CN115304525A - Green preparation method of sulfonated dihalogenated monomer - Google Patents
Green preparation method of sulfonated dihalogenated monomer Download PDFInfo
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- CN115304525A CN115304525A CN202211104590.3A CN202211104590A CN115304525A CN 115304525 A CN115304525 A CN 115304525A CN 202211104590 A CN202211104590 A CN 202211104590A CN 115304525 A CN115304525 A CN 115304525A
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- sulfonated
- sulfuric acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000178 monomer Substances 0.000 title claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002253 acid Substances 0.000 claims abstract description 66
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 28
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005457 ice water Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 68
- 239000000047 product Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 239000012295 chemical reaction liquid Substances 0.000 claims description 23
- 230000007062 hydrolysis Effects 0.000 claims description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims description 22
- -1 polytetrafluoroethylene Polymers 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 20
- 239000003011 anion exchange membrane Substances 0.000 claims description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 6
- 230000035699 permeability Effects 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 claims description 4
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical group C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 4
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical group C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 claims description 3
- LFABNOYDEODDFX-UHFFFAOYSA-N bis(4-bromophenyl)methanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=C(Br)C=C1 LFABNOYDEODDFX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- QBNABJXQGRVIRA-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)sulfonylbenzene Chemical compound C1=CC(Br)=CC=C1S(=O)(=O)C1=CC=C(Br)C=C1 QBNABJXQGRVIRA-UHFFFAOYSA-N 0.000 claims description 2
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003595 mist Substances 0.000 abstract description 19
- 238000011033 desalting Methods 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 9
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 5
- 238000001704 evaporation Methods 0.000 abstract description 4
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 150000008366 benzophenones Chemical class 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000001694 spray drying Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000909 electrodialysis Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000003457 sulfones Chemical class 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005341 cation exchange Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005185 salting out Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical class C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 125000001174 sulfone group Chemical group 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- ZTQWFLSVSUXFBO-UHFFFAOYSA-N FC1=CC=C(C(=O)C2=CC=C(C=C2)F)C=C1.[Na] Chemical compound FC1=CC=C(C(=O)C2=CC=C(C=C2)F)C=C1.[Na] ZTQWFLSVSUXFBO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- YKINVWJZGOCCRS-UHFFFAOYSA-N ClC1=CC=C(C(=O)C2=CC=C(C=C2)Cl)C=C1.[Na] Chemical compound ClC1=CC=C(C(=O)C2=CC=C(C=C2)Cl)C=C1.[Na] YKINVWJZGOCCRS-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FJPKZVUTEXZNPN-UHFFFAOYSA-N chromium copper molybdenum nickel Chemical compound [Ni][Cu][Cr][Mo] FJPKZVUTEXZNPN-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000001599 direct drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005612 types of electricity Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a green preparation method of a sulfonated dihalogenated monomer, which adopts fuming sulfuric acid as a sulfonating agent and a solvent, heats up to dissolve dihalogenated diphenyl sulfone or dihalogenated benzophenone, then injects the mixture into a two-section metal coil reactor at a constant speed, and injects a completely sulfonated product into an ice-water mixture through heating and cooling respectively to realize a continuous, controllable and sealed sulfonation process; then the aqueous solution is simply filtered and then is introduced into an electrodialyzer to basically remove the sulfuric acid component, and meanwhile, dilute sulfuric acid is recovered; adding alkali into the deacidified liquid for neutralization, then feeding the deacidified liquid into an electrodialyzer, quickly desalting, and then evaporating, crystallizing or spray drying to obtain the sulfonated dihalogenated monomer product. The preparation method has the advantages of stable and controllable reaction process, no acid mist pollution, concise and efficient purification process and no generation of waste acid and mixed salt, so the whole preparation process is green and environment-friendly, and the industrial production is easy to realize.
Description
Technical Field
The invention belongs to the technical field of fine chemical manufacturing, and particularly relates to a green preparation method of a sulfonated dihalogenated monomer.
Background
The preparation method comprises the steps of completely sulfonating dihalogenated diphenyl sulfone (such as 4,4' -dichlorodiphenyl sulfone) or dihalogenated benzophenone (such as 4,4' -difluorobenzophenone) to obtain a sulfonated monomer, and then carrying out polycondensation with 4,4' -biphenol, bisphenol A, bisphenol F or bisphenol S to prepare a soluble linear polymer with a sulfonic acid group on a main chain, wherein the soluble linear polymer is widely applied to the fields of hydrophilic modification of porous filter membranes, manufacture of cation exchange membranes (including proton exchange membranes), production of medical adsorbing materials and the like. Compared with the Post-sulfonation preparation method of sulfonating the linear polymer, the Direct polymerization preparation method of preparing the sulfonated monomer and polycondensing the sulfonated monomer into the linear ionic polymer has a series of advantages of more uniform distribution of sulfonic acid groups, higher sulfonation degree, no damage to a high-molecular main chain (when the Post-sulfonation is carried out, the damage to main chain aromatic ether bonds caused by a sulfonating agent is difficult to avoid), less crosslinking side reaction energy (the side crosslinking mainly comes from the fact that the sulfonic acid groups attack non-sulfonated benzene rings to form sulfone groups under the catalysis of concentrated sulfuric acid), better repeatability and controllability of cation exchange capacity (the actual cation exchange capacity obtained by the Direct polymerization preparation method is basically consistent with a theoretical value calculated according to the feeding proportion of the sulfonated monomer), and the like. Thus, sulfonated dihalodiphenylsulfones and sulfonated dihalobenzophenones as important starting industrial raw materials are crucial for their efficient preparation technology.
However, the existing preparation technology of the sulfonated dihalodiphenyl sulfone and the sulfonated dihalodiphenyl ketone has a plurality of disadvantages. For example, 3,3 '-sodium disulfonate-4,4' -dichlorodiphenyl sulfone (ref: fine chemical intermediate, published 12/2020, vol. 50, no. 6, page 67 to 71) is generally used in excess of oleum, and strong acid mist is easily emitted during high temperature reaction; after sulfonation, a crude product is obtained by carrying out salting-out operation for multiple times, and a high-concentration waste sulfuric acid/mixed salt (sodium chloride and sodium sulfate) solution is generated incidentally, so that the treatment is difficult, and the preparation process is not environment-friendly; when in refining, organic solvents such as isopropanol and the like are required to be used for recrystallization to obtain the product, organic wastewater is inevitably generated, and the production cost of recycling the organic solvents is increased. The Chinese invention patent (application number: 200810154671.8) discloses a liquid seal type nitrogen protection mode, which reduces the loss of sulfur trioxide in fuming sulfuric acid in the sulfonation process of dihalogenated diphenylsulfone, and can not completely stop acid mist although the acid mist is reduced to some extent; in addition, a purification method of sulfonated monomers is also proposed, which requires repeated salting-out operations, and inevitably generates a large amount of waste sulfuric acid and waste liquid of mixed salts, which become hazardous waste difficult to treat. Furthermore, the preparation of 3,3 '-sodium disulfonate-4,4' -difluorobenzophenone (reference: synthesis and performance research of novel proton exchange membranes for fuel cells, gilin university Press, 2011 published in 12 months, pages 61-63) uses higher concentration oleum (50% sulfur trioxide content), and the overflowing acid mist during high temperature reaction is more; meanwhile, the method still adopts the steps of salting out (adding sodium chloride), organic solvent (using methanol) recrystallization and the like after sulfonation, and the product can be obtained. Obviously, the preparation process is still not environment-friendly and does not belong to a green preparation technology.
