CN114736367B - Green and safe gas-liquid heterogeneous synthesis method for polyarylether - Google Patents
Green and safe gas-liquid heterogeneous synthesis method for polyarylether Download PDFInfo
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- 229920000090 poly(aryl ether) Polymers 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 239000007864 aqueous solution Substances 0.000 claims abstract description 36
- 150000002989 phenols Chemical class 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 19
- 229910001882 dioxygen Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 11
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- CCGUNQAEPVRLEL-UHFFFAOYSA-N acetic acid copper ethane-1,2-diamine Chemical compound [Cu].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN CCGUNQAEPVRLEL-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010981 drying operation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 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
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 229920001955 polyphenylene ether Polymers 0.000 description 12
- 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
- 239000004815 dispersion polymer Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012673 precipitation polymerization Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 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 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
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- CIRRFAQIWQFQSS-UHFFFAOYSA-N 6-ethyl-o-cresol Chemical compound CCC1=CC=CC(C)=C1O CIRRFAQIWQFQSS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 150000001844 chromium Chemical class 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
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- -1 potassium ferricyanide Chemical compound 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
- 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 description 1
- NAILKKRDWBJCNH-UHFFFAOYSA-N 2,6-dipropylphenol Chemical compound CCCC1=CC=CC(CCC)=C1O NAILKKRDWBJCNH-UHFFFAOYSA-N 0.000 description 1
- MTUHNOQQFRNDBN-UHFFFAOYSA-N 2-(2,6-dimethylphenyl)phenol Chemical compound CC1=CC=CC(C)=C1C1=CC=CC=C1O MTUHNOQQFRNDBN-UHFFFAOYSA-N 0.000 description 1
- KTIRRDOBTNZKNL-UHFFFAOYSA-N 2-bromo-6-ethylphenol Chemical compound CCC1=CC=CC(Br)=C1O KTIRRDOBTNZKNL-UHFFFAOYSA-N 0.000 description 1
- YXZPTVOCJLCMRO-UHFFFAOYSA-N 2-bromo-6-methylphenol Chemical compound CC1=CC=CC(Br)=C1O YXZPTVOCJLCMRO-UHFFFAOYSA-N 0.000 description 1
- XNJCFOQHSHYSLG-UHFFFAOYSA-N 2-chloro-6-ethylphenol Chemical compound CCC1=CC=CC(Cl)=C1O XNJCFOQHSHYSLG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- NXSQQKKFGJHACS-UHFFFAOYSA-N 2-methyl-6-propylphenol Chemical compound CCCC1=CC=CC(C)=C1O NXSQQKKFGJHACS-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
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- UPABQMWFWCMOFV-UHFFFAOYSA-N benethamine Chemical compound C=1C=CC=CC=1CNCCC1=CC=CC=C1 UPABQMWFWCMOFV-UHFFFAOYSA-N 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
- 239000012267 brine Substances 0.000 description 1
- 230000005587 bubbling Effects 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
- 150000001879 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 229910000366 copper(II) sulfate Inorganic materials 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
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 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
- 238000004880 explosion 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
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- XHFGWHUWQXTGAT-UHFFFAOYSA-N n-methylpropan-2-amine Chemical compound CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 229920001187 thermosetting polymer Polymers 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
Abstract
The invention belongs to the technical field of polymer synthesis, and particularly relates to a green and safe gas-liquid heterogeneous synthesis method of polyarylether. The invention takes alkaline aqueous solution of phenol derivative and high oxygen-containing gas as raw materials and metal salt-amine complex as catalyst, the phenol derivative and the catalyst are firstly introduced into a direct-flow type micro-channel reactor for preheating by a metering pump, then are injected into a reaction module formed by connecting a plurality of enhanced mixed type continuous flow micro-channel reactors in series, meanwhile, oxygen-containing gas is synchronously introduced into each enhanced mixed type continuous flow micro-channel reactor for reaction, then polyarylether dispersion liquid is obtained, and finally the polyarylether is obtained after filtration, washing and drying. The invention synthesizes the polyarylether by utilizing the continuous flow micro-channel reactor, has no use of organic solvent in the whole process, has simple operation, safe and controllable polymerization process, high yield, narrow molecular weight distribution and high production efficiency, and can realize continuous industrialized mass production.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a green and safe gas-liquid heterogeneous synthesis method of polyarylether.
