enhanced mixed continuous flow microchannel reactor is in the shape of any one or a combination of a plurality of heart-shaped, drop-shaped, T-shaped and spherical shapes; in S2, the cross-sectional shape of the straight-flow microchannel reactor is circular.
In the invention, the hydraulic diameter of the channel of the enhanced mixed continuous flow microchannel reactor and the straight flow microchannel reactor is 0.5-20.0mm, and the material of the enhanced mixed continuous flow microchannel reactor and the straight flow microchannel reactor can be any one of glass, metal simple substance, alloy, ceramic, monocrystalline silicon, fluorine-containing resin and high cross-linking thermosetting resin. Of course, the anti-corrosion layer is added on the material, so that the safety and the high efficiency are achieved.
In addition, in the serial module, the number of the intensified hybrid type continuous flow micro-channel reactors is 2-20.
The further preferred technical scheme is as follows: in S4, the polyarylether product has a number average molecular weight of less than or equal to 10000.
In the invention, the number of the repeating structural units of the polyarylether product is 6-450.
The present invention has the following advantages.
Firstly, in an alkaline aqueous solution, the solubility of the phenol derivative in water is increased due to the generation of corresponding salt, the subsequent reaction is ensured to be mainly polymerized in a C-O coupling mode, the generation of byproducts is inhibited, and the yield and the selectivity of the polymer are improved.
Secondly, the method utilizes the continuous flow microchannel reactor to synthesize the polyarylether, does not use organic solvent in the whole process, has simple operation, safe, controllable and green polymerization process, high yield, narrow molecular weight distribution and high production efficiency, and can realize continuous industrial batch production.
And thirdly, the preparation method has mild preparation conditions, low production cost, strong universality, easy mass and large-scale production, and good industrial production basis and wide application prospect.
Detailed Description
The following description is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention.
Example 1
Preparing 4wt% of 2, 6-dimethylphenol sodium hydroxide aqueous solution, controlling the pH value to be 10, adding 0.75wt% of lauryl sodium sulfate and 1.2wt% of copper-ethylene diamine tetraacetic acid complex, and slowly and uniformly stirring to obtain the 2, 6-dimethylphenol sodium hydroxide aqueous solution.
And (3) pumping the sodium hydroxide aqueous solution of the 2, 6-dimethylphenol into a straight channel module of the corning high-flux micro-channel reactor through a metering pump for preheating, setting the preheating temperature to be 35 ℃ and the preheating retention time to be 30s, and controlling the flux of the sodium hydroxide aqueous solution of the 2, 6-dimethylphenol in the straight channel module to be 3 mL/min.
Selecting pure oxygen and controlling phenol derivative and O2Mole betweenThe ratio was 1: 1.03. The preheated sodium hydroxide aqueous solution of 2, 6-dimethylphenol directly enters a reaction module formed by connecting 3 corning high-flux microchannel reactors with heart-shaped channels in series for mixed reaction, wherein 60v/v% of pure oxygen is pumped into the reaction system by a first corning high-flux microchannel reactor in the reaction module, 30v/v% of pure oxygen is pumped into the reaction system by a second corning high-flux microchannel reactor in the reaction module, 10v/v% of pure oxygen is pumped into the reaction system by a third corning high-flux microchannel reactor in the reaction module, the reaction temperature is also controlled at 35 ℃, and the reaction residence time is 1800 s.
And collecting the aqueous dispersion solution of the polyphenyl ether flowing out of the outlet of the Corning heart type channel module, filtering, washing with methanol and drying to obtain a polyphenyl ether product. The number average molecular weight of the polyphenylene ether product was 4200 and the polymer dispersibility index PDI =1.88 as determined by GPC measurement.
Example 2
Preparing 4wt% of 2, 6-dimethylphenol sodium hydroxide aqueous solution, controlling the pH value to be 11, adding 0.75wt% of lauryl sodium sulfate and 1.2wt% of copper-ethylene diamine tetraacetic acid complex, and slowly and uniformly stirring to obtain the 2, 6-dimethylphenol sodium hydroxide aqueous solution.
And pumping the 2, 6-dimethylphenol sodium hydroxide aqueous solution into a straight channel module of the Corning high-flux microchannel reactor through a metering pump for preheating, setting the preheating temperature to be 45 ℃ and the preheating retention time to be 40s, and controlling the flux of the 2, 6-dimethylphenol sodium hydroxide aqueous solution in the straight channel module to be 3 mL/min.