Therefore, in view of the defects of the prior art such as more acid mist, difficult treatment of high-concentration waste acid/mixed salt solution, and having to use organic solvent, it is necessary to develop an environment-friendly preparation method for the above two sulfonated monomers.
Disclosure of Invention
The invention aims to overcome the defects and provide a green preparation method of the sulfonated dihalogenated monomer, which can reduce the acid consumption and the acid mist pollution in the sulfonation reaction process, avoid the generation of waste salt and the use of organic solvent in the product purification process and simultaneously realize the timely recovery of waste acid, so as to meet the application requirements of the related industrial fields.
The purpose of the invention is realized by the following technical scheme:
the green preparation method of the sulfonated dihalogen monomer comprises the following steps:
(1) Putting a dihalogenated reactant into a reaction kettle, covering the reaction kettle, vacuumizing, filling nitrogen, completely replacing air, injecting a proper amount of fuming sulfuric acid, starting stirring, heating to a target temperature, and completely dissolving reactant solids to obtain a reaction solution;
(2) Continuously injecting the reaction liquid into a two-section coil reactor, immersing a first section of coil into an oil bath to perform sulfonation reaction, and immersing a second section of coil into cold water to rapidly cool the reaction liquid;
(3) Connecting the outlet of the second section of coil pipe with a polytetrafluoroethylene pipeline, inserting the second section of coil pipe into an ice-water mixture, and continuously introducing the sulfonation reaction liquid for hydrolysis to obtain a hydrolysis acid liquid;
(4) Mechanically filtering the hydrolyzed acid solution, continuously introducing into a two-compartment electrodialyzer provided with a compact anion exchange membrane, introducing direct current, gradually removing sulfuric acid components to obtain a deacidified solution, and recovering from a concentration chamber to obtain a clean dilute sulfuric acid solution;
(5) Adding alkali into the deacidified liquid to neutralize the deacidified liquid until the pH value is slightly larger than 7, introducing the deacidified liquid into an electrodialyzer again, introducing direct current, and quickly removing residual salt to obtain a sulfonate aqueous solution only containing sulfonate products;
(6) And dehydrating and drying the aqueous solution of the sulfonate to obtain the sulfonated dihalogeno-monomer.
Preferably, the dihalo-reactant is dihalodiphenylsulfone or dihalobenzophenone, and correspondingly, the sulfonated dihalomonomer is sulfonated dihalodiphenylsulfone or sulfonated dihalobenzophenone.
Preferably, the dihalodiphenylsulfone is 4,4 '-difluorodiphenylsulfone, 4,4' -dichlorodiphenylsulfone or 4,4 '-dibromodiphenylsulfone and the dihalobenzophenone is 4,4' -difluorobenzophenone, 4,4 '-dichlorobenzophenone or 4,4' -dibromobenzophenone.
Preferably, in the step (1), the concentration of fuming sulfuric acid is 105 to 120% by mass of sulfuric acid, and the amount of fuming sulfuric acid added is 3 to 6 times the mass of the dihalo-reacted product.
Preferably, in the step (1), the target temperature is 50 to 100 ℃, preferably 60 to 90 ℃.
Preferably, in the step (2), the residence time of the reaction solution in the first-stage coil is 60 to 200 minutes, preferably 90 to 150 minutes.
Preferably, in the step (2), the oil bath temperature is 120-200 ℃, and preferably 140-180 ℃; the second section of coil pipe is immersed in cold water to ensure that the temperature of the reaction liquid in the second section of coil pipe is not lower than 60 ℃, and preferably 60-90 ℃.
Preferably, in the step (3), the amount of the ice-water mixture added is 2 to 5 times the mass of the sulfonation reaction liquid.
Preferably, in the step (4), the compact anion exchange membrane is a membrane with a differential pressure permeability coefficient of water of less than or equal to 0.002 mL/(cm) 2 h.MPa) anion exchange membranes.
Preferably, in the step (4) and the step (5), the electrodialyzer is operated at a current density of 5 to 30mA/cm 2 The effective membrane area.
Compared with the prior art, the invention has the beneficial effects that:
(1) The whole sulfonation process comprises three steps of low-temperature dissolution, high-temperature sulfonation and cooling, and is carried out under a completely closed condition, so that the utilization efficiency of fuming sulfuric acid used as a sulfonating agent and a solvent is higher, the overflow is less, and the pollution of generated acid mist is less;
(2) Because the two-section coil reactor is adopted, the three steps of low-temperature dissolution, high-temperature sulfonation and cooling are simply connected in series, the process is simple and easy to realize, the uniformity, controllability, reproducibility and high efficiency of the tubular reaction can be exerted, and the sulfonation reaction liquid with very uniform sulfonation degree can be continuously obtained; meanwhile, because the utilization rate of fuming sulfuric acid is increased, the sulfonation reaction time can be greatly shortened compared with the conventional kettle type reaction;
(3) The method has the advantages that the electrodialyzer with two compartments and a compact anion exchange membrane is used, an electrically driven membrane separation mode is adopted, sulfuric acid molecules with small molecular weight can be basically removed, sulfonated products with large molecular weight can be retained, clean recovery of residual sulfuric acid is realized at high efficiency, a salting-out step is avoided, the problem of treatment of hazardous waste liquid containing high-concentration waste acid and double-component mixed salt is solved, and green preparation is smoothly realized;
(4) The product solution deacidified and desalted by the electrodialysis technology has simple components, only contains the required sulfonated dihalogeno-diphenyl sulfone or sulfonated dihalogeno-diphenyl ketone sulfonate form product, and can easily obtain the product directly by the conventional drying method, thereby avoiding the steps of organic solvent recrystallization and purification process; therefore, the method is simple, efficient, green and environment-friendly and has low cost.
