CN115286543B - 利用全氟烷基磺酸离子液体制备4,4′-二氯二苯砜的工艺 - Google Patents
利用全氟烷基磺酸离子液体制备4,4′-二氯二苯砜的工艺 Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 105
- -1 perfluoroalkyl sulfonic acid Chemical compound 0.000 title claims abstract description 92
- 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 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 118
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 71
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 22
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical group [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 16
- 238000005580 one pot reaction Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 31
- 238000004128 high performance liquid chromatography Methods 0.000 description 29
- 239000003054 catalyst Substances 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 17
- 238000012544 monitoring process Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- 238000011084 recovery Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 238000005070 sampling Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910018286 SbF 6 Inorganic materials 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 4
- 235000019647 acidic taste Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- KJGYFISADIZFEL-UHFFFAOYSA-N 1-chloro-4-(4-chlorophenyl)sulfinylbenzene Chemical compound C1=CC(Cl)=CC=C1S(=O)C1=CC=C(Cl)C=C1 KJGYFISADIZFEL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 2
- ZMSRCMWBEGLBAI-UHFFFAOYSA-N 3,3,4,4-tetrafluorooxathietane 2,2-dioxide Chemical compound FC1(F)OS(=O)(=O)C1(F)F ZMSRCMWBEGLBAI-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 1
- GLCNLZSZEJDFLP-UHFFFAOYSA-N 3,3,4-trifluoro-4-(trifluoromethyl)oxathietane 2,2-dioxide Chemical compound FC(F)(F)C1(F)OS(=O)(=O)C1(F)F GLCNLZSZEJDFLP-UHFFFAOYSA-N 0.000 description 1