Selecting pure oxygen and controlling phenol derivative and O2The molar ratio of the two is 1: 1.1. The preheated sodium hydroxide aqueous solution of 2, 6-dimethylphenol directly enters a reaction module consisting of 3 corning high-flux microchannel reactors with heart-shaped channels in series for mixed reaction, wherein 50v/v% of pure oxygen is pumped into the reaction system by a first corning high-flux microchannel reactor in the reaction module, 30v/v% of pure oxygen is pumped into the reaction system by a second corning high-flux microchannel reactor in the reaction module, and 20v/v% of pure oxygen is pumped into the reaction system by the reaction moduleThe third corning high-flux microchannel reactor in the module is pumped into a reaction system, the reaction temperature is also controlled at 45 ℃, and the reaction residence time is 1800 s.
And collecting the aqueous dispersion solution of the polyphenyl ether flowing out of the outlet of the Corning heart type channel module, filtering, washing with methanol and drying to obtain a polyphenyl ether product. The number average molecular weight of the polyphenylene ether product was 4500, polymer dispersibility index PDI =1.82 as determined by GPC testing.
Example 3
Preparing 8wt% of 2, 6-dimethylphenol sodium hydroxide aqueous solution, controlling the pH value to be 11, adding 1.25wt% of sodium dodecyl sulfate and 1.5wt% of copper-ethylene diamine tetraacetic acid complex, and slowly and uniformly stirring to obtain the 2, 6-dimethylphenol sodium hydroxide aqueous solution.
And (3) pumping the sodium hydroxide aqueous solution of the 2, 6-dimethylphenol into a straight channel module of the corning high-flux micro-channel reactor through a metering pump for preheating, setting the preheating temperature to be 45 ℃ and the preheating retention time to be 40s, and controlling the flux of the sodium hydroxide aqueous solution of the 2, 6-dimethylphenol in the straight channel module to be 2 mL/min.
Selecting pure oxygen and controlling phenol derivative and O2The molar ratio of the two is 1: 1.1. The preheated sodium hydroxide aqueous solution of the 2, 6-dimethylphenol directly enters a reaction module formed by connecting 3 corning high-flux microchannel reactors with heart-shaped channels in series for mixing reaction, wherein 50v/v% of pure oxygen is pumped into the reaction system from a first corning high-flux microchannel reactor in the reaction module, 30v/v% of pure oxygen is pumped into the reaction system from a second corning high-flux microchannel reactor in the reaction module, 20v/v% of pure oxygen is pumped into the reaction system from a third corning high-flux microchannel reactor in the reaction module, the reaction temperature is also controlled at 45 ℃, and the reaction residence time is 2300 s.
And collecting the aqueous dispersion solution of the polyphenyl ether flowing out of the outlet of the Corning heart type channel module, filtering, washing with methanol and drying to obtain a polyphenyl ether product. The number average molecular weight of the polyphenylene ether product was 5300 and the polymer dispersibility index PDI =1.83 as determined by GPC testing.
Example 4
Preparing 10wt% of 2, 6-diethylphenol sodium hydroxide aqueous solution, controlling the pH value to be 11.5, adding 2.0wt% of sodium dodecyl sulfate and 2.0wt% of copper-ethylene diamine tetraacetic acid complex, and slowly and uniformly stirring to obtain the 2, 6-diethylphenol sodium hydroxide aqueous solution.
And pumping the sodium hydroxide aqueous solution of the 2, 6-diethylphenol into a straight channel module of the corning high-flux microchannel reactor through a metering pump for preheating, setting the preheating temperature to be 50 ℃ and the preheating residence time to be 50s, and controlling the flux of the sodium hydroxide aqueous solution of the 2, 6-diethylphenol in the straight channel module to be 2 mL/min.
Selecting pure oxygen and controlling phenol derivative and O2The molar ratio of the two is 1: 1.1. The preheated sodium hydroxide aqueous solution of the 2, 6-diethylphenol directly enters a reaction module consisting of 3 corning high-flux microchannel reactors with heart-shaped channels in series for mixing reaction, wherein 50v/v% of pure oxygen is pumped into the reaction system from a first corning high-flux microchannel reactor in the reaction module, 30v/v% of pure oxygen is pumped into the reaction system from a second corning high-flux microchannel reactor in the reaction module, 20v/v% of pure oxygen is pumped into the reaction system from a third corning high-flux microchannel reactor in the reaction module, the reaction temperature is also controlled at 50 ℃, and the reaction residence time is 2300 s.
And collecting the aqueous dispersion solution of the polyphenyl ether flowing out of the outlet of the Corning heart type channel module, filtering, washing with methanol and drying to obtain a polyphenyl ether product. The number average molecular weight of the polyphenylene ether product was 5900 and the polymer dispersibility index PDI =1.75 as determined by GPC testing.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various modifications can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. These are non-inventive modifications, which are intended to be protected by patent laws within the scope of the claims appended hereto.