Drawings
FIG. 1 is a chemical structural diagram of sulfonated dihalodiphenyl sulfone and sulfonated dihalobenzophenone;
FIG. 2 is a flow chart of the preparation process of sulfonated dihalodiphenyl sulfone and sulfonated dihalodiphenyl ketone and the main equipment used in each step; in the figure: a represents a dissolving kettle, B1 represents a first section coil, B2 represents a second section coil, C represents an ice water diluting tank, D represents a filter, E represents a finished product solution tank, F represents an electrodialyzer, G represents an acid recovery tank, H represents a salt recovery tank, and I represents a dryer.
Detailed Description
The following detailed description of embodiments according to the present invention is provided in conjunction with the drawings, in which:
a green preparation method of sulfonated dihalogenated monomer (namely sulfonated dihalogenated diphenyl sulfone or sulfonated dihalogenated benzophenone) comprises the following steps: (1) Firstly, putting dihalogenated diphenyl sulfone or dihalogenated diphenyl ketone into an acid-resistant metal reaction kettle, covering the kettle, vacuumizing the kettle, filling nitrogen, completely replacing air, injecting a proper amount of fuming sulfuric acid, starting stirring, and moderately heating until the solid is completely dissolved; (2) Continuously filling nitrogen, opening a bottom valve and a metering pump, continuously injecting the dissolved reaction liquid into the two-section type acid-resistant metal coil reactor, balancing the opening degrees of a nitrogen gas inlet valve, the bottom valve and the metering pump, and enabling the reaction liquid to enter the coil at a constant speed; (3) Immersing the first section coil pipe into an oil bath, and performing sulfonation reaction at high temperature; immersing the second section of coil pipe into cold water, and quickly cooling the reaction liquid; (4) Connecting the outlet of the second section of coil pipe with a polytetrafluoroethylene pipeline, inserting the second section of coil pipe into an ice-water mixture, continuously introducing a sulfonation reaction solution, and hydrolyzing in time to obtain a hydrolysis acid solution; (5) Mechanically filtering the hydrolyzed acid solution, continuously introducing into a two-compartment electrodialyzer provided with a compact anion exchange membrane, introducing direct current, gradually removing sulfuric acid components, and recovering from a concentration chamber to obtain a clean dilute sulfuric acid solution; (6) Adding alkali into the deacidified liquid to neutralize the deacidified liquid until the pH value is slightly larger than 7, introducing the deacidified liquid into an electrodialyzer again, introducing direct current, and quickly removing residual salt to obtain an aqueous solution only containing a sulfonate product; (7) Dehydrating and drying the sulfonate aqueous solution to obtain the product in the form of sulfonate of the sulfonated dihalogenodiphenyl sulfone or the sulfonated dihalogenobenzophenone.
The sulfonated dihalo-diphenyl sulfone and sulfonated dihalo-benzophenone refer to the complete sulfonation products of dihalo-diphenyl sulfone and dihalo-benzophenone, and can only be the 'double sulfonation' products in which two benzene rings are respectively sulfonated. Since the sulfonation mechanism is an electrophilic substitution reaction of an aromatic ring, the structure of the sulfonation reaction product is necessarily affected by the substituent positioning effect. In combination with the positioning effect of the halogen atom, the carbonyl group or the sulfone group, the result is that the sulfonic acid group formed after sulfonation can be positioned only in the ortho position to the carbon atom of the benzene ring to which the halogen atom is attached, i.e., in the meta position to the carbon atom of the benzene ring to which the sulfone group or carbonyl group is attached. The chemical structural formula of the compounds is shown in figure 1, X is fluorine, chlorine or bromine atom, and the structural characteristics of dihalogen are illustrated; y is carbonyl or sulfonyl, which indicates that the compound has the structural characteristics of benzophenone or diphenyl sulfone; m is a hydrogen, sodium or potassium atom, illustrating the structural features of having a disulfonate or disulfonate group. In particular, the chemical names of the sulfonated dihalodiphenylsulfones and sulfonated dihalobenzophenones in the form of their sodium disulfonates mentioned above specifically include: 3,3 '-disulfonic acid sodium-4,4' -difluorodiphenyl sulfone, 3,3 '-disulfonic acid sodium-4,4' -dichlorodiphenyl sulfone, 3,3 '-disulfonic acid sodium-4,4' -dibromodiphenyl sulfone, as well as 3,3 '-disulfonic acid sodium-4,4' -difluorobenzophenone, 3,3 '-disulfonic acid sodium-4,4' -dichlorobenzophenone, 3,3 '-disulfonic acid sodium-4,4' -dibromobenzophenone. If no base is added for neutralization, the sulfonated product is in the form of a disulfonic acid with free hydrogen ions, for example 3,3 '-disulfonic acid-4,4' -dichlorodiphenyl sulfone or 3,3 '-disulfonic acid-4,4' -difluorobenzophenone. Similarly, if potassium hydroxide (rather than sodium hydroxide) is used for neutralization, the sulfonation product is in the form of a potassium disulfonate salt, such as 3,3 '-potassium disulfonate-4,4' -dichlorodiphenyl sulfone or 3,3 '-potassium disulfonate-4,4' -difluorobenzophenone. In fact, other forms of monovalent cation salts, such as lithium or ammonium salts, are also possible (obtained by neutralizing the sulfonation reaction solution with lithium hydroxide and aqueous ammonia, respectively), but are not unusual and are not specifically listed here.
In the step (1), the acid-resistant metal reaction kettle (i.e. a shown in figure 2) and the two-stage acid-resistant metal coil reactor in the step (2) are composed of the first-stage coil (i.e. B1 shown in figure 2) in the step (3) and the second-stage coil (i.e. B2 shown in figure 2) in the step (4), and the materials of the two-stage acid-resistant metal coil reactor and the two-stage acid-resistant metal coil reactor can be common carbon steel or cast iron, or special alloy No. 20 (i.e. chromium-nickel-molybdenum-copper alloy) or tantalum alloy, and are not particularly limited as long as the two-stage acid-resistant metal coil reactor can resist the corrosion of fuming sulfuric acid for a long time. And, the cauldron body is best to be cast in one piece to guarantee to have higher withstand internal pressure. The upper limit of the withstand internal pressure is 1.0MPa, so that the withstand pressure requirement in the process of pressurizing nitrogen and pumping fluid is met, and the leakage of sulfur trioxide acid mist can be thoroughly avoided. The pipes, valves and metering pumps connecting them are also preferably made of the same acid-resistant metal material and can withstand sufficient internal pressure.