- JCWBGXXPAPSAFE-UHFFFAOYSA-N 4-chlorobenzenesulfinyl chloride Chemical compound ClC1=CC=C(S(Cl)=O)C=C1 JCWBGXXPAPSAFE-UHFFFAOYSA-N 0.000 description 1
- 206010024229 Leprosy Diseases 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VLKQQIZFPCDLRZ-UHFFFAOYSA-N OO[S](=O)=O Chemical compound OO[S](=O)=O VLKQQIZFPCDLRZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0291—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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Abstract
本发明属于4,4´‑二氯二苯砜的制备工艺技术领域,具体涉及一种利用全氟烷基磺酸离子液体制备4,4´‑二氯二苯砜的工艺。所述的利用全氟烷基磺酸离子液体制备4,4´‑二氯二苯砜的工艺,包括以下步骤:向反应釜中加入全氟烷基磺酸离子液体、氯苯,搅拌加入氯化亚砜,进行傅克反应;继续加入过氧化氢,进行氧化反应;反应结束,后处理即得到4,4´‑二氯二苯砜结晶,并且处理后的全氟烷基磺酸离子液体回收循环利用;所述的全氟烷基磺酸离子液体,具有以下的结构通式:。本发明提供一种利用全氟烷基磺酸离子液体制备4,4´‑二氯二苯砜的工艺,实现氯化亚砜“一锅”制备4,4´‑二氯二苯砜,提高生产效率,降低企业生产成本。
Description
技术领域
本发明属于4,4´-二氯二苯砜的制备工艺技术领域,具体涉及一种利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺。
背景技术
4,4´-二氯二苯砜常被用作聚砜的单体和治疗麻风病的中间体药物,在众多领域有着广泛的应用。CN104402780A公开了一种制备4,4´-二氯二苯砜的方法,氯化亚砜、氯苯在无水三氯化铝催化下发生傅克反应,反应结束后降温加水,再升温溶解,冷却有晶体析出,过滤得到4,4´-二氯二苯亚砜,将其溶于冰醋酸中,滴加双氧水进行氧化反应,反应完毕后降温,过滤,得到4,4´-二氯二苯砜。CN106349126A公开了一种制备4,4´-二氯二苯砜的方法,以4,4´-二氯二苯亚砜为原料,1,2-二氯丙烷为溶剂,催化剂硫酸的用量为4,4´-二氯二苯亚砜质量的6% -12%,冰醋酸的用量为4,4´-二氯二苯亚砜质量的15% -20%,过氧化氢为氧化剂制备4,4´-二氯二苯砜。
以上发明专利制备4,4´-二氯二苯砜都存在一定的问题。以氯化亚砜为原料制备4,4´-二氯二苯砜,都是需要经过傅克酰基化反应和氧化反应来制备目标产物,这两步反应涉及的原料性质、反应机理均不相同。傅克酰基化反应通常使用无水氯化铝等路易斯酸作为催化剂,在常温下就能制备一定量的中间体,但反应过程存在诸多问题。首先是该反应无水氯化铝的加入量和氯化亚砜几乎是等摩尔数的,所以需要消耗大量的催化剂;其次加水淬灭活性络合物来获取中间体产物会剧烈放热,容易引发物料飞溅,高温也会带来较多副反应,所以工业上通过加入冰水等方式来实现控温;氯化铝极易溶于水而无法回收,大量酸性废液带来了储存、环保等问题也有待解决。因此,该反应存在制备工艺流程复杂,反应难控制,催化剂用量大,催化剂不可回收,生产成本高,环境污染等问题。4,4´-二氯二苯亚砜的氧化反应,一般选用过氧化氢作为氧化剂,乙酸、浓硫酸作为反应的催化剂。这类小分子催化剂容易与溶剂形成均相体系,具有反应速率快、产品纯度高的特点,但小分子易溶于氧化反应所生成的副产物水中,从而导致多组分物质难以分离,无机强酸还存在腐蚀设备、污染环境的问题。