Background
The continuous flow micro-channel reactor is a small reaction system, the pipeline size of the reactor is far smaller than that of a conventional reactor, the miniaturization of the reaction channel can obviously increase the contact area between the channel and a heat exchange medium, and the heat exchange efficiency is improved.
The extremely strong turbulent flow process in the micro-channel can lead the mass transfer effect to exponentially increase, and particularly for heterogeneous reaction, the mass transfer enhancement effect is more obvious. In addition, the continuous flow micro-channel reactor can realize multi-step continuous reaction, step-by-step raw material addition and other operations, can directly amplify and realize batch production without pilot scale, and has the advantages of high safety, controllable production process, high reaction selectivity and the like.
In the present stage, the continuous flow micro-channel reactor is mainly applied to the synthesis of small molecules and the industrialized production thereof, and compared with the synthesis and modification fields of polymers in industrialization, the research and the report are not very much, and most of the continuous flow micro-channel reactor is only in the laboratory stage.
In 2004 Nagaki et al reported for the first time cationic polymerization of vinyl butyl ether in microreactors (American society of chemistry, 2004, 126 (45): 14702-14703.). In 2005 Iwasaki et al prepared polybutyl acrylate with mn=20800 and pdi=3.16 by free radical polymerization in a microreactor (macromolecules, 2005, 38 (4): 1159-1163.). Nagaki et al have in turn achieved anionic polymerization of styrene in microreactors by 2008 (macromolecules, 2008, 41 (17): 6322-6330.).
Furthermore, the polycondensation reaction can also be carried out in a microreaction system, for example, in which Kuboyama et al have achieved a polycondensation reaction between p-diaminodiphenyl ether and isophthaloyl chloride (American society of chemical Engineers, 2005:132 d.).
On the other hand, as a typical representative of polyarylether, polyphenylene ether has become one of the resins with the largest consumption among five engineering plastics. Polyphenylene ether 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 electric industry, communication industry, mechanical industry and the like.
Since the earliest commercial production of polyphenylene ether by the american GE company in 1965, various synthetic means such as bulk polymerization, solution polymerization, precipitation polymerization and all-aqueous medium polymerization have been developed.
Among them, the bulk polymerization method is also first introduced by the GE company, and the method avoids the use of solvent, but has the disadvantages of long reaction time, difficult control of polymerization process and difficult separation, and finally fails to realize industrialized production. The solution polymerization method usually uses toluene and xylene as solvents, the product polyphenyl ether is completely dissolved in the solvents after the reaction is finished, and then the poor solvents of the polyphenyl ether such as methanol are injected to separate out and precipitate the polyphenyl ether. In the precipitation polymerization method, the organic solvent is selected from mixed solution of good solvent and poor solvent of polyphenyl ether, and along with the progress of polymerization reaction, when the molecular weight of the polyphenyl ether is increased to a certain degree, the polyphenyl ether automatically precipitates and precipitates from the polymerization solution.
At present, sabic, xudi formation and Mitsubishi gas all adopt a solution polymerization method, and blue star chemical industry in China adopts a precipitation polymerization method. The solution polymerization method and the precipitation polymerization method both consume a large amount of energy in the subsequent process, and various organic solvents such as toluene, methanol and the like are treated and recovered through complex operation procedures, so that the production cost is high, the environmental pollution is serious, the danger coefficient is high, people are forced to develop a green polyphenyl ether synthesis method using water as a single solvent, and a certain result is achieved. Japanese scholars Saito et al prepared polyphenylene ether having a molecular weight of 1.3 ten thousand in an aqueous medium using sodium hydroxide as a pH adjustor, sodium dodecyl sulfate as a surfactant, and potassium ferricyanide as a catalyst (German application chemistry, 2004, 43 (6): 730-733). Gu Cheng et al selected a magnetic supported metal ion-polyamidoamine complex as a catalyst to further increase the molecular weight of polyphenylene ether prepared by the all aqueous medium polymerization to 3.7 tens of thousands (chinese patent CN 200910096196).