In the step (1), the concentration of the injected fuming sulfuric acid is 105-120%, and most commonly used are industrial 105 acid (which means 105 g of pure sulfuric acid can be obtained after 100 g of fuming sulfuric acid with the specification absorbs water) and 120 acid (which means 120 g of pure sulfuric acid can be obtained after 100 g of fuming sulfuric acid with the specification absorbs water), or the industrial fuming sulfuric acid with the two specifications is mixed to a specified concentration. If the concentration is too low, the sulfonation effect is poor, and a product completely sulfonated is difficult to obtain; if the concentration of oleum exceeds 120%, too much sulfur trioxide remains after sulfonation, and the reaction is severe thereafter upon hydrolysis in ice water, resulting in significant acid mist. Further, the concentration of fuming sulfuric acid as a sulfonating agent is not so high from the viewpoint of the raw material utilization rate and the sulfuric acid recovery rate. The mass ratio of the added amount of fuming sulfuric acid (the density is about 1.9g/mL at normal temperature) to the dihalogenodiphenyl sulfone or dihalogenobenzophenone is 3:1-6:1, and the incomplete dissolution of the dihalogenodiphenyl sulfone and the dihalogenobenzophenone can be caused when the added amount is too small, and then the completely homogeneous sulfonation reaction process is difficult to implement; if the addition amount is too large, the sulfonating agent is far excessive, which inevitably causes the waste of raw materials and the increase of the recovery amount of sulfuric acid. When the mixture in the kettle is dissolved, the mixture in the kettle is heated properly, for example, from room temperature to 50-100 ℃, preferably 60-90 ℃, so that the dihalogenated diphenyl sulfone or dihalogenated diphenyl ketone can be quickly and completely dissolved in oleum to obtain a yellowish or yellow clear liquid. Generally, although the dissolution process is also accompanied by some degree of sulfonation, practice has proven that: significant sulfonation effects are only achieved at higher temperatures, for example, above 120 ℃. Before adding oleum, it is necessary to completely displace the air in the kettle with nitrogen; in order to "drive" the air rapidly, it is preferable to repeat the process of vacuum-pumping and nitrogen-charging several times after adding the solid raw material of dihalodiphenylsulfone or dihalodiphenylketone, and then carefully open the feeding valve of oleum to slowly flow oleum into the dissolution kettle by using natural pressure difference to avoid air entrainment.
In the step (2), the reaction liquid is injected into the two-section type acid-resistant metal coil reactor, and after a bottom valve of the dissolving kettle is opened, the flow entering the coil is stably controlled by depending on the air pressure of nitrogen filled in the dissolving kettle and the opening degree of a metering pump (a numerical control precise plunger pump is suggested); the flow rate is calculated in advance based on the residence time of the reaction solution in the coil and set in advance. After the liquid in the kettle is completely injected into the coil, the unidirectional flow of the reaction liquid in the coil is mainly maintained by controlling the nitrogen gas inlet pressure (not only the opening degree of a metering pump). In addition to the coil material being required to withstand oleum, it is also required to be able to withstand internal pressures of at least 1.0MPa, which can be formed by crimping a seamless metal tube of sufficient wall thickness (e.g., not less than 3 mm) and length to avoid unnecessary welding.
In the step (3), the first section of coil pipe is subjected to high-temperature sulfonation reaction in an oil bath, wherein the oil bath temperature is 120-200 ℃, and is preferably 140-180 ℃. The oil bath temperature is low, the heat transfer speed to the first section of metal coil pipe is very slow, and the reaction liquid in the coil pipe cannot be rapidly heated to the required sulfonation reaction temperature; if the temperature is too high, a sharp rise in the coil internal pressure (due to the reaction liquid being prevented from expanding sharply) may result, increasing the risk of leakage. It has also been found that too high an oil bath temperature can cause excessive sulfonation side reactions, producing dark brown sulfonated products. This may be due to partial carbonization of the starting material or the sulfonated product, although the exact mechanism is not known. The residence time of the reaction solution in the first coil pipe is 60 to 200 minutes, preferably 90 to 150 minutes. The length of the residence time must be matched with the oil bath temperature. That is, the higher the oil bath temperature, the shorter the residence time to avoid excessive sulfonation; slightly lower oil bath temperatures require longer residence times to ensure complete sulfonation. Practice of the invention proves that sulfur trioxide in fuming sulfuric acid can be more effectively utilized in a completely sealed tube reactor with pressure plates, which can lead the sulfonation reaction time to be greatly shortened compared with the sulfonation time required in a single-batch normal-pressure reaction kettle. The reaction liquid is cooled in the process that the second section of coil is immersed in cold water, and the temperature of the reaction liquid in the second section of coil is always higher than 60 ℃, preferably between 60 and 90 ℃; if the temperature is low, the reaction product can be partially solidified, so that the flow in the coil pipe is not smooth and even blocked; if the outlet temperature is high, namely the reaction liquid is not cooled enough, the use amount of ice water is greatly increased during hydrolysis; otherwise, the temperature of the hydrolysis solution rises rapidly, and the acid mist overflows in a large amount and is difficult to be completely absorbed by the ice water.
In the step (4), the ice-water mixture is contained in an ice-water dilution tank (i.e. C in the attached figure 2) and is used as the absorption liquid of the hydrolysis liquid and the residual acid mist of the sulfonation reaction liquid, and the mass ratio of the amount of the ice-water mixture to the reaction liquid is 2:1-5:1. If the dosage is too small, the heat absorption capacity is not enough, the temperature can not be ensured to be less than 70 ℃ during hydrolysis, and the acid mist overflows quickly as a result; if the amount is too large, although the effect of hydrolysis and acid mist absorption is significantly increased, it directly results in a significant decrease in both product concentration and dilute sulfuric acid concentration, which will make the costs of drying and dilute sulfuric acid recovery go up and go unnoticed. The ratio of ice to water in the ice-water mixture is not particularly limited depending on the heat absorption effect, but it is necessary to ensure that at least a layer of floating ice (preferably crushed ice) of sufficient thickness can significantly increase the effect of blocking the escape of acid mist.