为了解决以上存在的问题,本领域技术人员花费了大量时间去研究制备4,4´-二氯二苯砜的催化剂,例如液体酸、固体酸、金属配位化合物、离子液体等催化剂,其中离子液体因自身独特的物理化学性质而受到广大研究者的喜爱,常被用作反应的溶剂和催化剂。在亚砜的氧化反应中,技术人员常选用绿色环保、廉价易得的过氧化氢作为氧化剂,反应不可避免的有水产生,这将导致上述的几类催化剂失活或利用率降低,甚至会出现催化剂无法回收利用的情况,从而增加了生产成本和环境污染。结合现状,4,4´-二氯二苯砜的制备技术需要一种生产效率高,催化剂便于回收,过程绿色环保的生产技术来解决这些问题。
发明内容
本发明要解决的技术问题是提供一种利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,实现氯化亚砜“一锅”制备4,4´-二氯二苯砜,简化了生产工艺流程,提高了生产效率,降低企业生产成本,符合绿色环保的理念。
本发明所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,包括以下步骤:向反应釜中加入全氟烷基磺酸离子液体、氯苯,搅拌加入氯化亚砜,进行傅克反应;每隔0.5h取样用HPLC来检测反应进程,待氯化亚砜转化率达到98%以上,继续加入过氧化氢,进行氧化反应;反应结束,后处理即得到4,4´-二氯二苯砜结晶,并且处理后的全氟烷基磺酸离子液体回收循环利用;
所述的全氟烷基磺酸离子液体,具有以下的结构通式:
简写为[MC2F3RSO3H]X,
其中R= CnF2n+1,n≥0且为整数,n优选为2、3、4、5;
M+为咪唑阳离子、吡啶阳离子、季铵阳离子或季磷阳离子;
X-为双三氟甲基磺酰亚胺负离子([Tf2N]-)、六氟锑酸负离子([SbF6]-)或六氟磷酸负离子([PF6]-)。
氯苯:氯化亚砜:过氧化氢的摩尔比为2:1:(1.1~3)。
全氟烷基磺酸离子液体的加入质量为氯化亚砜质量的3~6倍。
傅克反应温度为30℃~50℃,反应时间为1h~8h。
氧化反应温度为70℃~100℃,反应时间为1h~5h。
后处理包括降温、过滤,得到4,4´-二氯二苯砜结晶粗品,并对其进行清洗,烘干,得到4,4´-二氯二苯砜产品。
降温至温度为5℃~25℃;烘干温度为80℃~100℃。
后处理还包括对过滤后的滤液进行分液,将分离出的全氟烷基磺酸离子液体干燥后用于下一轮反应,分离出的水相用于尾气吸收氯化氢。
具体的,本发明中全氟烷基磺酸离子液体的制备方法,包括以下步骤:
在带有回流装置的反应容器中加入醇溶液作为反应溶剂,加入离子液体的阳离子组成物质(M),置于冰水浴中。打开磁力搅拌,以1~3滴/s的速度滴加全氟烷烃-β-磺内酯,反应12~24h,有不溶盐结晶析出;升温至60℃~90℃,加入离子液体的阴离子组成物质(X),保持搅拌,反应5~12h;反应结束后,分出下层离子液体,用去离子水冲洗三次。将离子液体放入真空烘箱80℃~200℃,干燥5~12h,即可得到全氟烷基磺酸离子液体。
上述制备全氟烷基磺酸离子液体中,阳离子组成:全氟烷基磺内酯:阴离子组成摩尔比为1:1:1;醇溶液是一元醇或多元醇的溶液,加入量为全氟烷基磺酸离子液体理论质量的1~3倍。
所述的全氟烷烃-β-磺内酯为四氟乙烷-β-磺内酯、六氟丙烷-β-磺内酯、八氟丁烷-β-磺内酯、十氟戊烷-β-磺内酯中的一种。
全氟烷烃-β-磺内酯的制备方法,包括以下步骤:将三氧化硫与全氟烯烃按照摩尔比=1:1.1,通入反应器混合,反应压力为0.2-0.5MPa,反应5h后,降温至15℃,气液分离,加入三氧化硫质量30%-50%的氯苯。向液体中加入等体积的3%氢氧化钠溶液,在15℃搅拌2h,静置,可得到油相与水相,取出油相进行蒸馏即可得到全氟烷烃-β-磺内酯。
反应式为:
所述的全氟烷基磺酸离子液体的通式为:
其中R=CnF2n+1,n≥0。
具体的,所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,包括以下步骤:
(1)在反应釜中加入全氟烷基磺酸离子液体、氯苯,开启搅拌并加入氯化亚砜,在30℃~50℃进行傅克反应;反应生成的氯化氢气体通入尾气吸收装置,每间隔0.5h取样,用层析薄板或HPLC来监测反应进程,待氯化亚砜转化率达到98%以上,滴加速度控制在1-3滴/s,滴加过氧化氢,升温至70℃~100℃进行氧化反应1~5h;
所述的氯苯:氯化亚砜:过氧化氢的摩尔比为2:1:(1.1~3);
所述的全氟烷基磺酸离子液体的加入质量为氯化亚砜质量的3~6倍;
(2)反应结束后,降温至5℃~25℃,过滤,即可得到4,4´-二氯二苯砜晶体粗品,冲洗粗品,在80℃~100℃烘干,得到产物4,4´-二氯二苯砜,并计算其收率,测试纯度;
(3)将过滤后的滤液进行分液处理,分离的全氟烷基磺酸离子液体干燥后可直接用于下一轮反应,分离出的水相可用于吸收尾气氯化氢。
具体的,本发明利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的反应过程,如下所示:
本发明利用全氟烷基磺酸离子液体催化合成4,4´-二氯二苯砜,以氯化亚砜作为酰化试剂,与氯苯发生亲电取代反应生成亚砜中间体,继续滴加过氧化氢完成氧化反应,全氟烷基磺酸离子液体作为整个合成反应的催化剂兼溶剂。傅克酰基化反应过程是氯化亚砜与强质子酸作用,生成氯化氢和亚硫酰氯正离子,该步骤也是傅克反应的决速步。因为氯苯分子中氯原子的对位富电子和空间位阻小,所以亚硫酰氯正离子一旦形成后会优先进攻更容易反应的氯苯,而不是离子液体中电子效应和空间位阻都不占优势的全氟阴离子。同理,对氯苯亚磺酰氯在强质子酸催化下重复上述反应过程,与氯苯反应生成4,4´-二氯二苯亚砜。氧化反应主要是利用强酸性环境下,磺酸基可以与过氧化氢作用生成过氧磺酸,达到快速、彻底氧化4,4´-二氯二苯亚砜的目的。待反应结束后,通过分液分出离子液体,简单处理即可实现回收再用。因此,全氟烷基磺酸离子液体催化氯化亚砜合成4,4´-二氯二苯砜是一种新颖、高效、绿色的合成方法。
本发明的离子液体,可通过改变离子液体中阴/阳离子的烷基链长或者在阴/阳离子上引入不同的官能团使离子液体的性质产生变化,因此可以在分子水平上对离子液体进行设计和调控,从而得到特定性质和功能的离子液体。
本发明采用的全氟烷基磺酸离子液体在制备4,4´-二氯二苯砜的工艺中,有效解决现有技术的制备方法所带来的问题,以氯化亚砜为原料制备4,4´-二氯二苯砜的反应过程中,通常需要经过傅克酰基化反应和过氧化氢参与的氧化反应。本发明将这两种反应通过共用一种全氟烷基磺酸离子液体,作为整个反应的溶剂和催化剂,实现“一锅”产出4,4´-二氯二苯砜,简化了工艺流程,提高了生产效率,全氟烷基磺酸离子液体催化剂的溶解性随温度变化而变化,其同时作为一种溶剂,当温度升高时,与有机物、水等都有较好的溶解性,当温度较低时与水形成分层,完美解决了溶剂和催化剂回收的难题。全氟烷基磺酸离子液体中氟原子的电负性大、原子半径小、碳氟键能大、键长短,使碳氟链疏水作用远比碳氢链强烈,所以全氟烷基磺酸离子液体具有特殊的耐水性,全氟烷基磺酸离子液体属于全氟氧超酸,酸性超过100%硫酸,其酸性在水溶液中排序是第一位的(Acidities of strongneutral Brønsted acids indifferent media,2012,Journal of Physical OrganicChemistry)。在全氟烷基强拉电子效应的协同下,电荷产生高度离域化,烷基磺酸链又降低了其结构的对称性,这些因素都有利于降低离子液体的粘度和熔点。因此,本发明采用的全氟烷基磺酸离子液体是氯化亚砜法合成4,4´-二氯二苯砜的理想溶剂和催化剂,其显著特点是溶解性的变化和强酸性、耐水性、低熔点、低粘度。
与现有技术相比,本发明具有的有益效果是:
(1)本发明采用全氟烷基磺酸离子液体参与氯化亚砜合成4,4´-二氯二苯砜,所涉及的两类反应共用一种离子液体催化剂兼溶剂,“一锅”制备4,4´-二氯二苯砜,解决了氯化铝、乙酸、硫酸等催化剂溶于水或溶剂带来的多组分分离难题,具有工艺流程简短、反应过程安全可靠的特点,提高产品质量,极大的节约了生产成本。
(2)本发明中采用的全氟烷基磺酸离子液体具有催化剂和溶剂效果,可设计性强,不挥发,熔点低,粘度低,耐水性好,易于分离,可反复使用,符合绿色清洁生产要求。