Essentially, the synthesis of polyphenylene ether is accomplished by oxidative condensation polymerization of 2, 6-dimethylphenol. Each of the conventional polyarylether synthesis processes described above is usually carried out by using a tank reactor, and the oxidative condensation polymerization is initiated by bubbling an oxygen-containing gas into the phenol derivative solution. However, because the heat release amount in the polymerization process is large, only gas with the oxygen content lower than 25v/v% is generally selected, and particularly 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 explosion polymerization from generating danger, so that the whole reaction period is longer and the energy consumption is higher. No research work has been reported to date on the preparation of polyphenylene ether or polyarylether by oxygen oxidation in an all-aqueous medium using a continuous flow microchannel reactor, and no industrial mass production by an all-aqueous medium method has been realized yet.
Disclosure of Invention
The invention provides a green and safe gas-liquid heterogeneous synthesis method of polyarylether, which can realize the green and safe synthesis process of polyphenylene ether in a continuous flow micro-channel reactor by firstly punching the reinforced mixed continuous flow micro-channel reactor, then preheating a phenol derivative alkaline aqueous solution, then injecting an oxygen-containing gas into a serial module of the reinforced mixed continuous flow micro-channel reactor, and finally performing post-treatment on an oxidative condensation polymerization product.
The invention adopts the technical proposal that: the green and safe gas-liquid heterogeneous synthesis method of the polyarylether comprises the following steps in sequence:
s1, arranging a gas inlet on each reactor of the enhanced mixed continuous flow micro-channel reactor serial module;
s2, adding a phenol derivative alkaline aqueous solution into the direct-current microchannel reactor, and performing preheating operation to obtain a preheating solution;
s3, adding the preheating liquid into the serial modules of the enhanced mixed continuous flow micro-channel reactors, injecting oxygen-containing gas at all gas inlets, heating for reaction, and flowing out polyarylether dispersion liquid in the last reactor;
and 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 into the direct flow type microchannel reactor by a metering pump.
The further preferable 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, wherein the pH value of the phenol derivative alkaline aqueous solution is more than or equal to 9.
In the present invention, sodium hydroxide is added for adjusting the pH of the alkaline aqueous solution of the phenol derivative.
The further preferable 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 in the aqueous alkali solution of the phenol derivative is 0.5 to 30% by weight.
In the present invention, the surfactant is a usual anionic surfactant, and the amount thereof is 0.01 to 3wt% based on the alkaline aqueous solution of the phenol derivative.
The further preferable technical scheme is as follows: in S2, the metal salt in the metal salt-amine complex catalyst is any one or a mixture of a plurality of copper salt, manganese salt and chromium salt, wherein 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-phenethylamine, N-dimethylbutylamine and N, N-dialkyl ethylenediamine and pyridine, and the concentration of the metal salt-amine complex catalyst in the phenol derivative alkaline aqueous solution is 0.1-45wt%.
In the invention, the metal salt is any one or a mixture of a plurality of copper halide, cuprous halide, cupric sulfate, cuprous sulfate, cupric nitrate, cuprous nitrate, cupric acetate, cuprous acetate, cupric propionate, cuprous propionate, cupric dodecanoate, cupric hexadecanoate and cuprous benzoate, and corresponding manganese salt and chromium salt.
The further preferable technical scheme is as follows: in S2, the temperature of the preheating operation 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 direct-current microchannel reactor is 0.3-40mL/min.
In the invention, the enhanced mixed continuous flow micro-channel reactor and the direct flow micro-channel reactor are heated when in use and are heated by an external heat exchanger, wherein the heating medium is any one of heat conduction oil, water, brine ice and ethanol.
The further preferable 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) to 1.
The further preferable technical scheme is as follows: s3, the amount of the injected oxygen at the gas inlet of the first enhanced mixed type continuous flow micro-channel reactor accounts for 50-100% of the total amount of oxygen, and the amount of the injected oxygen at the gas inlet of the second enhanced mixed type continuous flow micro-channel reactor accounts for 0-40% of the total amount of oxygen.
The further preferable technical scheme is as follows: in S3, the total reaction time of the preheating solution in the enhanced mixed continuous flow micro-channel reactor serial module is 30-2400S.
The further preferable technical scheme is as follows: in the S1, the vertical section of the channel of the enhanced mixed continuous flow micro-channel reactor is any one or the combination of a plurality of heart-shaped, drop-shaped, T-shaped and spherical; in S2, the cross-sectional shape of the channel of the direct-current microchannel reactor is circular.