In the step (5), the hydrolysate is mechanically filtered (i.e., D in fig. 2), and common solid-liquid filtration methods are adopted, such as activated carbon column chromatography, flat membrane filtration, and medium control fiber microfiltration membrane filtration, as long as the filtration material and equipment can tolerate dilute sulfuric acid (mass concentration is less than 30%). Generally, it is recommended to use a flat-plate type microfilter membrane module made of polytetrafluoroethylene with an average pore size of less than 5 μm to completely retain the trace amount of solid particles (presumed as the very small amount of residual material that is not completely reacted or the carbonized black spots that are over sulfonated) in the acidic hydrolysate, and to obtain a completely clarified pale yellow solution, which is temporarily stored in the finished solution tank (i.e., E in fig. 2). The two-compartment electrodialyzer (i.e., F in FIG. 2) equipped with the compact anion exchange membrane, i.e., having a desalting compartment and a concentrating compartment, has special requirements for the installed anion exchange membrane. The common standard anion exchange membrane is difficult to permeate sulfate ions (the relative molecular weight is 96), and simultaneously, sulfonated product anions are efficiently intercepted (the relative molecular weight of the sulfonated product anions subtracting two sodium ions is 445 by taking 3,3 '-sodium disulfonate-4,4' -dichlorodiphenyl sulfone as an example). Therefore, it is necessary to customize the anion exchange membrane by considering the thickness, swelling ratio, ion exchange channel structure, etc. comprehensively to improve the compactness and increase the degree of discrimination of anions of different sizes, and preferably to achieve a retention ratio of the sulfonated product anions with molecular weight significantly larger than sulfate radicals of more than 95%, so as to avoid significant product loss. After repeated tests, the pressure difference permeability coefficient of water can be simply used for measuring the compactness of the compact anion-exchange membrane and the actual retention effect on sulfonated product anions. The conclusion is that: according to the people's republic of China seaIn the detection method described in the ocean industry standard HY/T166.1-2013, the pressure difference permeability coefficient of water is not more than 0.002 mL/(cm) 2 h.MPa), the above-mentioned requirements for the rejection rate of anions of the sulfonated product over 95% can be met. Although commercial dense anion exchange membranes have been available to meet this requirement, electrodialysers still do not operate at current densities exceeding 30mA/cm 2 Active membrane area (referring to the area of the membrane that passes direct current); otherwise, the driving force of the direct current electric field is too large, and the sulfonated product anions still possibly migrate through the anion exchange membrane along with sulfate radicals, so that considerable product loss is caused. This means that the dilute sulfuric acid solution recovered from the concentrating compartment is not sufficiently clean and may contain a significant amount of sulfonated product anion. However, the lower limit of the current density cannot be lower than 5mA/cm 2 In order to avoid that both sulfate and hydrogen ions migrate too slowly and the electrodialysis deacidification process takes too long.
In the step (6), alkali is added to neutralize the deacidification solution, and preferably solid sodium hydroxide or potassium hydroxide is directly added to avoid the increase of the volume of the solution. In addition to neutralizing the residual sulfuric acid that was not completely removed in the previous step, the base also neutralizes the free hydrogen ions that pair with the sulfonated product, converting it from the hydrogen form to the sodium or potassium form. In general, all sulfonated products can be completely transformed by adding alkali to neutralize the solution until the pH value is slightly greater than 7, such as 7.0-8.5; this means that the sulfonated product no longer contains free hydrogen ions but is completely converted into the disodium or dipotassium salt. Before the direct current is connected again and the electrodialyzer is started, the dilute sulfuric acid in the concentration chamber needs to be completely emptied and recycled to the acid recycling tank (i.e. G in figure 2), and then the corresponding dilute brine (i.e. the dilute salt solution corresponding to the sodium sulfate or potassium sulfate to be removed in the concentration chamber) is introduced, wherein the concentration is generally 0.5-2%. Thus, after the direct current is switched on again, the resistances of the concentration chamber and the desalination chamber are both small, so that the residual salt in the concentration chamber can be rapidly removed, and then the residual salt is recovered to the salt recovery tank (namely H in the attached figure 2). Similarly, the current density of the electrodialysis desalination process should be 5-30 mA/cm 2 The effective membrane area. The conductivity of the chamber to be concentrated or the desalination chamber is substantially constant, meaning that the salt is substantially removed, i.e. theThe resulting aqueous solution containing only the sulfonate product in the concentrating compartment can still be stored in the finished solution tank (in practice, the neutralization of the deacidified solution with base can also be accomplished in this tank).
In the step (7), the dehydration and the drying may be performed by filtering and concentrating the sulfonate solution with a nanofiltration membrane, for example, by increasing the sulfonate concentration to more than 25%, and then performing evaporation, crystallization and drying to obtain a sulfonate crystal. Or directly heating and evaporating water to obtain dry product; or spray drying to obtain powder. Of course, the purity of the crystalline product will be slightly higher than that of the dry powder product obtained by direct drying. The latter may have a very small amount of sulfate, but if the desalting effect of the electrodialysis in the previous step is controlled to ensure complete desalting, the purity requirement of industrial qualified products (for example, more than 98.5%) can be easily achieved.
The invention is further illustrated by the following specific examples:
example 1:
preparation of 3,3 '-sodium disulfonate-4,4' -dichlorodiphenyl sulfone: the preparation conditions, process parameters and results are summarized in table 1, and the specific steps are as follows:
(1) A cast iron kettle with the volume of 800 ml (the kettle body is integrally cast, the thickness is 5 mm; the surface is sprayed with a polytetrafluoroethylene treatment 304 stainless steel flange cover, the thickness is 18 mm, a high pressure resistant toughened glass sight glass is embedded, a polytetrafluoroethylene gasket is sealed and then leakage-tested by using 3.0MPa compressed air, 100 g of 4,4' -dichlorodiphenyl sulfone solid (348 mmol, analytically pure, shanghai Aladdin chemical reagent company) is added, a magnetic stirrer is put in, the flange cover is covered, the flange cover is screwed, the kettle is vacuumized and screwed again, and industrial nitrogen is filled until the pressure is 0.4MPa; opening a bottom valve, and slowly discharging nitrogen from the two-section coil pipe (realized by controlling the opening degree of a one-way valve at the joint of the second section coil pipe and the polytetrafluoroethylene pipe); and continuously carrying out operations of vacuumizing, nitrogen filling and nitrogen discharging for three times, and completely replacing the air in the reaction kettle and the coil pipe with nitrogen. Unscrewing a stainless steel feed valve connected to a flange cover and a glass constant pressure funnel (500 ml, graduated) containing oleum, and slowly adding 250 ml oleum (industrial 105 acid, measured as 105.3% of the sulfuric acid content); closing the feed valve, closing the system, starting magnetic stirring, switching on a power supply of a winding heating belt on the outer wall of the kettle body, gradually increasing the temperature of the kettle body until a temperature measuring probe (tightly attached to the outer wall of the reaction kettle) shows 65 ℃; the floating of the solid is observed through a glass sight glass on the flange cover, the stirring is gradually smooth, the solid in the kettle is completely dissolved after 15 minutes, and the stirring is very smooth.
