CN115304525B - Green preparation method of sulfonated dihalogen monomer - Google Patents
Green preparation method of sulfonated dihalogen monomer Download PDFInfo
- Publication number
- CN115304525B CN115304525B CN202211104590.3A CN202211104590A CN115304525B CN 115304525 B CN115304525 B CN 115304525B CN 202211104590 A CN202211104590 A CN 202211104590A CN 115304525 B CN115304525 B CN 115304525B
- Authority
- CN
- China
- Prior art keywords
- sulfonated
- sulfuric acid
- dihalogen
- coil
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000178 monomer Substances 0.000 title claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000002253 acid Substances 0.000 claims abstract description 59
- 239000000243 solution Substances 0.000 claims abstract description 49
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 43
- 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 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000005457 ice water Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- 239000012295 chemical reaction liquid Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 29
- -1 polytetrafluoroethylene Polymers 0.000 claims description 25
- 230000007062 hydrolysis Effects 0.000 claims description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 20
- 239000003011 anion exchange membrane Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000035699 permeability Effects 0.000 claims description 6
- 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
- 239000003595 mist Substances 0.000 abstract description 18
- 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 17
- 238000011033 desalting Methods 0.000 abstract description 14
- 238000000909 electrodialysis Methods 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 11
- 150000008366 benzophenones Chemical class 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 238000001704 evaporation Methods 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
- 239000000047 product Substances 0.000 description 39
- 229910052708 sodium Inorganic materials 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- 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 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 238000010612 desalination reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000003960 organic solvent Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000463 material Substances 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
- 239000002994 raw material Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical class C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 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
- 239000000413 hydrolysate Substances 0.000 description 4
- 238000005185 salting out Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 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
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 description 2
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012965 benzophenone Substances 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
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004132 cross linking 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
- 238000002156 mixing Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920000642 polymer Polymers 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
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 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
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 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 description 1
- PZDAAZQDQJGXSW-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)benzene Chemical group C1=CC(F)=CC=C1C1=CC=C(F)C=C1 PZDAAZQDQJGXSW-UHFFFAOYSA-N 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 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
- 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
- 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 class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 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 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 238000007334 copolymerization reaction 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
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 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
- 238000006251 dihalogenation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 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
- 239000000543 intermediate Substances 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
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing 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
- 238000001179 sorption measurement Methods 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
- 125000001424 substituent group Chemical group 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
- 239000002351 wastewater Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
Landscapes
- 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 green preparation method of the sulfonated dihalogenated monomer adopts fuming sulfuric acid as a sulfonating agent and a solvent, and comprises the steps of heating to dissolve dihalogenated diphenyl sulfone or dihalogenated benzophenone, then injecting the solution into a two-section metal coil reactor at a constant speed, and injecting a complete sulfonated product into an ice-water mixture after heating and cooling respectively to realize a continuous, controllable and sealed sulfonation process; then the aqueous solution is filtered simply and then is led into an electrodialysis device, sulfuric acid components are basically removed, and dilute sulfuric acid is recovered at the same time; adding alkali into the deacidified solution to neutralize, then introducing the deacidified solution into an electrodialysis device, and evaporating and crystallizing or spray-drying after the quick desalting to obtain the sulfonated dihalogen monomer product. The preparation method has the advantages of stable and controllable reaction process, no acid mist pollution, simple and efficient purification process, no waste acid and mixed salt generation, and environment friendliness and easy realization of industrial production.
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 dihalogen monomer.
Background
Dihalogenated diphenyl sulfone (such as 4,4' -dichloro diphenyl sulfone) or dihalogenated diphenyl ketone (such as 4,4' -difluoro diphenyl ketone) is completely sulfonated to obtain sulfonated monomer, and then the sulfonated monomer is polycondensed with 4,4' -diphenyl diphenol, bisphenol A, bisphenol F or bisphenol S to prepare soluble linear polymer with sulfonic acid groups on the main chain, which is widely applied to the fields of hydrophilic modification of porous filtering membranes, manufacture of cation exchange membranes (including proton exchange membranes), production of medical adsorption materials and the like. And, this preparation method of "direct polymerization (Direct copolymerization)" that prepares sulfonated monomer and then polycondenses into linear ionic polymer first, compared with "Post sulfonation" preparation method that sulfonate linear polymer, it has more even distribution of sulfonic acid group, sulfonation degree can be higher, there is no damage to the main chain of macromolecule ("Post sulfonation" when, it is difficult to avoid the damage to main chain aromatic ether bond by sulfonating agent), the side reaction of cross-linking is less (the side cross-linking mainly comes from sulfonic acid group under the catalysis of concentrated sulfuric acid, form sulfonyl) and repeatability and controllability of cation exchange capacity are better ("the actual cation exchange capacity obtained by direct polymerization" preparation method is basically the same as theoretical value calculated according to the feeding proportion of sulfonated monomer), etc. Thus, sulfonated dihalodiphenylsulfones and sulfonated dihalodiphenylketones are important starting industrial raw materials for which efficient production techniques are critical.
However, the existing preparation technology of sulfonated dihalodiphenylsulfone and sulfonated dihalodiphenylketone has a plurality of defects. For example, the preparation of sodium 3,3 '-disulfonate-4, 4' -dichlorodiphenyl sulfone (reference: fine chemical intermediates, published under 12 months 2020, volume 50, 6, pages 67-71) generally uses an excess of fuming sulfuric acid, and tends to overflow a strong acid mist during high temperature reaction; after sulfonation, a plurality of salting-out operations are needed to be carried out to obtain a crude product, and a high-concentration waste sulfuric acid/mixed salt (sodium chloride and sodium sulfate) solution is additionally generated, so that the solution is difficult to treat, and the preparation process is not environment-friendly; in the refining process, an organic solvent such as isopropanol is needed to be recrystallized to obtain a product, organic wastewater is inevitably generated, and the production cost for recycling the organic solvent is increased. Chinese 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 process of sulfonation of dihalogenated diphenyl sulfone, and acid mist is reduced but still cannot be completely eradicated; in addition, a purification method for sulfonated monomers is also proposed, salting-out operation is required to be repeated for a plurality of times, and a large amount of waste sulfuric acid and waste liquid of mixed salt are inevitably generated, so that the waste is difficult to treat. Furthermore, the preparation of 3,3 '-sodium disulfonate-4, 4' -difluorobenzophenone (reference: synthesis and performance study of proton exchange membranes for novel fuel cells, jilin university Press, 12 th 2011, pages 61-63) uses fuming sulfuric acid (50% sulfur trioxide content) with higher concentration, and more acid mist overflows during high temperature reaction; meanwhile, the method still adopts salting out (adding sodium chloride) and organic solvent (using methanol) recrystallization after sulfonation, and the product can be obtained. Obviously, the preparation process is still not environment-friendly and does not belong to the green preparation technology.