In the invention, the hydraulic diameters of the channels of the enhanced mixed continuous flow micro-channel reactor and the direct flow micro-channel reactor are all 0.5-20.0mm, and the materials of the enhanced mixed continuous flow micro-channel reactor and the direct flow micro-channel reactor can be any one of glass, metal simple substance, alloy, ceramic, monocrystalline silicon, fluorine-containing resin and high-crosslinking thermosetting resin. Of course, the above materials are safer and more efficient by adding the anti-corrosion layer.
In addition, the number of the enhanced hybrid continuous flow micro-channel reactors in the series module is 2-20.
The further preferable technical scheme is as follows: s4, the number average molecular weight of the polyarylether product is less than or equal to 10000.
In the invention, the number of the repeated structural units of the polyarylether product is 6-450.
The present invention has the following advantages.
First, in alkaline aqueous solution, phenol derivatives increase their solubility in water due to formation of the corresponding salts, and ensure polymerization of the subsequent reaction mainly in a C-O coupling manner, inhibit formation of by-products, and improve yield and selectivity of the polymer.
Secondly, the invention synthesizes the polyarylether by utilizing the continuous flow micro-channel reactor, the whole process has no use of organic solvent, the operation is simple, the polymerization process is safe and controllable, green, the yield is high, the molecular weight distribution is narrower, the production efficiency is high, and the continuous industrialized mass production can be realized.
Thirdly, the preparation method has the advantages of mild preparation conditions, low production cost, easiness in batch and large-scale production, strong universality, good industrial production foundation and wide application prospect.
Detailed Description
The following description is of the preferred embodiments of the invention and is not intended to limit the scope of the invention.
Example 1
Preparing 4wt% sodium hydroxide aqueous solution of 2, 6-dimethylphenol, controlling the pH value to be 10, adding 0.75wt% sodium dodecyl sulfate and 1.2wt% copper-ethylenediamine tetraacetic acid complex, and slowly and uniformly stirring to obtain the sodium hydroxide aqueous solution of 2, 6-dimethylphenol.
And (3) pumping the sodium hydroxide aqueous solution of the 2, 6-dimethylphenol into a straight channel module of a corning high-flux microchannel reactor through a metering pump for preheating, wherein the preheating temperature is set to be 35 ℃, the preheating residence time is set to be 30s, and the flux of the sodium hydroxide aqueous solution of the 2, 6-dimethylphenol in the straight channel module is controlled to be 3mL/min.
Pure oxygen gas is selected and the phenol derivative and O are controlled 2 The molar ratio between the two is 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 micro-channel reactors with heart-shaped channels in series for mixed reaction, wherein 60v/v% of pure oxygen gas is injected into the reaction system from a first corning high-flux micro-channel reactor in the reaction module, 30v/v% of pure oxygen gas is injected into the reaction system from a second corning high-flux micro-channel reactor in the reaction module, 10v/v% of pure oxygen gas is injected into the reaction system from a third corning high-flux micro-channel reactor in the reaction module, and the reaction temperature is controlled to be 35 ℃ and the reaction residence time is 1800s.
Collecting the water-dispersed solution of the polyphenyl ether flowing out of the outlet of the corning type channel module, and then filtering, washing with methanol and drying to obtain a polyphenyl ether product. The number average molecular weight of the polyphenylene ether product was 4200 as determined by GPC testing, and the polymer dispersion index pdi=1.88.
Example 2
Preparing 4wt% sodium hydroxide aqueous solution of 2, 6-dimethylphenol, controlling the pH value to be 11, adding 0.75wt% sodium dodecyl sulfate and 1.2wt% copper-ethylenediamine tetraacetic acid complex, and slowly and uniformly stirring to obtain sodium hydroxide aqueous solution of 2, 6-dimethylphenol.
And (3) pumping the sodium hydroxide aqueous solution of the 2, 6-dimethylphenol into a straight channel module of a corning high-flux microchannel reactor through a metering pump for preheating, wherein the preheating temperature is set to be 45 ℃, the preheating residence time is set to be 40s, and the flux of the sodium hydroxide aqueous solution of the 2, 6-dimethylphenol in the straight channel module is controlled to be 3mL/min.