(2) And opening a nitrogen gas inlet valve (maintaining the pressure to be 0.15MPa through a precision pressure reducing valve), a bottom valve of the reaction kettle and a metering pump, screwing off a one-way valve at the outlet of the second section of coil pipe, continuously injecting the reaction liquid in the reaction kettle into the two-section type acid-resistant metal coil pipe reactor, and setting the flow of the corrosion-resistant precision plunger pump to be 5.0 ml/min.
(3) Completely immersing a first section of coil (with the outer diameter of 14 mm, the inner diameter of 8 mm, the length of 10.0 m and the internal volume of 500 ml, which is formed by winding a seamless carbon steel tube) into an oil bath, wherein the temperature of the oil bath is set to 162 ℃, and completely sealed sulfonation reaction is realized in the coil; and completely immersing the second section of coil pipe (the material and specification of which are the same as those of the first section of coil pipe, the length of which is 2.0 m, and the internal volume of which is 100 ml) into cold water, setting the temperature of a cold water bath at 45 ℃, and cooling the reaction liquid in the coil pipe by using cold water external circulation refrigeration.
(4) The cooled reaction solution continuously flows into the bottom of an ice water dilution tank (containing 1700 g of ice/water mixture with the ice/water mass ratio of about 1/3) through a polytetrafluoroethylene tube, and the temperature displayed by a thermometer at the joint of a second section of coil and the polytetrafluoroethylene tube (with the outer diameter of 14 mm and the inner diameter of 8 mm) is 74 ℃, so that the hydrolysis is carried out immediately and the heat release is carried out continuously; finally, the temperature of the hydrolysate is raised to 57 ℃, and no acid mist overflows all the time, thereby obtaining 1980 ml of hydrolysate acid liquid with the sulfuric acid content of 16.8 percent.
(5) The hydrolysis acid solution is clamped into a single wafer filter membrane (PTFE microfiltration membrane with the diameter of 120 mm, the thickness of 0.15 mm and the average pore diameter of 2 microns) through a suction filter for decompression and suction filtration; then assembling electrodialyzer (EX-3 BT desktop type, available from hangzhou blue technology corporation, electrified effective membrane area 55cm 2 One sheet of membrane), 10 sheets of compact anion exchange membrane (supplied by thoroughfare blue new materials, ltd., AHM type of electricity) were packedThe anion exchange membrane for electrophoretic coating has the wet film thickness of 0.50 mm and the differential pressure permeability coefficient of water of 0.0013 mL/(cm) 2 H.mpa)) and 11 sheets of standard cation exchange membranes (supplied by thoroughfare blue new materials ltd., CIM type homogeneous membrane, wet membrane thickness 0.21 mm, differential pressure permeability coefficient of water 0.065 mL/(cm) 2 h.MPa)); introducing the filtrate into desalting chamber of electrodialyzer, introducing 1500 ml 0.5% dilute sulfuric acid solution into the concentrating chamber, introducing 1000 ml 5% sodium sulfate solution into the polar chamber, simultaneously starting the solution internal circulation of the concentrating chamber, desalting chamber and polar chamber, immediately introducing direct current, operating in constant current mode, and setting current to be 1.1A (corresponding to current density of 20 mA/cm) 2 ) Removing sulfuric acid from the desalting chamber to the concentrating chamber; sampling 1.0 ml from the desalting chamber every 20 minutes, titrating the concentration of the residual acid until the concentration of the residual acid is less than 1 percent (the deacidification rate is calculated to be about 94 percent), and consuming about 120 minutes, namely closing the power supply and the three-chamber circulation, and respectively recovering the dilute sulfuric acid solution in the concentration chamber to the acid recovery tank and the deacidification solution in the desalting chamber to the finished product solution tank.
(6) Gradually adding 32.3 g of sodium hydroxide tablet alkali particles into a finished product solution tank, and stirring and neutralizing until the pH value is 7.5; introducing the neutralized solution into the desalting chamber of the electrodialyzer again, and simultaneously introducing 1500 ml of 1% sodium sulfate solution into the concentrating chamber while introducing 1000 ml of 5% sodium sulfate solution into the polar chamber; starting three-chamber internal circulation, accessing direct current, operating in constant current mode, and setting current to be 1.4A (corresponding to current density of 25.5 mA/cm) 2 ) And (3) removing salt from the desalting chamber to the concentrating chamber, wherein the conductivity of the concentrating chamber rapidly rises to the maximum value (which is constant around 16.5ms/cm after about 28 minutes), namely, turning off the power supply and the three-chamber circulation, and respectively recovering the saline water in the concentrating chamber to a saline water recovery tank and the desalted liquid in the desalting chamber to obtain 1840 ml of desalted liquid.
(7) Gradually decompressing, evaporating and dehydrating the desalted liquid by using a rotary evaporator, respectively placing the desalted liquid in a white enamel tray, firstly drying the desalted liquid by blowing air at 85 ℃ until no visible water exists on the surface, and then drying the desalted liquid by blowing air at 120 ℃ until the weight is constant; the dry product was carefully collected to yield 169.7 g (about 345 mmol), from which a yield of 99.2% was calculated. Thus illustrating that: sulfonation is substantially complete and product loss during electrodialysis deacidification and desalination is minimal. The relative molecular weight of the main peak is 491 determined by high resolution mass spectrometry, and is identified as 3,3 '-sodium disulfonate-4,4' -dichlorodiphenylsulfone, and the purity is 98.6% by HPLC (RP 18 chromatographic column (5 microns, 3.9 x 150 mm), the mobile phase is acetonitrile/water (volume ratio is 6/4), the flow rate is 1.0 ml/min, and the internal standard method).