Therefore, in view of a series of defects that the prior art generally has a lot of acid mist, high-concentration waste acid/mixed salt solution is difficult to process, organic solvent is required to be used, and the like, it is necessary to develop a green and environment-friendly preparation method aiming at the two sulfonated monomers.
Disclosure of Invention
The invention aims to overcome the defects, and provides a green preparation method of the sulfonated dihalogenated monomer, which can reduce acid consumption and acid mist pollution in the sulfonation reaction process, avoid waste salt and organic solvent in the product purification process, and realize timely recovery of waste acid, so as to meet the application requirements of related industrial fields.
The aim 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 dihalogenated reactant into a reaction kettle, covering, vacuumizing, filling nitrogen, completely replacing air, injecting a proper amount of fuming sulfuric acid, starting stirring, and heating to a target temperature until reactant solids are completely dissolved 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 for sulfonation reaction, immersing a second section of coil into cold water for rapid cooling of the reaction liquid;
(3) Connecting an 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 hydrolysis acid solution;
(4) Mechanically filtering the hydrolyzed acid solution, continuously introducing into a two-compartment electrodialyzer with a compact anion exchange membrane, introducing direct current, gradually removing sulfuric acid components to obtain a dehydrated acid solution, and recovering from a concentrating chamber to obtain a clean dilute sulfuric acid solution;
(5) Adding alkali into the deacidification liquid to neutralize until the pH value is slightly more than 7, then introducing an electrodialyzer again, and introducing direct current to rapidly remove residual salt so as to obtain sulfonate aqueous solution only containing sulfonate products;
(6) And dehydrating and drying the sulfonate aqueous solution to obtain the sulfonated dihalogenated monomer.
Preferably, the dihalogenated reactant is dihalogenated diphenyl sulfone or dihalogenated benzophenone, and the sulfonated dihalogenated monomer is sulfonated dihalogenated diphenyl sulfone or sulfonated dihalogenated benzophenone.
Preferably, the dihalodiphenylsulfone is 4,4 '-difluorodiphenyl sulfone, 4' -dichlorodiphenyl sulfone or 4,4 '-dibromodiphenyl sulfone, and the dihalodiphenylketone is 4,4' -difluorodiphenyl ketone, 4 '-dichlorodiphenyl ketone or 4,4' -dibromodiphenyl ketone.
In the preferred scheme, in the step (1), the mass percentage concentration of fuming sulfuric acid is 105-120% of sulfuric acid, and the addition amount of fuming sulfuric acid is 3-6 times of the mass of dihalogenated reactant.
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 coil is 60 to 200 minutes, preferably 90 to 150 minutes.
Preferably, in the step (2), the temperature of the oil bath is 120-200 ℃, preferably 140-180 ℃; immersing the second-stage coil in cold water ensures that the temperature of the reaction liquid in the second-stage coil is not lower than 60 ℃, preferably 60-90 ℃.
Preferably, in the step (3), the addition amount of the ice-water mixture is 2 to 5 times of the mass of the sulfonation reaction liquid.
Preferably, in the step (4), the pressure difference permeability coefficient of the compact anion exchange membrane for water is less than or equal to 0.002 mL/(cm) 2 h.multidot.MPa).
As a preferenceIn the scheme, in the step (4) and the step (5), the current density of the operation of the electrodialyzer is 5-30 mA/cm 2 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, wherein the three steps are performed under a completely airtight condition, the utilization efficiency of fuming sulfuric acid serving as a sulfonating agent and a solvent is higher, the overflow is less, and the generated acid mist pollution is also less;
(2) Because a two-section coil reactor is adopted, three steps of low-temperature dissolution, high-temperature sulfonation and cooling are simply connected in series, the process is very concise and easy to realize, the uniformity, the controllability, the recapitulation and the high efficiency of the tubular reaction can be brought into play, and the sulfonation reaction liquid with very uniform sulfonation degree can be continuously obtained; meanwhile, as 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 two-compartment electrodialyzer with compact anion exchange membrane is used, and the sulfuric acid molecules with smaller molecular weight can be basically removed by adopting an electric drive membrane separation mode, and the sulfonated products with larger molecular weight can be reserved, so that the clean recovery of residual sulfuric acid is realized very efficiently, the salting-out step is avoided, the dangerous waste liquid disposal problem of mixed salt containing high-concentration waste acid and bi-components is avoided, and the green preparation is realized smoothly;
(4) The product solution after deacidification and desalination by electrodialysis technology has simple components, only contains the product in the form of sulfonate of the required sulfonated dihalogenated diphenyl sulfone or sulfonated dihalogenated benzophenone, can be directly obtained by a conventional drying method, and avoids the recrystallization step and the purification process of an organic solvent; therefore, the method is simple, efficient, environment-friendly and low in cost.