附图说明
图1为实施例2合成的4,4´-二氯二苯亚砜的HPLC图;
图2为实施例2合成的4,4´-二氯二苯砜的HPLC图。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
所述的全氟烷基磺酸离子液体为[Py(CF2)2SO3H]Tf2N、[BuimC2F3(CF3)SO3H]PF6、[NEt 3C2F3(C2F5)SO3H]SbF6、[PBu3 C2F3(C3F7) SO3H] Tf2N;其制备方法分别为以下步骤。
(1)全氟烷基磺酸离子液体[Py(CF2)2SO3H]Tf2N的制备:
第一步:在带有回流装置的2L烧瓶中加入550.00g乙醇、79.11g(1mol)吡啶,置于冰水浴中,打开磁力搅拌,以1滴/s的速度逐滴加入180.08g(1mol)四氟乙烷-β-磺内酯,反应24h。
第二步:升温至60℃,加入281.15g(1mol)双三氟甲磺酰亚胺,搅拌反应12h,反应结束后,分出下层离子液体,用去离子水冲洗三次。将离子液体放入真空烘箱100℃,保持12h,制得全氟烷基磺酸离子液体[Py(CF2)2SO3H]Tf2N。
上述合成过程涉及的化学反应式如下:
(2)全氟烷基磺酸离子液体[BuimC2F3(CF3)SO3H]PF6的制备:
第一步:在带有回流装置的2L烧瓶中加入800.00g乙醇、124.18g(1mol)N-丁基咪唑,置于冰水浴中,打开磁力搅拌,以1滴/s的速度逐滴加入230.08g(1mol)六氟丙烷-β-磺内酯,反应18h。
第二步:升温至70℃,加入243.30g(1mol)60%水溶液的六氟磷酸,搅拌反应10h,反应结束后,分出下层离子液体,用去离子水冲洗三次。将离子液体放入真空烘箱140℃,保持10h,制得全氟烷基磺酸离子液体[BuimC2F3(CF3)SO3H]PF6。
(3)全氟烷基磺酸离子液体[NEt 3C2F3(C2F5)SO3H]SbF6的制备:
第一步:在带有回流装置的2L烧瓶中加入800.00g乙醇、101.19g(1mol)三乙胺,置于冰水浴中,打开磁力搅拌,以1滴/s的速度逐滴加入330.08g(1mol)八氟丁烷-β-磺内酯,反应15h。
第二步:升温至80℃,加入364.85g(1mol)六氟锑酸六水化合物,搅拌反应8h,反应结束后,分出下层离子液体,用去离子水冲洗三次。将离子液体放入真空烘箱180℃,保持8h,制得全氟烷基磺酸离子液体[NEt 3C2F3(C2F5)SO3H]SbF6。
(4)全氟烷基磺酸离子液体[PBu3 C2F3(C3F7) SO3H] Tf2N的制备:
第一步:在带有回流装置的2L烧瓶中加入700.00g乙醇、202.00g(1mol)三丁基膦,置于冰水浴中,打开磁力搅拌,以1滴/s的速度逐滴加入180.08g(1mol)十氟戊烷-β-磺内酯,反应12h。
第二步:升温至90℃,加入243.30g(1mol)双三氟甲磺酰亚胺,搅拌反应5h,反应结束后,分出下层离子液体,用去离子水冲洗三次。将离子液体放入真空烘箱200℃,保持5h,制得全氟烷基磺酸离子液体[PBu3 C2F3(C3F7) SO3H] Tf2N。
实施例1
所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,包括以下步骤:
(1)在反应釜中加入357.00g上述制备的[Py(CF2)2SO3H]Tf2N、225.12g氯苯,开启搅拌逐滴加入氯化亚砜118.97g,油浴控制反应温度为30℃,反应生成的氯化氢气体通入尾气吸收装置,每间隔0.5h取样,通过HPLC来监测反应进程,3.5h后反应结束;
(2)升温至70℃,取125.70g 30%过氧化氢滴加到反应釜中;通过HPLC来监测反应进程,5h后反应结束,降至5℃,过滤,80℃真空干燥至恒重,即可得到258.96g 4,4´-二氯二苯砜;计算其收率,利用HPLC测其纯度;
(3)将滤液进行分液处理,干燥后[Py(CF2)2SO3H]Tf2N回收356.41g,分离出的水相用于吸收尾气氯化氢,计算[Py(CF2)2SO3H]Tf2N回收率。
实施例2
