CN106554359B - Application of the sulfonated graphene resin type catalyst in Baeyer-Villiger oxidation reactions - Google Patents
Application of the sulfonated graphene resin type catalyst in Baeyer-Villiger oxidation reactions Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000011347 resin Substances 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 title claims abstract description 38
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 title claims description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229960002163 hydrogen peroxide Drugs 0.000 claims abstract description 26
- 150000002576 ketones Chemical class 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 12
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 239000002798 polar solvent Substances 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 3
- 239000000284 extract Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- LFSAPCRASZRSKS-UHFFFAOYSA-N 2-methylcyclohexan-1-one Chemical class CC1CCCCC1=O LFSAPCRASZRSKS-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- PJXHBTZLHITWFX-UHFFFAOYSA-N 2-heptylcyclopentan-1-one Chemical compound CCCCCCCC1CCCC1=O PJXHBTZLHITWFX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000004431 polycarbonate resin Substances 0.000 claims description 2
- 229920005668 polycarbonate resin Polymers 0.000 claims description 2
- 229920005990 polystyrene resin Polymers 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 239000000805 composite resin Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 24
- 239000012074 organic phase Substances 0.000 description 24
- 239000002904 solvent Substances 0.000 description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 239000002024 ethyl acetate extract Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000001737 promoting effect Effects 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- -1 sulfonated graphite Alkene Chemical class 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000002596 lactones Chemical class 0.000 description 5
- 238000006277 sulfonation reaction Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 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 2
- 229910016287 MxOy Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 150000003997 cyclic ketones Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QRPLZGZHJABGRS-UHFFFAOYSA-N xi-5-Dodecanolide Chemical compound CCCCCCCC1CCCC(=O)O1 QRPLZGZHJABGRS-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical class [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Catalysts (AREA)
Abstract
The invention discloses application of the sulfonated graphene resin type catalyst in Beayer Villiger oxidative synthesis, and using hydrogen peroxide as Green Oxidant, sulfonated graphene resin composite materials are catalyst, catalysis oxidation ketone synthetic ester.Ketone is dissolved in organic solvent first, then hydrogenperoxide steam generator and sulfonated graphene resin type catalyst is added, it is stirred to react completely, polar solvent is added after reaction catalyst is precipitated, the mixed liquor after catalyst is precipitated to be centrifuged to obtain supernatant, supernatant is washed again, extracts, obtains esters product after distillation.The sulfonated graphene resin type catalyst of the present invention is prepared simply, and the catalyst in being reacted using sulfonated graphite olefine resin as Beayer Villiger improves the conversion ratio of ketone；Sulfonated graphene resin type catalyst is reusable；No spent acid processing, energy-saving and emission-reduction；Selectivity is good, and atomic efficiency is high；Reaction condition is mild, and the characteristics such as clean environment are suitable for Industrial Engineering application.
Description
Technical field
The present invention relates to application of the sulfonated graphene resin type catalyst in Baeyer-Villiger oxidation reactions, i.e.,
Using ketone as raw material, using hydrogen peroxide as Green Oxidant, pass through for catalyst using sulfonated graphene resin composite materials
The method of Baeyer-Villiger oxidation reaction catalysis ketone synthetic esters, belongs to technical field of organic chemistry.
Background technology
It it is inserted into oxygen in open chain ketone or cyclic ketones molecule generates the reaction of corresponding ester or lactone and be known as Baeyer-
Villiger (BV) oxidation reaction.Different according to the oxidant applied in reaction, BV oxidation reactions can be divided mainly into peroxy acid oxygen
Change, hydrogen peroxide oxidation and dioxygen oxidation etc..Now with the most commonly used of hydrogen peroxide and oxygen, the two is easy to extensive
Industrial applications and environmental protection.However it is usually relatively low as the reaction selectivity of oxidant and conversion ratio using hydrogen peroxide and oxygen,
Therefore developing corresponding effective catalyst is particularly important.