Drawings
FIG. 1 is a chemical structure diagram of sulfonated dihalodiphenylsulfones and sulfonated dihalodiphenylketones;
FIG. 2 is a flow chart of a process for preparing sulfonated dihalodiphenylsulfone and sulfonated dihalodiphenylketone and the main equipment used in each step; in the figure: a represents a dissolution kettle, B1 represents a first section of coil, B2 represents a second section of coil, C represents an ice water dilution tank, D represents a filter, E represents a finished 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 the embodiments according to the present invention is provided with reference to the accompanying drawings, in which:
a green process for preparing a sulfonated dihalogen monomer (i.e., a sulfonated dihalogen diphenyl sulfone or a sulfonated dihalogen benzophenone) comprising the steps of: (1) Firstly, putting dihalogenated diphenyl sulfone or dihalogenated benzophenone into an acid-resistant metal reaction kettle, covering the kettle, vacuumizing, filling nitrogen, completely replacing air, injecting a proper amount of fuming sulfuric acid, starting stirring, and heating moderately 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 acid-resistant metal coil reactor, and balancing the opening of a nitrogen inlet valve, the bottom valve and the metering pump to ensure that the reaction liquid enters the coil at a constant speed; (3) Immersing the first section of coil pipe into an oil bath, and carrying out sulfonation reaction at high temperature; immersing the second section of coil pipe into cold water, and rapidly cooling the reaction liquid; (4) Connecting an 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 hydrolysis acid solution; (5) Mechanically filtering the hydrolyzed acid liquor, continuously introducing into a two-compartment electrodialyzer with a compact anion exchange membrane, introducing direct current, gradually removing sulfuric acid components, and recovering from a concentrating chamber to obtain clean dilute sulfuric acid solution; (6) Adding alkali into the deacidification liquid to neutralize until the pH value is slightly more than 7, then introducing an electrodialyzer again, and introducing direct current to rapidly remove residual salt to obtain an aqueous solution only containing sulfonate products; (7) And dehydrating and drying the sulfonate aqueous solution to obtain the product in the form of sulfonate of the sulfonated dihalogenated diphenyl sulfone or the sulfonated dihalogenated diphenyl ketone.
Wherein, the sulfonated dihalogenated diphenyl sulfone and sulfonated dihalogenated benzophenone refer to the complete sulfonation products of dihalogenated diphenyl sulfone and dihalogenated benzophenone, and can only be the 'double sulfonation' products in which the sulfonation reaction of two benzene rings respectively occurs. In view of the sulfonation mechanism being electrophilic substitution of aromatic rings, the structure of the sulfonation reaction product is necessarily affected by the substituent positioning effect. The positioning effect of the halogen atom, carbonyl group or sulfone group is integrated, and as a result, the sulfonic acid group generated after the sulfonation reaction can only be positioned at the ortho position of the carbon atom of the benzene ring connected with the halogen atom, namely at the meta position of the carbon atom of the benzene ring connected with the sulfone group or carbonyl group. The chemical structural formula is shown in figure 1, X is fluorine, chlorine or bromine atom, and the structural characteristics of dihalogenation are shown; y is carbonyl or sulfonyl, which indicates that the structural characteristics of benzophenone or diphenyl sulfone are provided; m is a hydrogen, sodium or potassium atom, indicating structural features of disulfonate or disulfonate groups. In particular, the chemical names of the sulfonated dihalodiphenylsulfones and sulfonated dihalodiphenylketones in the form of the sodium disulfonate salts described above specifically include: sodium 3,3 '-disulfonate-4, 4' -difluorodiphenyl sulfone, sodium 3,3 '-disulfonate-4, 4' -dichlorodiphenyl sulfone, sodium 3,3 '-disulfonate-4, 4' -dibromodiphenyl sulfone, sodium 3,3 '-disulfonate-4, 4' -difluorobenzophenone, sodium 3,3 '-disulfonate-4, 4' -dichlorobenzophenone, sodium 3,3 '-disulfonate-4, 4' -dibromobenzophenone. If no base is added for neutralization, the sulphonation product is in the form of a disulphonic acid with free hydrogen ions, for example 3,3 '-disulphonic acid-4, 4' -dichlorodiphenyl sulphone or 3,3 '-disulphonic acid-4, 4' -difluorobenzophenone. Similarly, if potassium hydroxide (rather than sodium hydroxide) is added for neutralization, the sulfonation product is in the form of a potassium disulfonate salt, such as potassium 3,3 '-disulfonate-4, 4' -dichlorodiphenyl sulfone or potassium 3,3 '-disulfonate-4, 4' -difluorobenzophenone. In fact, other forms of monovalent cation salts, such as lithium salts or ammonium salts, are also possible (obtained by neutralization of the sulfonation reaction solution with lithium hydroxide and aqueous ammonia, respectively), but are not common and are not specifically listed here.
In the step (1), the acid-resistant metal reaction kettle (i.e. a of fig. 2), the two-stage acid-resistant metal coil reactor in the step (2) is composed of the first-stage coil (i.e. B1 of fig. 2) in the step (3) and the second-stage coil (i.e. B2 of fig. 2) in the step (4), and the materials of the two-stage acid-resistant metal coil reactor can be ordinary carbon steel or cast iron, or special 20 # alloy (i.e. chrome-nickel-molybdenum-copper alloy) or tantalum alloy, so long as the two-stage acid-resistant metal coil reactor can resist corrosion caused by fuming sulfuric acid for a long time. And, the cauldron body is best integrated casting to guarantee to have higher resistant internal pressure. The upper limit of the internal pressure resistance is 1.0MPa, so that the pressure resistance requirement of nitrogen pressurization and fluid pumping can be met, and leakage of sulfuric acid trioxide mist can be thoroughly avoided. The pipes, valves and metering pumps connecting them are also preferably of the same acid resistant metal material and are capable of withstanding sufficient internal pressure.
In the step (1), the concentration of the injected fuming sulfuric acid is 105-120% of sulfuric acid, and the most common is industrial 105 acid (100 g of fuming sulfuric acid with the specification can obtain 105 g of pure sulfuric acid after absorbing water) and 120 acid (100 g of fuming sulfuric acid with the specification can obtain 120 g of pure sulfuric acid after absorbing water), or the two specifications of industrial fuming sulfuric acid are mixed to the specified concentration. If the concentration is too low, the sulfonation effect is poor, and it is difficult to obtain a completely sulfonated product; if the fuming sulfuric acid concentration exceeds 120%, it is easy to cause too much sulfur trioxide residue after sulfonation, and thereafter the reaction is extremely intense when hydrolyzed in ice water, producing a remarkable acid mist. In addition, the concentration of fuming sulfuric acid as a sulfonating agent is not too high from the viewpoints of the raw material utilization and sulfuric acid recovery. The adding amount of fuming sulfuric acid (the density at normal temperature is about 1.9 g/mL), the mass ratio of the fuming sulfuric acid to dihalogenated diphenyl sulfone or dihalogenated benzophenone is 3:1-6:1, and too little adding amount can cause incomplete dissolution of the dihalogenated diphenyl sulfone and the dihalogenated benzophenone, and then the complete homogeneous sulfonation reaction process is difficult to implement; too large an amount of the sulfonating agent is excessively large, which inevitably leads to waste of raw materials and increase of sulfuric acid recovery. When the mixture in the kettle is dissolved, the mixture is heated appropriately, for example, the temperature is raised to 50-100 ℃, preferably 60-90 ℃, so that the dihalogenated diphenyl sulfone or dihalogenated benzophenone can be dissolved in fuming sulfuric acid completely, and light yellow or yellow clear liquid can be obtained. In general, although the dissolution process is also accompanied by some degree of sulphonation, practice has proven: only at higher temperatures, for example exceeding 120 c, will a significant sulphonation effect be exerted. Before fuming sulfuric acid is added, the air in the kettle is necessarily completely replaced by nitrogen; in order to quickly drive off the air, the process of vacuumizing and filling nitrogen is preferably repeated for a plurality of times after the solid raw material of dihalodiphenylsulfone or dihalodiphenylketone is added, then a feeding valve of fuming sulfuric acid is carefully opened, and fuming sulfuric acid slowly flows into the dissolution kettle by utilizing a natural pressure difference so as to avoid bringing in air.