Example 2:
preparation of 3,3 '-sodium disulfonate-4,4' -difluorodiphenyl sulfone: the preparation conditions, process parameters and results are summarized in table 1, and the specific steps are as follows: (1) Using the same dissolution vessel and two-stage coil reactor as in example 1, 100 g of 4,4' -difluorodiphenylsulfone solid (393 mmol, analytical grade, shanghai Aladdin Chemicals) and 200 ml of oleum (mixed with 105 and 120 acids, measured as 110.3% sulfuric acid content) were charged, and the temperature probe was raised to 72 ℃ and the rest of the procedure was the same as in example 1, and the solid was found to be completely dissolved after stirring for about 20 minutes. (2) The flow rate of the corrosion-resistant precision plunger pump was set to 3.4 ml/min, and the remaining procedure was the same as in step (2) of example 1, and the dissolved reaction solution was injected into the two-stage coil reactor. (3) The oil bath temperature was set to 145 ℃ and the remaining process was the same as in the step (3) of example 1, and the sulfonation reaction and the temperature of the reaction solution were successively carried out. (4) The temperature displayed by a thermometer at the joint of the second section of coil and the polytetrafluoroethylene tube is 75 ℃, the cooled reaction solution continuously flows into the bottom of an ice water dilution tank (containing 1500 g of ice/water mixture, wherein the mass ratio of ice/water is about 1/4) through the polytetrafluoroethylene tube, the temperature of the hydrolysis solution rises to 55 ℃ after the hydrolysis is finished, no acid mist overflows, 1730 ml of hydrolysis acid solution is obtained, and the sulfuric acid content is 16.4%. (5) The electrodialyzer used was the same as in example 1, and the electric current for deacidification by electrodialysis was set to 1.3A (corresponding to a current density of 23.6 mA/cm) 2 ) About 90 minutes was consumed, the sulfuric acid in the desalting compartment was removed to less than 1% (from which about 94% deacidification was calculated), and the remaining processes and equipment used were the same as in step (5) of example 1. (6) The deacidification solution was neutralized with 33.1 g of sodium hydroxide flake alkali particles, and the rest of the procedure and the equipment used were the same as in the step (6) of example 1, to obtain 1600 ml of a desalted solution. (7) The rotary evaporation dehydration and drying method and apparatus were the same as in the step (7) of example 1, and 179 g (about 391 mmol) of a dried product was obtained, from which the yield was calculatedThe content was 99.4%. The mass spectrum (equipment and analytical method as in example 1) was identified as 3,3 '-disulfonic acid sodium-4,4' -difluorodiphenyl sulfone (relative molecular weight 458), and the HPLC (equipment and analytical method as in example 1) detected purity as 98.7%.
Example 3:
preparation of 3,3 '-sodium disulfonate-4,4' -difluorobenzophenone: the preparation conditions, process parameters and results are summarized in table 1, and the specific steps are as follows: (1) Using the same dissolution vessel and two-stage coil reactor as in example 1, 100 g of 4,4' -difluorobenzophenone solid (458 mmol, analytical pure, shanghai Aladdin Chemicals) and 180 ml of oleum (114.6% sulfuric acid content measured by mixing 105 and 120 acids) were added, and the temperature was raised until the probe showed 75 ℃ and the rest of the procedure was the same as in example 1, and the solid was found to be completely dissolved after about 20 minutes of stirring. (2) The flow rate of the corrosion-resistant precision plunger pump was set to 5.3 ml/min, and the remaining procedure was the same as in step (2) of example 1, and the dissolved reaction solution was injected into the two-stage coil reactor. (3) The oil bath temperature was set to 165 ℃ and the remaining process was the same as in the step (3) of example 1, and the sulfonation reaction and the temperature of the reaction solution were successively carried out. (4) The temperature displayed by a thermometer at the joint of the second section of coil pipe and the polytetrafluoroethylene pipe is 70 ℃, the cooled reaction solution continuously flows into the bottom of an ice water dilution tank (containing 1600 g of ice/water mixture, wherein the mass ratio of ice/water is about 1/3) through the polytetrafluoroethylene pipe, the temperature of the hydrolysis solution rises to 57 ℃ after the hydrolysis is finished, no acid mist overflows, 1800 ml of hydrolysis acid solution is obtained, and the sulfuric acid content is 14.9%. (5) The electrodialyzer used was the same as in example 1, and the electric current for deacidification by electrodialysis was set to 1.2A (corresponding to a current density of 21.8 mA/cm) 2 ) About 90 minutes was consumed, the sulfuric acid in the desalting compartment was removed to less than 1% (from which about 93% deacidification was calculated), and the remaining processes and the used equipment were the same as in the step (5) of example 1. (6) Neutralizing the deacidified solution with 39.2 g sodium hydroxide powder to pH 7.4, and performing electrodialysis desalination at a current of 1.1A (corresponding to a current density of 20 mA/cm) 2 ) The procedure and the equipment used were the same as in (6) of example 1, except that the concentration chamber was stopped when the conductivity rose to around 17.4ms/cm, to obtain 1690 ml of a desalted liquid. (7) Rotary steaming dewatering and drying method and equipment and its productThe same procedure as in step (7) of example 1 gave 191.4 g (about 453 mmol) of a dried product, from which the calculated yield was 99.1%. Mass spectrometry (equipment and analytical method as in example 1) was identified as 3,3 '-disulfonic acid sodium-4,4' -difluorobenzophenone (relative molecular weight 422), with an HPLC (equipment and analytical method as in example 1) purity of 98.9%.
Example 4:
preparation of 3,3 '-Potassium disulfonate-4,4' -dibromobenzophenone: the preparation conditions, process parameters and results are summarized in table 1, and the specific steps are as follows: (1) Using the same dissolution vessel and two-stage coil reactor as in example 1, 100 g of 4,4' -dibromobenzophenone solid (294 mmol, analytical grade, shanghai Aladdin Chemicals) and 280 ml of oleum (106.8% sulfuric acid content measured by mixing with 105 and 120 acids) were charged, and the temperature was raised until the probe showed 80 ℃ and the rest of the procedure was the same as in example 1, and the solid was found to be completely dissolved after stirring for about 20 minutes. (2) The flow rate of the corrosion-resistant precision plunger pump was set to 4.2 ml/min, the remaining procedure was the same as in step (2) of example 1, and the dissolved reaction solution was injected into the two-stage coil reactor. (3) The oil bath temperature was set to 170 ℃ and the remaining process was the same as in the step (3) of example 1, and the sulfonation reaction and the temperature of the reaction solution were successively carried out. (4) The temperature displayed by a thermometer at the joint of the second section of coil pipe and the polytetrafluoroethylene pipe is 66 ℃, the cooled reaction solution continuously flows into the bottom of an ice water dilution tank (containing 3000 g of ice/water mixture, wherein the mass ratio of ice/water is about 1/2) through the polytetrafluoroethylene pipe, the temperature of the hydrolysis solution rises to 53 ℃ after the hydrolysis is finished, and no acid mist overflows, so that 3290 ml of hydrolysis acid solution is obtained, and the sulfuric acid content is 11.3%. (5) The electrodialyzer used was the same as in example 1, and the electric current for deacidification by electrodialysis was set to 1.1A (corresponding to a current density of 20 mA/cm) 2 ) About 120 minutes was consumed, the sulfuric acid in the desalting compartment was removed to less than 1% (from which about 91% deacidification was calculated), and the remaining processes and equipment used were the same as in step (5) of example 1. (6) Neutralizing the deacidification solution with 34.0 g potassium hydroxide powder to pH 7.5, introducing 1500 ml 1% potassium sulfate solution into the concentration chamber during electrodialysis desalination, and setting the operation current at 1.5A (corresponding to current density of 27.3 mA/cm) 2 ) Until the conductivity of the concentration chamber rises to 19.3ms/cmToward the end, the remaining process and the equipment used were the same as in step (6) of example 1, yielding 3160 ml of desalted solution. (7) The desalted solution was directly spray-dried to obtain 157.8 g (about 274 mmol) of dried product, from which the calculated yield was 93.1% (a small amount of powder in the dryer was difficult to clean). The mass spectrum (equipment and analytical method as in example 1) was identified as 3,3 '-potassium disulfonate-4,4' -dibromobenzophenone (relative molecular weight 576), and the purity by HPLC (equipment and analytical method as in example 1) was 99.2%.