Using hydrogenperoxide steam generator as in the BV oxidation reaction systems of oxidant, be broadly divided into homogeneous catalysis, enzymatic and
3 major class of heterogeneous catalysis (The Baeyer-Villiger reaction on heterogeneous catalysts, Ce ' sar
64 (2008) 2011-2026 of Jime ' nez-Sanchidria ' n, Joes ' Rafael Ruiz, Tetrahedron).Homogeneously urge
Agent has preferable catalytic effect, but is difficult to detach from product, and recycling rate of waterused is low.Biological enzyme agent has efficient
Property, highly selective and specificity, but enzyme-catalyzed reaction condition need to accurately control, and the catalytic efficiency of enzyme in organic solvent is low simultaneously
It is difficult to recycle.Heterogeneous catalyst high temperature resistant easily removes, and can be recycled, and catalytic performance is convenient for monitoring in reaction process.
It is mostly metallic compound and solid acid catalyst to apply the heterogeneous catalyst in BV reactions at present.Metallic compound
There is higher catalytic activity and selectivity in BV reactions, be easy to get the smaller cyclic ketones of steric hindrance to high conversion and single
Product lactone (synthesis and catalyzing ketone Beayer-Villiger oxidation reaction researchs of tin compound catalyst, Yang Zhiwang).But
Metallic compound especially metal organic complex is expensive, and it is very big to do catalyst cost with it；And part metallization
Close object has corrosivity for equipment, this also affects their application in certain degree.Solid acid catalyst can be divided into
Immobilized liquid acid, oxide, sulfide, metal salt, zeolite molecular sieve, heteropoly acid, cation exchange resin, natural clay mine
With solid super-strong acid this nine major class (classification of solid acid and Recent Research, Liu Qinghui, Zhan Hongchang, the quick thumb of soup, Chemical Industry in Guangzhou
2008(36)14-17).Wherein, SO4 2-/ MxOy type solid super-strong acids, including SO4 2-Based on oxides such as Fe, Ti, Sn, Zr and Hf
Solid super-strong acid has the following advantages:1. water stability is fine, such as SO4 2-/ZrO2In air after a long time placement, it only needs
Heating 1 hour can activity recovery by the water removing of adsorption；2. the SO of its adsorption4 2-Stabilization is combined with carrier surface；
3. can use at high temperature；4. corrosivity very little.SO4 2-The above-mentioned advantage of/MxOy type solid super-strong acids makes it on Lipase absobed
It is widely used.
Invention content
The application and its application side that the present invention provides a kind of sulfonated graphene resin type catalysts in BV oxidation reactions
Method, using hydrogen peroxide as Green Oxidant, sulfonated graphene resin composite materials be catalyst, catalysis oxidation ketone synthetic ester, newly
Method reaction condition is mild, and good, the high income of selectivity, no spent acid generates, and is suitable for engineering to convert, the sulfonated graphene tree
Epoxy-type catalyst is the compound of sulfonated graphene and resin.
Realize the technical scheme is that：
Application process of the sulfonated graphene resin type catalyst in BV oxidation reactions, includes the following steps：
Ketone is dissolved in organic solvent, hydrogenperoxide steam generator and sulfonated graphene resin type catalyst, stirring is then added
The reaction was complete, polar solvent is added after reaction, catalyst is precipitated, and the mixed liquor after catalyst is precipitated and is centrifuged
To supernatant, last supernatant is washed, extracts, obtains esters product after distillation.
The sulfonated graphene resin type catalyst is prepared by following steps：
Graphene is dissolved in organic solvent, sulfonating reaction is carried out at room temperature after the concentrated sulfuric acid is added, after reaction centrifugation point
From, it is dried to obtain sulfonated graphene, then sulfonated graphene and resin are dissolved in organic solvent, after ultrasonic disperse is uniform, analysis
Go out, filter, being drying to obtain sulfonated graphene resin type catalyst.
The resin is the hydrophobic resin of solid, and preferable plasticity is easily isolated and had in multiphase solvent system,
Preferably in polystyrene resin, ABS resin, polyvinyl resin, acrylic resin, polycarbonate resin and Corvic
One kind.
The mass ratio of the graphene and the concentrated sulfuric acid is 1:3.5~5, the sulfonating reaction time be 18~for 24 hours, sulfonated graphite
The molar ratio of alkene and resin is 1:4~5, ultrasonic time is 20~25h.
The ketone in 2- Buddha's warrior attendants alkanone, alismone, 2- methyl cyclohexanones, cyclopentanone and cyclohexanone one
Kind.
The organic solvent is preferably one kind in dichloromethane, ethyl acetate, dichloroethanes, ether and chloroform.