In the step (2), the reaction liquid is injected into the two-stage acid-resistant metal coil reactor, and after the bottom valve of the dissolution kettle is opened, the flow rate entering the coil is controlled smoothly by means of the air pressure of the nitrogen gas filled in the dissolution kettle and the opening degree of a metering pump (a numerical control precise plunger pump is recommended); the flow rate is calculated in advance according to the residence time of the reaction liquid in the coil pipe and is set in advance. After all of the liquid in the tank is injected into the coil, the unidirectional flow of the reaction liquid in the coil is maintained mainly by controlling the inlet pressure of nitrogen (not just the opening degree of the metering pump). In addition to the requirement that the coil material withstand fuming sulfuric acid, it is also required to withstand an internal pressure of at least 1.0MPa, which can be achieved by one-time crimping using a seamless metal tube of sufficient wall thickness (e.g., not less than 3 mm) and sufficient length to avoid unnecessary welding.
In the step (3), the first coil is subjected to high-temperature sulfonation reaction in an oil bath at 120-200 ℃, 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 quickly heated to the required sulfonation reaction temperature; if the temperature is too high, the internal pressure of the coil increases sharply (due to the resistance of the reaction solution to rapid expansion), and the risk of leakage increases. It was also found that too high an oil bath temperature caused excessive sulfonation side reactions, producing a dark brown sulfonated product. This may be due to partial carbonization of the starting material or sulfonated product, although the exact mechanism is not known. The residence time of the reaction solution in the first coil is 60 to 200 minutes, preferably 90 to 150 minutes. The length of the residence time must be matched to the oil bath temperature. That is, the higher the oil bath temperature, the shorter the residence time can be to avoid excessive sulfonation; the residence time needs to be extended to ensure complete sulfonation if the oil bath temperature is somewhat lower. The practice of the invention proves that in a fully sealed pressure-tube reactor, sulfur trioxide in fuming sulfuric acid can be more effectively utilized, which can lead to a greatly shortened sulfonation reaction time than that required in a single-batch atmospheric reactor. The second-section coil is immersed in cold water to cool the reaction liquid, so that the temperature of the reaction liquid in the second-section 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 is not smooth and even is jammed; if the outlet temperature is high, namely the cooling of the reaction liquid is insufficient, the use level of ice water is greatly increased during hydrolysis; otherwise, the temperature of the hydrolysis solution rises rapidly, and the acid mist overflows greatly and is difficult to be absorbed by ice water completely.
In the step (4), the ice-water mixture is contained in an ice-water diluting tank (i.e. C in fig. 2) and used as the hydrolysate of the sulfonation reaction liquid and the absorption liquid of the residual acid mist, and the mass ratio of the hydrolysate to the reaction liquid is 2:1-5:1. If the amount is too small, the heat absorption capacity is insufficient, the temperature during hydrolysis cannot be ensured to be not higher than 70 ℃, and the acid mist overflows rapidly as a result; if the amount is too much, although the effect of hydrolysis and absorption of acid mist is remarkably increased, the concentration of the product and the concentration of dilute sulfuric acid are obviously reduced, so that the cost of drying and recovering the dilute sulfuric acid is increased directly, and the cost is not reduced. The ratio of ice to water in the ice-water mixture is not particularly limited depending on the endothermic effect, but it is necessary to secure at least a sufficiently thick layer of floating ice (preferably crushed ice) so that the effect of blocking the overflow of acid mist can be remarkably increased.
In the step (5), the hydrolysate is mechanically filtered (i.e. D of fig. 2), and conventional solid-liquid filtration methods, such as activated carbon column chromatography, flat membrane suction filtration, and medium-control fiber microfiltration membrane filtration, are adopted, so long as the filtration materials and equipment can withstand dilute sulfuric acid (mass concentration is less than 30%). In general, it is recommended to use a polytetrafluoroethylene flat-plate microfiltration membrane unit with an average pore size of less than 5 μm to completely retain trace solid particles (presumably very small residual raw materials that do not react completely, or carbonized black spots that do not react too much) in the acidic hydrolysate to obtain a completely clear pale yellow solution, which is temporarily stored in a final solution tank (i.e., E of FIG. 2)Is a kind of medium. The two-compartment electrodialyser (i.e. F of fig. 2) provided with a dense anion exchange membrane, i.e. having a desalting compartment and a concentrating compartment, is particularly desirable for the anion exchange membrane to be installed. It is difficult for a common standard anion exchange membrane to efficiently entrap sulfonated product anions (for example, sodium 3,3 '-disulfonate-4, 4' -dichlorodiphenyl sulfone, the relative molecular weight of the sulfonated product anions minus two sodium ions is 445) while permeating sulfate ions (relative molecular weight is 96). Therefore, the anion exchange membrane needs to be customized from the aspects of thickness, swelling rate, ion exchange channel structure and the like to improve compactness and increase the division of permeation areas of anions with different sizes, and the rejection rate of the anions of the sulfonated product with obviously larger molecular weight than sulfate radical is preferably more than 95 percent, so that the significant product loss can be avoided. After repeated experiments, the degree of compactness of the compact anion exchange membrane and the actual interception effect of anions of a sulfonated product can be measured by simply using the differential pressure permeability coefficient of water. The conclusion is that: according to the detection method described in the ocean industry standard HY/T166.1-2013 of the people's republic of China, the differential pressure permeability coefficient of water is not more than 0.002 mL/(cm) 2 h.multidot.MPa), the above requirement for an anion retention of the sulphonated product of more than 95% can be met. Although the commercial dense anion exchange membranes can meet this requirement, the current density of the electrodialyser operation still cannot exceed 30mA/cm 2 Effective membrane area (refers to the area of the membrane area that passes direct current); otherwise, the driving force of the direct current electric field is too large, and anions of the sulfonated products still possibly migrate through the anion exchange membrane along with sulfate, so that considerable product loss is caused. That is, the dilute sulfuric acid solution recovered from the concentrating compartment is not sufficiently clean and may contain significant amounts of sulfonate product anions. But the lower limit of the current density is not lower than 5mA/cm 2 In order to avoid that both sulphate and hydrogen ions migrate too slowly, which makes the electrodialysis deacidification process too time-consuming.