Claims (10)
1. A green and safe polyarylether gas-liquid heterogeneous synthesis method is characterized by sequentially comprising the following steps:
s1, arranging a gas inlet on each reactor of the series module of the enhanced mixed continuous flow microchannel reactor;
s2, adding a phenol derivative alkaline aqueous solution into the straight-flow type microchannel reactor, and carrying out preheating operation to obtain a preheating solution;
s3, adding the preheating liquid into the series module of the enhanced mixed continuous flow microchannel reactor, injecting oxygen-containing gas at all gas inlets, heating for reaction, and flowing out polyarylether dispersion liquid in the last reactor;
s4, sequentially carrying out standing, filtering, washing and drying operations on the polyarylether dispersion liquid to obtain a final polyarylether product.
2. The method for the green and safe heterogeneous synthesis of polyarylether gas-liquid according to claim 1, wherein the method comprises the following steps: in S2, the material composition of the phenol derivative alkaline aqueous solution comprises a phenol derivative, a surfactant and a metal salt-amine complex catalyst, and the pH value of the phenol derivative alkaline aqueous solution is not less than 9.
3. The green and safe polyarylether gas-liquid heterogeneous synthesis method according to claim 2, characterized in that: in S2, the phenol derivative is any one of 2, 6-dimethylphenol, 2, 6-diethylphenol, 2, 6-di-n-propylphenol, 2, 6-diphenylphenol, 2, 6-xylylphenol, 2,3, 6-trimethylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-tolylphenol, 2-methyl-6-bromophenol, and 2-ethyl-6-chlorophenol, and the concentration of the phenol derivative in the alkaline aqueous solution is 0.5 to 30 wt%.
4. The green and safe polyarylether gas-liquid heterogeneous synthesis method according to claim 2, characterized in that: in S2, the metal salt in the metal salt-amine complex catalyst is any one or a mixture of copper salt, manganese salt and chromium salt, the amine is any one or a mixture of dimethylamine, diethylamine, dipropylamine, dibutylamine, dibenzylamine, dicyclohexylamine, diethanolamine, methylethylamine, N-methylisopropylamine, N-methylcyclohexylamine, N-ethylisopropylamine, N-benzylmethylamine, N-benzyl-1-phenylethylamine, N-dimethylbutylamine and any one or a mixture of N, N-dialkylethylenediamine and pyridine, and the concentration of the metal salt-amine complex catalyst in the phenol derivative alkaline aqueous solution is 0.1 to 45 wt%.
5. The method for the green and safe heterogeneous synthesis of polyarylether gas-liquid according to claim 1, wherein the method comprises the following steps: in S2, the preheating operation temperature is less than or equal to 60 ℃, the time is 5-300S, and the flow rate of the phenol derivative alkaline aqueous solution in the straight-flow type microchannel reactor is 0.3-40 mL/min.
6. The green and safe polyarylether gas-liquid heterogeneous synthesis method according to claim 1, characterized in that: in S3, the oxygen concentration of the oxygen-containing gas is 80-100v/v%, and the molar ratio of the total amount of oxygen injected from all the gas inlets to the added amount of the phenol derivative is (0.8-1.3): 1.
7. The method for the green and safe heterogeneous synthesis of polyarylether gas-liquid according to claim 1, wherein the method comprises the following steps: in S3, the amount of oxygen injected at the gas inlet of the first intensive mixing type continuous flow microchannel reactor is 50-100% of the total amount of oxygen, and the amount of oxygen injected at the gas inlet of the second intensive mixing type continuous flow microchannel reactor is 0-40% of the total amount of oxygen.
8. The method for the green and safe heterogeneous synthesis of polyarylether gas-liquid according to claim 1, wherein the method comprises the following steps: in S3, the total reaction time of the preheating liquid in the series module of the enhanced mixed type continuous flow microchannel reactor is 30-2400S.
9. The green and safe polyarylether gas-liquid heterogeneous synthesis method according to claim 1, characterized in that: in S1, the vertical cross-section of the channel of the enhanced mixed continuous flow microchannel reactor is in the shape of any one or a combination of a plurality of heart-shaped, drop-shaped, T-shaped and spherical shapes; in S2, the cross-sectional shape of the straight-flow type microchannel reactor is circular.
10. The method for the green and safe heterogeneous synthesis of polyarylether gas-liquid according to claim 1, wherein the method comprises the following steps: in S4, the number average molecular weight of the polyarylether product is less than or equal to 10000.
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