Table 1 preparation conditions, process parameters and results for examples 1-4
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.
Claims (10)
1. The green preparation method of the sulfonated dihalogenated monomer is characterized by comprising the following steps:
(1) Putting a dihalogenated reactant into a reaction kettle, covering the reaction kettle, vacuumizing, filling nitrogen, completely replacing air, injecting a proper amount of fuming sulfuric acid, starting stirring, heating to a target temperature, and completely dissolving reactant solids to obtain a reaction solution;
(2) Continuously injecting the reaction liquid into a two-section coil reactor, immersing a first section of coil into an oil bath to perform sulfonation reaction, and immersing a second section of coil into cold water to rapidly cool the reaction liquid;
(3) Connecting the outlet of the second section of coil pipe with a polytetrafluoroethylene pipeline, inserting the second section of coil pipe into an ice-water mixture, and continuously introducing a sulfonation reaction solution for hydrolysis to obtain a hydrolysis acid solution;
(4) Mechanically filtering the hydrolyzed acid solution, continuously introducing the hydrolyzed acid solution into a two-compartment electrodialyzer provided with a compact anion exchange membrane, introducing direct current, gradually removing sulfuric acid components to obtain a deacidified solution, and recovering from a concentration chamber to obtain a clean dilute sulfuric acid solution;
(5) Adding alkali into the deacidified liquid to neutralize the deacidified liquid until the pH value is slightly larger than 7, introducing the deacidified liquid into an electrodialyzer again, introducing direct current, and quickly removing residual salt to obtain a sulfonate aqueous solution only containing sulfonate products;
(6) And dehydrating and drying the sulfonate aqueous solution to obtain the sulfonated dihalogenated monomer.
2. The method for the green production of a sulfonated dihalogenomonomer according to claim 1, wherein the dihalogenoreactant is a dihalodiphenylsulfone or a dihalodiphenylketone, and correspondingly, the sulfonated dihalogenomonomer is a sulfonated dihalodiphenylsulfone or a sulfonated dihalodiphenylketone.
3. The method for the green preparation of a sulfonated dihalogeno-monomer according to claim 2, wherein the dihalodiphenylsulfone is 4,4 '-difluorodiphenyl sulfone, 4,4' -dichlorodiphenyl sulfone or 4,4 '-dibromodiphenyl sulfone, and the dihalogeno-ketone is 4,4' -difluorobenzophenone, 4,4 '-dichlorobenzophenone or 4,4' -dibromobenzophenone.
4. The process for the green production of a sulfonated dihalogeno-monomer according to claim 1, wherein in the step (1), the concentration of fuming sulfuric acid is 105 to 120% by mass, and the amount of fuming sulfuric acid added is 3 to 6 times by mass as much as that of the dihalogeno-reaction product.
5. The process for the green production of a sulfonated dihalogen monomer according to claim 1, wherein in the step (1), the target temperature is 50 to 100 ℃, preferably 60 to 90 ℃.
6. The process for the green production of a sulfonated dihalogen monomer according to claim 1, wherein in the step (2), the residence time of the reaction solution in the first-stage coil is 60 to 200 minutes, preferably 90 to 150 minutes.
7. The process for the green production of a sulfonated dihalogeno-monomer according to claim 1, wherein in the step (2), the oil bath temperature is 120 to 200 ℃, preferably 140 to 180 ℃; the second section of coil pipe is immersed in cold water to ensure that the temperature of the reaction liquid in the second section of coil pipe is not lower than 60 ℃, and preferably 60-90 ℃.
8. The method for greenly producing a sulfonated dihalogeno-monomer according to claim 1, wherein in the step (3), the amount of the ice-water mixture added is 2 to 5 times by mass as much as the mass of the sulfonation reaction solution.
9. The process for the green production of a sulfonated dihalogeno-monomer according to claim 1, wherein in the step (4), the compact anion exchange membrane is water having a differential pressure permeability coefficient of 0.002 mL/(cm) or less 2 h.MPa) anion exchange membranes.
10. The process for the green production of a sulfonated dihalogenomonomer according to claim 1, wherein in the steps (4) and (5), the electrodialyzer is operated at a current density of 5 to 30mA/cm 2 The effective membrane area.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005132762A (en) * | 2003-10-30 | 2005-05-26 | Mitsui Chemicals Inc | Method for producing alkali metal salt of carbonylbis(halogenobenzenesulfonic acid) and alkali metal salt of carbonylbis(halogenobenzenesulfonic acid) |
| CN101475516A (en) * | 2008-12-30 | 2009-07-08 | 天津师范大学 | Efficient preparation method of sulfonated polyethersulfone monomer |
| CN101550094A (en) * | 2009-05-12 | 2009-10-07 | 天津师范大学 | Method for preparing important monomer dihalo-disulfonic acid benzophenone of sulfonated polyetheretherketone and salt thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005132762A (en) * | 2003-10-30 | 2005-05-26 | Mitsui Chemicals Inc | Method for producing alkali metal salt of carbonylbis(halogenobenzenesulfonic acid) and alkali metal salt of carbonylbis(halogenobenzenesulfonic acid) |
| CN101475516A (en) * | 2008-12-30 | 2009-07-08 | 天津师范大学 | Efficient preparation method of sulfonated polyethersulfone monomer |
| CN101550094A (en) * | 2009-05-12 | 2009-10-07 | 天津师范大学 | Method for preparing important monomer dihalo-disulfonic acid benzophenone of sulfonated polyetheretherketone and salt thereof |
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