In the step (6), the alkali is added to neutralize the dealkylation liquid, and preferably, the solid of sodium hydroxide or potassium hydroxide is directly added to avoid the increase of the volume of the solution. Removal ofIn addition to neutralizing the residual sulfuric acid that was not completely removed in the previous step, the base neutralizes the free hydrogen ions paired with the sulfonated product, converting it from the hydrogen form to the sodium or potassium form. Generally, all sulphonated products are completely transformed by neutralization with alkali to a pH slightly above 7, for example 7.0 to 8.5; that is, the sulfonated product no longer contains dissociable hydrogen ions, but is entirely disodium or dipotassium salt. Before the direct current is connected again and the electrodialyzer is started, the dilute sulfuric acid in the concentrating chamber is thoroughly emptied and recycled to the acid recycling tank (namely G in the figure 2), and then the corresponding dilute brine (namely dilute salt solution corresponding to sodium sulfate or potassium sulfate to be removed in the concentrating chamber) is introduced, wherein the concentration is generally 0.5-2%. Thus, after the direct current is switched in again, the resistances of the concentration chamber and the desalination chamber are smaller, so that the residual salt in the concentration chamber can be rapidly removed, and then the salt can be recovered to a salt recovery tank (namely H in the figure 2). In the same way, the current density of the electrodialysis desalination process should be 5-30 mA/cm 2 Effective membrane area. The conductivity of the concentrating chamber or the desalting chamber is basically unchanged, which means that the salt is basically removed, so that the aqueous solution only containing sulfonate products in the concentrating chamber can be obtained and still can be stored in a finished solution tank (in practice, the deacidification liquid can be added with alkali for neutralization and can be completed in the tank).
In the step (7), the solution of sulfonate may be filtered and concentrated with nanofiltration membrane, for example, the concentration of sulfonate may be increased to 25% or more, and then evaporated, crystallized and dried to obtain sulfonate crystals. Or directly heating and evaporating water to obtain dry product; or spray drying to obtain powder. Naturally, the purity of the crystalline product will be slightly higher than the dry powder product obtained by direct drying. The latter may have very small amounts of sulphate but as long as the effect of the electrodialysis desalination of the previous step is controlled, it is ensured that the desalination is complete or the purity requirements of the technical grade quality (e.g. more than 98.5%) can be easily met.
The invention is further illustrated by the following examples:
example 1:
preparation of sodium 3,3 '-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 (the kettle body is integrally cast, the thickness is 5 mm, a polytetrafluoroethylene-treated 304 stainless steel flange cover is sprayed on the surface, the thickness is 18 mm, a high-pressure-resistant tempered glass sight glass is embedded, a polytetrafluoroethylene gasket is used for sealing, 3.0MPa compressed air is used for leakage test, 100 g of 4,4' -dichloro diphenyl sulfone solid (348 mmol, analytical grade, shanghai A Ding Huaxue reagent company) is added, a magnetic stirrer is put in, the flange cover is covered, the flange cover is screwed, the flange cover is evacuated and then screwed, and industrial nitrogen is filled to the pressure of 0.4MPa; the bottom valve is opened, and nitrogen is slowly discharged from the two-section coiled pipe (by controlling the opening of the one-way valve at the joint of the second-section coiled pipe and the polytetrafluoroethylene pipe); and continuing the operations of vacuumizing, filling nitrogen and discharging nitrogen 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 with a flange cover and a glass constant pressure funnel (500 ml with scales) for holding fuming sulfuric acid, slowly putting 250 ml fuming sulfuric acid (industrial 105 acid, actual measurement of sulfuric acid content 105.3%); closing a feed valve, closing a 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 (which is tightly attached to the outer wall of the reaction kettle) shows 65 ℃; the floating of the solid is observed through the 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) The nitrogen inlet valve (pressure is maintained to be 0.15MPa through the precise pressure reducing valve), the bottom valve of the reaction kettle and the metering pump are opened, the one-way valve at the outlet of the second section of coil pipe is unscrewed, the reaction liquid in the reaction kettle is continuously injected into the two sections of acid-resistant metal coil pipe reactors, and the flow of the corrosion-resistant precise plunger pump is set to be 5.0 milliliters/minute.
(3) The first section of coil pipe (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 seamless carbon steel pipes) is fully immersed into an oil bath, the temperature of the oil bath is set to 162 ℃, and the fully sealed sulfonation reaction is realized in the coil pipe; the second section of coil pipe (the material and specification are the same as those of the first section of coil pipe, the length is 2.0 m, the internal volume is 100 ml) is completely immersed into cold water, the cold water bath is set to 45 ℃, and the reaction liquid in the coil pipe is cooled by cold water external circulation refrigeration.
(4) The cooled reaction solution continuously flows into the bottom of an ice water dilution tank (1700 g of ice/water mixture is contained, wherein the mass ratio of ice/water is about 1/3) through a polytetrafluoroethylene tube, at the moment, the temperature displayed by a thermometer at the joint of a second section of coil pipe and the polytetrafluoroethylene tube (with the outer diameter of 14 mm and the inner diameter of 8 mm) is 74 ℃, and the reaction solution is immediately hydrolyzed and continuously releases heat; finally, the temperature of the hydrolysis liquid is raised to 57 ℃, no acid mist overflows all the time, and 1980 ml of hydrolysis acid liquid with the sulfuric acid content of 16.8% is obtained.