所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,包括以下步骤:
(1)在反应釜中加入474.91g 上述制备的[BuimC2F3(CF3)SO3H]PF6、225.12g氯苯,开启搅拌逐滴加入氯化亚砜118.97g,油浴控制反应温度为40℃,反应生成的氯化氢气体通入尾气吸收装置,每间隔0.5h取样,通过HPLC来监测反应进程,3h后反应结束;
(2)升温至80℃,取195.70g 30%过氧化氢滴加到反应釜中;通过HPLC来监测反应进程,3h后反应结束,降至10℃,过滤,90℃真空干燥至恒重,即可得到260.31g4,4´-二氯二苯砜;计算其收率,利用HPLC测其纯度;
(3)将滤液进行分液处理,干燥后[BuimC2F3(CF3)SO3H]PF6回收473.91g,分离出的水相用于吸收尾气氯化氢,计算[BuimC2F3(CF3)SO3H]PF6回收率。
实施例3
所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,包括以下步骤:
(1)在反应釜中加入592.91g 上述制备的[NEt 3C2F3(C2F5)SO3H]SbF6、225.12g氯苯,开启搅拌逐滴加入氯化亚砜118.97g,油浴控制反应温度为50℃,反应生成的氯化氢气体通入尾气吸收装置,每间隔0.5h取样,通过HPLC来监测反应进程,2h后反应结束;
(2)升温至90℃,取266.70g 30%过氧化氢滴加到反应釜中;通过HPLC来监测反应进程,2.5h后反应结束,降至15℃,过滤,100℃真空干燥至恒重,即可得到258.14g4,4´-二氯二苯砜;计算其收率,利用HPLC测其纯度;
(3)将滤液进行分液处理,干燥后[NEt 3C2F3(C2F5)SO3H]SbF6回收591.31g,分离出的水相用于吸收尾气氯化氢,计算[NEt 3C2F3(C2F5)SO3H]SbF6回收率。
实施例4
所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,包括以下步骤:
(1)在反应釜中加入713.82g制备的[PBu3 C2F3(C3F7) SO3H] Tf2N、225.12g氯苯,开启搅拌逐滴加入氯化亚砜118.97g,油浴控制反应温度为40℃,反应生成的氯化氢气体通入尾气吸收装置,每间隔0.5h取样,通过HPLC来监测反应进程,3h后反应结束;
(2)升温至100℃,取340.10g 30%过氧化氢滴加到反应釜中;通过HPLC来监测反应进程,1.5h后反应结束,降至25℃,过滤,100℃真空干燥至恒重,即可得到258.42g4,4´-二氯二苯砜;计算其收率,利用HPLC测其纯度;
(3)将滤液进行分液处理,干燥后[PBu3 C2F3(C3F7) SO3H] Tf2N回收712.96g,分离出的水相用于吸收尾气氯化氢,计算[PBu3 C2F3(C3F7) SO3H] Tf2N回收率。
实施例5
所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,包括以下步骤:
(1)在反应釜中加入180.00g 实施例1第一次循环回收的[Py(CF2)2SO3H]Tf2N、112.56g氯苯,开启搅拌逐滴加入氯化亚砜59.49g,油浴控制反应温度为30℃,反应生成的氯化氢气体通入尾气吸收装置,每间隔0.5h取样,通过HPLC来监测反应进程,3.5h后反应结束;
(2)升温至70℃,取62.35g 30%过氧化氢滴加到反应釜中;通过HPLC来监测反应进程,5h后反应结束,降至5℃,过滤,80℃真空干燥至恒重,即可得到257.87,4,4´-二氯二苯砜;计算其收率,利用HPLC测其纯度;
(3)将滤液进行分液处理,干燥后回收[Py(CF2)2SO3H]Tf2N共179.60g,分离出的水相用于吸收尾气氯化氢,计算[Py(CF2)2SO3H]Tf2N回收率。
实施例6
所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,包括以下步骤:
(1)在反应釜中加入179.60g 实施例5循环得到的[Py(CF2)2SO3H]Tf2N、112.56g氯苯,开启搅拌逐滴加入氯化亚砜59.49g,油浴控制反应温度为30℃,反应生成的氯化氢气体通入尾气吸收装置,每间隔0.5h取样,通过HPLC来监测反应进程,3.5h后反应结束;
(2)升温至70℃,取62.35g30%过氧化氢滴加到反应釜中;通过HPLC来监测反应进程,5h后反应结束,降至5℃,过滤,80℃真空干燥至恒重,即可得到258.96g4,4´-二氯二苯砜;计算其收率,利用HPLC测其纯度;
(3)将滤液进行分液处理,干燥后[Py(CF2)2SO3H]Tf2N回收178.89g,分离出的水相用于吸收尾气氯化氢,计算[Py(CF2)2SO3H]Tf2N回收率。
实施例7
所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,包括以下步骤:
(1)在反应釜中加入178.89g实施例6循环得到的[Py(CF2)2SO3H]Tf2N、112.56g氯苯,开启搅拌逐滴加入氯化亚砜59.49g,油浴控制反应温度为30℃,反应生成的氯化氢气体通入尾气吸收装置,每间隔0.5h取样,通过HPLC来监测反应进程,3.5h后反应结束;
(2)升温至70℃,取62.35g30%过氧化氢滴加到反应釜中;通过HPLC来监测反应进程,5h后反应结束,降至5℃,过滤,80℃真空干燥至恒重,即可得到257.60 g4,4´-二氯二苯砜;计算其收率,利用HPLC测其纯度;
(3)将滤液进行分液处理,干燥后[Py(CF2)2SO3H]Tf2N回收178.26g,分离出的水相用于吸收尾气氯化氢,计算[Py(CF2)2SO3H]Tf2N回收率。
对比例1
无水氯化铝、乙酸、浓硫酸催化合成4,4´-二氯二苯砜,包括以下步骤:
(1)在反应釜中加入356.70g 1,2-二氯丙烷、225.12g氯苯、133.34g氯化铝,开启搅拌逐滴加入氯化亚砜118.97g,油浴控制反应温度为30℃,反应生成的氯化氢气体通入尾气吸收装置。每间隔0.5h取样,用HPLC来监测反应进程。5h后反应结束,缓慢加水控制为2滴/s,反应釜温度在十分钟升至92℃。完全淬灭后,分离出氯化铝水溶液。
(2)升温至85℃,分别滴加40.68g乙酸、16.26g浓硫酸、232g 30%过氧化氢到反应釜中。10h后反应结束,降温,过滤,80℃真空干燥至恒重,即可得到4,4´-二氯二苯砜,计算收率为91.77%,取样测试纯度为98.62%。
对比例2
1-乙基-3-甲基咪唑四氯铝酸盐离子液体、乙酸、浓硫酸催化合成4,4´-二氯二苯砜,包括以下步骤:(所述的离子液体催化剂产品编号:LDIM-607,浙江蓝德能源科技发展有限公司生产的)
(1)在反应釜中加入356.70g 1-乙基-3-甲基咪唑四氯铝酸盐离子液体、225.12g氯苯,开启搅拌逐滴加入氯化亚砜118.97g,油浴控制反应温度为30℃,反应生成的氯化氢气体通入尾气吸收装置,每间隔0.5h取样,通过HPLC来监测反应进程,6h后反应结束;
(2)升温至70℃,取124.70g 30%过氧化氢滴加到反应釜中;通过HPLC来监测反应进程,12h后纯度达到34.27%不再变化,降至5℃,过滤,80℃真空干燥至恒重,即可得到212.56g结晶物;
(3)滤液无法进行分液处理,1-乙基-3-甲基咪唑四氯铝酸盐离子液体通过减压蒸馏除去水分,120℃真空干燥8h,1-乙基-3-甲基咪唑四氯铝酸盐离子液体回收214.32g。
对比例3
将对比例2处理后的1-乙基-3-甲基咪唑四氯铝酸盐离子液体进行循环使用,合成4,4´-二氯二苯砜,包括以下步骤:
(1)在反应釜中加入178.35g 1-乙基-3-甲基咪唑四氯铝酸盐离子液体、112.56g氯苯,开启搅拌逐滴加入氯化亚砜59.49g,油浴控制反应温度为40℃,反应生成的氯化氢气体通入尾气吸收装置。每间隔0.5h取样,监测反应进程,12h后纯度为21.78%并不再变化。
(2)升温至70℃,取65.35g 30%过氧化氢滴加到反应釜中;通过HPLC来监测反应进程,12h后纯度达到30.69%不再变化,降至5℃,过滤,80℃真空干燥至恒重,即可得到26.53g结晶物。