Pure oxygen gas is selected and the phenol derivative and O are controlled 2 The molar ratio between the two is 1:1.1. The preheated sodium hydroxide aqueous solution of 2, 6-dimethylphenol directly enters a reaction module formed by connecting 3 corning high-flux micro-channel reactors with heart-shaped channels in series for mixed reaction, wherein 50v/v% of pure oxygen gas is injected into the reaction system from a first corning high-flux micro-channel reactor in the reaction module, 30v/v% of pure oxygen gas is injected into the reaction system from a second corning high-flux micro-channel reactor in the reaction module, 20v/v% of pure oxygen gas is injected into the reaction system from a third corning high-flux micro-channel reactor in the reaction module, and the reaction temperature is controlled to be 45 ℃ and the reaction residence time is 1800s.
Collecting the water-dispersed solution of the polyphenyl ether flowing out of the outlet of the corning type channel module, and then filtering, washing with methanol and drying to obtain a polyphenyl ether product. The number average molecular weight of the polyphenylene ether product was found to be 4500 by GPC testing, and the polymer dispersion index pdi=1.82.
Example 3
Preparing 8wt% of sodium hydroxide aqueous solution of 2, 6-dimethylphenol, controlling the pH value to be 11, adding 1.25wt% of sodium dodecyl sulfate and 1.5wt% of copper-ethylenediamine tetraacetic acid complex, and slowly and uniformly stirring to obtain the sodium hydroxide aqueous solution of 2, 6-dimethylphenol.
And (3) pumping the sodium hydroxide aqueous solution of the 2, 6-dimethylphenol into a straight channel module of a corning high-flux microchannel reactor through a metering pump for preheating, wherein the preheating temperature is set to be 45 ℃, the preheating residence time is set to be 40s, and the flux of the sodium hydroxide aqueous solution of the 2, 6-dimethylphenol in the straight channel module is controlled to be 2mL/min.
Pure oxygen gas is selected and the phenol derivative and O are controlled 2 The molar ratio between the two is 1:1.1. The preheated sodium hydroxide aqueous solution of 2, 6-dimethylphenol directly enters a reaction module formed by connecting 3 corning high-flux micro-channel reactors with heart-shaped channels in series for mixed reaction, wherein 50v/v% of pure oxygen gas is injected into the reaction system from a first corning high-flux micro-channel reactor in the reaction module, 30v/v% of pure oxygen gas is injected into the reaction system from a second corning high-flux micro-channel reactor in the reaction module, 20v/v% of pure oxygen gas is injected into the reaction system from a third corning high-flux micro-channel reactor in the reaction module, and the reaction temperature is controlled at 45 ℃ and the reaction residence time is 2300s.
Collecting the water-dispersed solution of the polyphenyl ether flowing out of the outlet of the corning type channel module, and then 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 dispersion index pdi=1.83 as determined by GPC testing.
Example 4
Preparing 10wt% sodium hydroxide aqueous solution of 2, 6-diethyl phenol, controlling the pH value at 11.5, adding 2.0wt% sodium dodecyl sulfate and 2.0wt% copper-ethylenediamine tetraacetic acid complex, and slowly stirring uniformly to obtain sodium hydroxide aqueous solution of 2, 6-diethyl phenol.
And (3) pumping the sodium hydroxide aqueous solution of the 2, 6-diethylphenol into a straight-running channel module of the corning high-flux microchannel reactor through a metering pump for preheating, wherein the preheating temperature is set to be 50 ℃, the preheating residence time is set to be 50s, and the flux of the sodium hydroxide aqueous solution of the 2, 6-diethylphenol in the straight-running channel module is controlled to be 2mL/min.
Pure oxygen gas is selected and the phenol derivative and O are controlled 2 The molar ratio between the two is 1:1.1. The preheated sodium hydroxide aqueous solution of 2, 6-diethyl phenol directly enters a reaction module formed by connecting 3 corning high-flux micro-channel reactors with heart-shaped channels in series for mixingAnd (3) a synthesis reaction, wherein 50v/v% of pure oxygen gas is injected into the reaction system from a first corning high-flux micro-channel reactor in the reaction module, 30v/v% of pure oxygen gas is injected into the reaction system from a second corning high-flux micro-channel reactor in the reaction module, 20v/v% of pure oxygen gas is injected into the reaction system from a third corning high-flux micro-channel reactor in the reaction module, and the reaction temperature is controlled to be 50 ℃ and the reaction residence time is 2300s.