(5) The hydrolyzed acid liquor passes through a suction filter and is clamped into a single disc filter membrane (PTFE micro-filtration membrane, the diameter is 120 mm, the thickness is 0.15 mm, and the average pore diameter is 2 microns) for vacuum suction filtration; then an electrodialyzer (EX-3 BT desktop, available from Hangzhou blue technology Co., ltd., effective membrane area of the energization 55 cm) was assembled 2 10 compact anion exchange membranes (supplied by Qu-lan Material Co., ltd., anion exchange membranes for AHM type electrophoretic coating, wet membrane thickness of 0.50 mm, differential pressure permeability coefficient of water of 0.0013 mL/(cm) 2 h.MPa)) and 11 standard cation exchange membranes (CIM type homogeneous membrane, 0.21 mm wet membrane thickness, 0.065 mL/(cm) water differential permeability coefficient 2 h.MPa)); introducing filtrate into desalting chamber of electrodialysis device, introducing 1500 ml of 0.5% dilute sulfuric acid solution into concentrating chamber, introducing 1000 ml of 5% sodium sulfate solution into polar chamber, simultaneously opening the internal circulation of concentrating chamber, desalting chamber and polar chamber, immediately introducing direct current, operating in constant current mode, and setting current to 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% (the deacidification rate is calculated to be about 94%), and taking about 120 minutes, namely, turning off a power supply and three-chamber circulation, respectively recovering the dilute sulfuric acid solution in the concentrating chamber to an acid recovery tank and the deacidification solution in the desalting chamber to a finished product solution tank.
(6) Gradually adding 32 into the finished solution tank3 g of sodium hydroxide tablet alkali particles, stirring and neutralizing until the pH value is 7.5; introducing the neutralization solution into the desalting chamber of the electrodialysis device again, and simultaneously introducing 1500 ml of 1% sodium sulfate solution into the concentrating chamber and still introducing 1000 ml of 5% sodium sulfate solution into the polar chamber; starting three-chamber circulation, accessing direct current, adopting constant current mode to operate, setting current to 1.4A (corresponding current density 25.5 mA/cm) 2 ) The salt is removed from the desalting chamber to the concentrating chamber, the conductivity of the concentrating chamber is rapidly increased to the maximum value (the conductivity is constant to be about 16.5ms/cm after about 28 minutes), namely, the power supply and the three-chamber circulation are closed, and the salt water in the concentrating chamber is respectively recovered to a salt water recovery tank and the desalted liquid in the desalting chamber, so as to obtain 1840 milliliters of desalted liquid.
(7) Gradually evaporating and dehydrating the desalted liquid by a rotary evaporator under reduced pressure, respectively placing the desalted liquid in a white enamel tray, drying by blowing at 85 ℃ until no visible moisture exists on the surface, and drying by blowing at 120 ℃ until the weight is constant; the dried product was collected carefully to yield 169.7 g (about 345 mmol), from which the yield was 99.2%. The following is explained: the sulfonation is substantially complete and the product losses of electrodialysis deacidification and desalination processes are minimal. The main peak relative molecular weight was 491 as determined by high resolution mass spectrometry, and the purity was 98.6% by HPLC (RP 18 column (5 μm, 3.9X106 mm), mobile phase acetonitrile/water (volume ratio 6/4), flow rate 1.0 ml/min, internal standard method) as identified as sodium 3,3 '-disulfonate-4, 4' -dichlorodiphenyl sulfone.
Example 2:
preparation of sodium 3,3 '-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' -difluorodiphenyl sulfone solid (393 mmol, analytically pure, shanghai ala Ding Huaxue reagent company) and 200 ml of fuming sulfuric acid (mixed with 105 acid and 120 acid, measured sulfuric acid content 110.3%) were added, the temperature probe was raised to 72 ℃, the rest of the procedure was the same as in step (1) of example 1, and after about 20 minutes of stirring the solid was found to be completely dissolved. (2) The flow rate of the corrosion-resistant precision plunger pump was set to 3.4 ml/min, and the other procedures were the same as in step (2) of example 1, and the dissolved reaction liquid was injected into the two-stage coil reactor. (3) Oil bathThe temperature was set at 145℃and the rest of the procedure was the same as in step (3) of example 1, followed by sulfonation and cooling of the reaction mixture. (4) The temperature displayed by a thermometer at the joint of the second section of coil pipe and the polytetrafluoroethylene pipe is 75 ℃, the cooled reaction liquid continuously flows into the bottom of an ice water dilution tank (containing 1500 g of ice/water mixture with the mass ratio of ice/water being about 1/4) through the polytetrafluoroethylene pipe, the temperature of the hydrolysis liquid rises to 55 ℃ after the hydrolysis is completed, no acid mist overflows, 1730 ml of hydrolysis acid liquid is obtained, and the sulfuric acid content is 16.4%. (5) The electrodialyzer used was the same as in example 1, and the current for electrodialyzed deacidification was set to 1.3A (corresponding to a current density of 23.6mA/cm 2 ) About 90 minutes is taken to remove the sulfuric acid from the desalting chamber to less than 1% (from which the deacidification rate is measured to about 94%), and the rest of the process and the equipment are the same as those in step (5) of example 1. (6) The same procedure and equipment as in step (6) of example 1 were used to neutralize the desalted liquid with 33.1 g of sodium hydroxide flake alkali particles, to give 1600 ml of desalted liquid. (7) Spin-drying and drying were carried out in the same manner as in step (7) of example 1, to obtain 179 g (about 391 mmol) of dried product, from which a yield of 99.4% was calculated. Mass spectrometry (apparatus and analytical method as in example 1) identified as sodium 3,3 '-disulfonate-4, 4' -difluorodiphenyl sulfone (relative molecular weight 458) and HPLC (apparatus and analytical method as in example 1) detected a purity of 98.7%.