将实施例1-7所合成的4,4´-二氯二苯砜,以及对比例1-3合成的4,4´-二氯二苯砜的收率、纯度以及催化剂的收率进行计算与检测,其结果如表1所示:
表1 检测结果
通过实施例,可知全氟烷基磺酸离子液体用于氯化亚砜法合成4,4´-二氯二苯砜十分有效,本发明的全氟烷基磺酸离子液体[Py(CF2)2SO3H]Tf2N经过3次重复使用而不减弱其使用效果。实施例与对比例进行比较,全氟烷基磺酸离子液体的优势是显而易见的,“一锅”产出4,4´-二氯二苯砜工艺简单;各组分易于分离,产物、溶剂和水通过简单分液或过滤即可实现分离;反应过程控制稳定,相应的产物品质稳定可靠,产品纯度高,而氯化铝及其离子液体参与反应放热明显。由对比例2可知,1-乙基-3-甲基咪唑四氯铝酸盐离子液体可用于傅克反应,不适用于氧化反应。对比例3是将对比例2中含1-乙基-3-甲基咪唑四氯铝酸盐离子液体的滤液进行减压蒸馏,获取一定量的1-乙基-3-甲基咪唑四氯铝酸盐离子液体重复用于氯化亚砜制备4,4´-二氯二苯砜的反应,从反应过程监测来看,回收的催化剂已经达不到使用要求,所以回收1-乙基-3-甲基咪唑四氯铝酸盐离子液体并让其具有原本的催化效果是一件高能耗、高难度的事情;众所周知,乙酸、浓硫酸易溶于水且无法分离,面临着回收成本高、污染环境的问题。经过对比,全氟烷基磺酸离子液体是氯化亚砜法制备4,4´-二氯二苯砜的理想催化剂及溶剂。
上述内容仅为本发明的较佳实施例,不能被认为用于限定对本发明的实施例范围。本发明也并不仅限于上述举例,本技术领域的普通技术人员在本发明的实质范围内所做出的均等变化与改进等,均应归属于本发明的专利涵盖范围内。
Claims (8)
1.一种利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,其特征在于:包括以下步骤:向反应釜中加入全氟烷基磺酸离子液体、氯苯,搅拌加入氯化亚砜,进行傅克反应;继续加入过氧化氢,进行氧化反应;反应结束,后处理即得到4,4´-二氯二苯砜结晶,并且处理后的全氟烷基磺酸离子液体回收循环利用;
所述的全氟烷基磺酸离子液体,具有以下的结构通式:
其中R= CnF2n+1,n≥0且为整数;
M+为咪唑阳离子、吡啶阳离子、季铵阳离子或季磷阳离子;
X-为双三氟甲基磺酰亚胺负离子、六氟锑酸负离子或六氟磷酸负离子。
2.根据权利要求1所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,其特征在于:氯苯:氯化亚砜:过氧化氢的摩尔比为2:1:(1.1~3)。
3.根据权利要求1所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,其特征在于:全氟烷基磺酸离子液体的加入质量为氯化亚砜质量的3~6倍。
4.根据权利要求1所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,其特征在于:傅克反应温度为30℃~50℃,反应时间为1h~8h。
5.根据权利要求1所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,其特征在于:氧化反应温度为70℃~100℃,反应时间为1h~5h。
6.根据权利要求1所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,其特征在于:后处理包括降温、过滤,得到4,4´-二氯二苯砜结晶粗品,并对其进行清洗,烘干,得到4,4´-二氯二苯砜产品。
7.根据权利要求6所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,其特征在于:降温至温度为5℃~25℃;烘干温度为80℃~100℃。
8.根据权利要求6所述的利用全氟烷基磺酸离子液体制备4,4´-二氯二苯砜的工艺,其特征在于:后处理还包括对过滤后的滤液进行分液,将分离出的全氟烷基磺酸离子液体干燥后用于下一轮反应,分离出的水相用于尾气吸收氯化氢。
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