Collecting the water-dispersed solution of the polyphenyl ether flowing out of the outlet of the corning type channel module, and then filtering, washing with methanol and drying to obtain a polyphenyl ether product. The number average molecular weight of the polyphenylene ether product was 5900 as determined by GPC testing, and the polymer dispersion index pdi=1.75.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the above embodiments, and various modifications may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. These are all non-inventive modifications which are intended to be protected by the patent laws within the scope of the appended claims.
Claims (4)
1. The green and safe gas-liquid heterogeneous synthesis method of the polyarylether is characterized by sequentially comprising the following steps of:
s1, arranging a gas inlet on each reactor of the enhanced mixed continuous flow micro-channel reactor serial module;
s2, adding a phenol derivative alkaline aqueous solution into the direct-current microchannel reactor, and performing preheating operation to obtain a preheating solution;
s3, adding the preheating liquid into the serial modules of the enhanced mixed continuous flow micro-channel reactors, 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,
in S2, the alkaline aqueous solution of the phenol derivative comprises the following materials: preparing 10wt% sodium hydroxide aqueous solution of 2, 6-diethyl phenol, controlling the pH value at 11.5, adding 2.0wt% sodium dodecyl sulfate and 2.0wt% copper-ethylenediamine tetraacetic acid complex, slowly stirring uniformly to obtain sodium hydroxide aqueous solution of 2, 6-diethyl phenol,
s3, the enhanced mixed continuous flow micro-channel reactor series module comprises 3 reactors, 50v/v% of pure oxygen gas is injected into the reaction system from a first reactor in the reaction module, 30v/v% of pure oxygen gas is injected into the reaction system from a second reactor in the reaction module, 20v/v% of pure oxygen gas is injected into the reaction system from a third reactor in the reaction module,
s3, the molar ratio of the total amount of oxygen injected from all the gas inlets to the added amount of the phenol derivative is 1.1:1,
s4, the number average molecular weight of the polyarylether product is less than or equal to 10000.
2. The green and safe gas-liquid heterogeneous synthesis method of polyarylether according to claim 1, which is characterized in that: in S2, the temperature of the preheating operation 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 direct-current microchannel reactor is 0.3-40mL/min.
3. The green and safe gas-liquid heterogeneous synthesis method of polyarylether according to claim 1, which is characterized in that: in S3, the total reaction time of the preheating solution in the enhanced mixed continuous flow micro-channel reactor serial module is 30-2400S.
4. The green and safe gas-liquid heterogeneous synthesis method of polyarylether according to claim 1, which is characterized in that: in the S1, the vertical section of the channel of the enhanced mixed continuous flow micro-channel reactor is any one or the combination of a plurality of heart-shaped, drop-shaped, T-shaped and spherical; in S2, the cross-sectional shape of the channel of the direct-current microchannel reactor is circular.
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| GB1347134A (en) * | 1970-05-27 | 1974-02-27 | Asahi Dow Ltd | Process for producing polyphenylene ether |
| CN101899150A (en) * | 2010-07-28 | 2010-12-01 | 中国蓝星（集团）股份有限公司 | Method for producing polyphenyl ether |
| CN110156982A (en) * | 2019-06-21 | 2019-08-23 | 常州中英新材料有限公司 | A kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether |
| CN110317336A (en) * | 2019-06-21 | 2019-10-11 | 常州中英新材料有限公司 | A method of heat curing type polyarylether is synthesized using continuous flow micro passage reaction |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1347134A (en) * | 1970-05-27 | 1974-02-27 | Asahi Dow Ltd | Process for producing polyphenylene ether |
| CN101899150A (en) * | 2010-07-28 | 2010-12-01 | 中国蓝星（集团）股份有限公司 | Method for producing polyphenyl ether |
| CN110156982A (en) * | 2019-06-21 | 2019-08-23 | 常州中英新材料有限公司 | A kind of liquid liquid homogeneous method using continuous flow micro passage reaction synthesis polyarylether |
| CN110317336A (en) * | 2019-06-21 | 2019-10-11 | 常州中英新材料有限公司 | A method of heat curing type polyarylether is synthesized using continuous flow micro passage reaction |
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