Example 3:
preparation of sodium 3,3 '-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, analytically pure, shanghai Aba Ding Huaxue reagent Co.) and 180 ml of fuming sulfuric acid (prepared by mixing 105 acid and 120 acid, measured sulfuric acid content 114.6%) were added, the temperature probe was raised to 75℃and the rest of the procedure was the same as in step (1) of example 1, and it was found that after stirring for about 20 minutes the solid was completely dissolved. (2) The flow rate of the corrosion-resistant precision plunger pump was set to 5.3 ml/min, and the other procedures were the same as in step (2) of example 1, and the dissolved reaction liquid was injected into the two-stage coil reactor. (3) The oil bath temperature was set to 165℃and the rest of the procedure was as in example 1And (3) carrying out sulfonation reaction and cooling the reaction liquid in sequence in the same step. (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 liquid continuously flows into the bottom of an ice water dilution tank (containing 1600 g of ice/water mixture with the mass ratio of ice/water being about 1/3) through the polytetrafluoroethylene pipe, the temperature of the hydrolysis liquid rises to 57 ℃ after the hydrolysis is completed, no acid mist overflows, 1800 ml of hydrolysis acid liquid is obtained, and the sulfuric acid content is 14.9%. (5) The electrodialyzer used was the same as in example 1, and the current for electrodialyzed deacidification was set to 1.2A (corresponding to a current density of 21.8mA/cm 2 ) About 90 minutes is taken to remove the sulfuric acid from the desalting chamber to less than 1% (from which the deacidification rate is measured to about 93%), and the rest of the process and the equipment are the same as those in step (5) of example 1. (6) The dealcoholized solution was neutralized to pH 7.4 with 39.2 g of sodium hydroxide powder, and the running current of electrodialysis desalination was 1.1A (corresponding to a current density of 20mA/cm 2 ) The rest of the procedure and the equipment used were the same as in step (6) of example 1, except that the concentration chamber was terminated until the conductivity rose to around 17.4ms/cm, to obtain 1690 ml of desalted liquid. (7) Spin-drying and drying were carried out in the same manner as in (7) in example 1, except that 191.4 g (about 453 mmol) of dried product was obtained, whereby a yield of 99.1% was obtained. Mass spectrometry (apparatus and analytical method as in example 1) identified as 3,3 '-sodium disulfonate-4, 4' -difluorobenzophenone (relative molecular weight 422) and HPLC (apparatus and analytical method as in example 1) detected a 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, analytically pure, shanghai Aba Ding Huaxue reagent Co.) and 280 ml of fuming sulfuric acid (prepared by mixing 105 acid and 120 acid, measured sulfuric acid content 106.8%) were added, the temperature was raised to 80℃with the temperature probe, and the rest of the procedure was the same as in step (1) of example 1, finding that after stirring for about 20 minutes the solid was completely dissolved. (2) The flow rate of the corrosion-resistant precision plunger pump was set to 4.2 ml/min, and the other procedures were the same as in step (2) of example 1, and the dissolved reaction solution was injected into the two-stage typeCoil reactor. (3) The oil bath temperature was set at 170℃and the rest of the procedure was the same as in step (3) of example 1, followed by successively carrying out sulfonation and cooling the reaction solution. (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 liquid 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 liquid rises to 53 ℃ after the hydrolysis is completed, acid mist is not overflowed, 3290 ml of hydrolysis acid liquid is obtained, and the sulfuric acid content is 11.3%. (5) The electrodialyzer used was the same as in example 1, and the current for electrodialyzed deacidification was set to 1.1A (corresponding to a current density of 20mA/cm 2 ) About 120 minutes is taken to remove the sulfuric acid from the desalting chamber to less than 1% (from which the deacidification rate is measured to about 91%), and the rest of the process and the equipment are the same as those in step (5) of example 1. (6) The dealcoholized liquid was neutralized with 34.0 g of potassium hydroxide powder to pH 7.5, and 1500 ml of 1% potassium sulfate solution was introduced into the concentrating chamber during electrodialysis desalination, and the running current was set to 1.5A (corresponding to a current density of 27.3 mA/cm) 2 ) After the concentration chamber was increased to around 19.3ms/cm, the rest of the procedure and the equipment were the same as those in the step (6) of example 1, to obtain 3160 ml of desalted liquid. (7) The desalted solution was directly spray-dried to obtain 157.8 g (about 274 mmol) of a dried product, from which a yield of 93.1% was calculated (a small amount of powder in the dryer was difficult to clean). Mass spectrometry (apparatus and analytical method as in example 1) identified as 3,3 '-potassium disulfonate-4, 4' -dibromobenzophenone (relative molecular weight 576) and HPLC (apparatus and analytical method as in example 1) detected a purity of 99.2%.
TABLE 1 preparation conditions, process parameters and results for examples 1-4
The foregoing is only illustrative of the preferred embodiments and principles of the present invention, and changes in specific embodiments will occur to those skilled in the art upon consideration of the teachings provided herein, and such changes are intended to be included within the scope of the invention as defined by the claims.
Claims (10)
1. The green preparation method of the sulfonated dihalogen monomer is characterized by comprising the following steps:
(1) Putting dihalogenated reactant into a reaction kettle, covering, vacuumizing, filling nitrogen, completely replacing air, injecting a proper amount of fuming sulfuric acid, starting stirring, and heating to a target temperature until reactant solids are completely dissolved 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 for sulfonation reaction, and immersing a second section of coil into cold water for rapidly cooling the reaction liquid;
(3) Connecting an 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 hydrolysis acid solution;
(4) Mechanically filtering the hydrolyzed acid solution, continuously introducing into a two-compartment electrodialyzer with a compact anion exchange membrane, introducing direct current, gradually removing sulfuric acid components to obtain a dehydrated acid solution, and recovering from a concentrating chamber to obtain a clean dilute sulfuric acid solution;
wherein the pressure difference permeability coefficient of the compact anion exchange membrane for water is less than or equal to 0.002 mL/(cm) 2 h.MPa) anion exchange membrane;
(5) Adding alkali into the deacidification liquid to neutralize until the pH value is slightly more than 7, then introducing an electrodialyzer again, and introducing direct current to rapidly remove residual salt so as to obtain sulfonate aqueous solution only containing sulfonate products;
in the step (4) and the step (5), the current density of the operation of the electrodialyzer is 5-30 mA/cm 2 Effective membrane area;
(6) And dehydrating and drying the sulfonate aqueous solution to obtain the sulfonated dihalogenated monomer.
2. The green process for the preparation of sulphonated dihalogen monomers according to claim 1 wherein the dihalogen reactant is dihalodiphenylsulphone or dihalodiphenylketone and the sulphonated dihalogen monomer is sulphonated dihalodiphenylsulphone or sulphonated dihalodiphenylketone, respectively.
3. The green process for the preparation of sulphonated dihalogen monomers according to claim 2 wherein the dihalodiphenylsulphone is 4,4 '-difluorodiphenyl sulphone, 4' -dichlorodiphenyl sulphone or 4,4 '-dibromodiphenyl sulphone and the dihalodiphenylketone is 4,4' -difluorodiphenyl ketone, 4 '-dichlorodiphenyl ketone or 4,4' -dibromodiphenyl ketone.
4. The green process for producing a sulfonated dihalogen monomer according to claim 1, wherein in said step (1), the concentration of fuming sulfuric acid by mass is 105 to 120% of sulfuric acid, and the amount of fuming sulfuric acid to be added is 3 to 6 times by mass of the dihalogen reactant.
5. The green process for producing a sulfonated dihalogen monomer according to claim 1, characterized in that in said step (1), the target temperature is 50 to 100 ℃.
6. The green process for producing a sulfonated dihalogen monomer according to claim 5, characterized in that in said step (1), the target temperature is 60 to 90 ℃.
7. The green process for producing a sulfonated dihalogen monomer according to claim 1, wherein in said step (2), the residence time of the reaction liquid in the first-stage coil is 60 to 200 minutes.
8. The green process for producing a sulfonated dihalogen monomer according to claim 1, characterized in that in said step (2), the oil bath temperature is 120 to 200 ℃; immersing the second coil in cold water ensures that the temperature of the reaction liquid in the second coil is not lower than 60 ℃.
9. The green process for producing a sulfonated dihalogen monomer according to claim 8, characterized in that in said step (2), the oil bath temperature is 140 to 180 ℃; immersing the second coil pipe in cold water ensures that the temperature of the reaction liquid in the second coil pipe is 60-90 ℃.
10. The green preparation method of the sulfonated dihalogen monomer according to claim 1, wherein in the step (3), the addition amount of the ice-water mixture is 2 to 5 times of the mass of the sulfonation reaction liquid by mass.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211104590.3A CN115304525B (en) | 2022-09-09 | 2022-09-09 | Green preparation method of sulfonated dihalogen monomer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211104590.3A CN115304525B (en) | 2022-09-09 | 2022-09-09 | Green preparation method of sulfonated dihalogen monomer |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115304525A CN115304525A (en) | 2022-11-08 |
CN115304525B true CN115304525B (en) | 2023-12-01 |
Family
ID=83867511
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211104590.3A Active CN115304525B (en) | 2022-09-09 | 2022-09-09 | Green preparation method of sulfonated dihalogen monomer |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115304525B (en) |
Citations (3)
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 |
-
2022
- 2022-09-09 CN CN202211104590.3A patent/CN115304525B/en active Active
Patent Citations (3)
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 |
Also Published As
Publication number | Publication date |
---|---|
CN115304525A (en) | 2022-11-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101607925A (en) | In microreactor with the SO 3 sulfonated method for preparing naphthalene sulfonic | |
Zeng et al. | Hydrophilic SPEEK/PES composite membrane for pervaporation desalination | |
CN105418921B (en) | A kind of highly sulfonated crosslinkable polyimide, preparation method and its application in terms of PEM | |
CN109097408A (en) | A kind of preparation method of 56 salt of nylon | |
CN112897488A (en) | Method for preparing bis (fluorosulfonyl) imide by using microchannel reactor | |
CN108250106B (en) | Method for preparing dimethyl isophthalate-5-sodium sulfonate and sodium sulfate from three-monomer process wastewater | |
CN115304525B (en) | Green preparation method of sulfonated dihalogen monomer | |
CN109721733B (en) | Preparation method of polysulfone resin | |
CN109971013A (en) | A kind of preparation method of cross-linked polyether-ether-ketone membrane material | |
CN112473395B (en) | Bipolar membrane based on pre-modified metal-organic framework material and preparation method and application thereof | |
CN102336690B (en) | Method for separating and purifying high-purity 4,4'-dihydroxydiphenylsulfone | |
CN112457495B (en) | Preparation method of homogeneous anion exchange membrane | |
CN112337318B (en) | Polyphenylene sulfide/porous carbon nanofiber composite membrane and preparation method thereof | |
CN109988327A (en) | A kind of non-fluorine ion exchange membrane and its preparation method and application | |
CN113769592A (en) | Quaternized modified polyarylether membrane material and preparation method and application thereof | |
CN101580584B (en) | Efficient preparation method of block sulfonated aromatic poly (thio) ether | |
CN112588327A (en) | Preparation method and application of organic solvent-resistant cation exchange membrane | |
CN113636969B (en) | Sulfonated bisphenol monomer and preparation method and application thereof | |
CN109988278A (en) | A method of improving polyether-ether-ketone sulfonation degree | |
KR100440895B1 (en) | Method for preparing sulphonated polysulphone polymer for cationic exchange membrane | |
CN117229178A (en) | Method for preparing clt acid by liquid phase baking method | |
CN1037326C (en) | High strength honeycomb ion filtering material and its prepn. method | |
CN104987507A (en) | Sulfonated polysulfone preparing method with microwaves as heat source | |
CN114471167A (en) | Process method for separating and decoloring mixed solution containing oxalic acid and glyoxylic acid | |
CN103910817A (en) | Method for preparing polystyrolsulfon acid aqueous solution through sodium p-styrenesulfonate polymerization |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
TA01 | Transfer of patent application right | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20230803 Address after: Building 11, No. 38 Haitang Road, Quzhou City, Zhejiang Province, 324000 Applicant after: Quzhou Lantong New Materials Co.,Ltd. Address before: No. 76, Houshiduntou, Jianjiang Village, Fengshan Street, Yuyao City, Ningbo City, Zhejiang Province 315400 Applicant before: Wu Yinqing |
|
GR01 | Patent grant | ||
GR01 | Patent grant |