The polar solvent is preferably one kind in ethyl alcohol, methanol, water, acetonitrile and dimethyl sulfoxide (DMSO).
The quality of the sulfonated graphene resin type catalyst is the 10%~20% of ketone, and the reaction temperature is 25
~55 DEG C, the reaction time is 10~20h, and the mass fraction of the hydrogenperoxide steam generator is 30%~50%；The peroxide
The molar ratio for changing hydrogen and ketone is 2~3.5:1.
The reaction mechanism of sulfonated graphene resin type catalyst catalysis oxidation ketone synthetic ester is as follows：
As shown above：That work in catalyst is-SO3H ,-SO3H plays the role of activating ketone in the reaction.
Compared with prior art, the present invention has following remarkable advantage：(1) compared with existing BV oxidation reaction catalysts,
The sulfonated graphene resin type catalyst high catalytic efficiency of the present invention, selectivity are good；(2) sulfonated graphene resin type catalyst can
It recycles and reuses；(3) when using low concentration hydrogen peroxide solution as oxidant, the catalysis of sulfonated graphene resin type catalyst
It is efficient, product yield is improved, and improve safety and the spatter property of industrially prepared reaction；(4) sulfonated graphene tree
The reaction condition of epoxy-type catalyst oxydone synthetic ester is mild, and not needing high temperature and pressure can react.
Specific implementation mode
The invention will be further described With reference to embodiment.
Embodiment 1
0.81g graphenes are added in three-necked bottle, add 10mL dichloromethane as solvent, it is in the case where adding ultrasound that its is complete
Full dispersion, is cooled to room temperature.The concentrated sulfuric acid of 4.05g 98wt% is then added as sulfonated reagent, carry out sulphur is stirred at room temperature
Change reaction, reaction time 18h.Ultrasonic Separation after reaction obtains sulfonated graphene after solid product drying.Take above-mentioned system
It obtains sulfonated graphene 0.50g to be placed in three-necked bottle, it is that solvent is completely dispersed that 10mL dichloromethane, which is added, adds 2.52g
Polystyrene is stirred to react 25h.After the reaction was complete, product is precipitated with ethyl alcohol, is filtered, it is dry after washing, obtain sulfonated graphite
Alkene polyphenylacetylene catalyst.
In 50mL three-necked flasks, 0.50g 2- Buddha's warrior attendant alkanones, 5mL dichloromethane, 0.10g sulfonated graphene polyphenyl is added
Catalyst for ethylene, is added dropwise 30wt% hydrogenperoxide steam generators, and hydrogen peroxide is 3.5 with 2- Buddha's warrior attendant alkanone molar ratios:1.At 45 DEG C
It is stirred to react 20h.Catalyst is precipitated with ethyl alcohol after reaction, reaction solution is extracted 3 times with 5mL ethyl acetate, has been isolated
Machine phase.It takes the sodium bicarbonate solution of 2mL 5% to wash organic phase 3 times, then organic phase is washed to neutrality with deionized water.With
Water phase is adjusted to alkalescent and is extracted with ethyl acetate by 5% sodium bicarbonate solution, by acetic acid ethyl acetate extract and organic phase
Merge, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The conversion ratio of 2- Buddha's warrior attendant alkanones is 96%, ε-
The yield of Buddha's warrior attendant alkanone lactone is 88%.
Embodiment 2
0.81g graphenes are added in three-necked bottle, add 10mL ethyl acetate as solvent, it is in the case where adding ultrasound that its is complete
Full dispersion, is cooled to room temperature.The concentrated sulfuric acid of 3.65g 98wt% is then added as sulfonated reagent, carry out sulphur is stirred at room temperature
Change reaction, reaction time 20h.Ultrasonic Separation after reaction obtains sulfonated graphene after solid product drying.Take above-mentioned system
It obtains sulfonated graphene 0.51g to be placed in three-necked bottle, it is that solvent is completely dispersed that 10mL ethyl acetate, which is added, is added
2.29gABS resins, are stirred to react 22h.After the reaction was complete, product is precipitated with methanol, is filtered, it is dry after washing, obtain sulfonation
Graphene ABS resin catalyst.
In 50mL three-necked flasks, 0.51g alismones, 5mL ethyl acetate, 0.10g sulfonated graphenes is added
ABS resin catalyst, is added dropwise 35wt% hydrogenperoxide steam generators, and hydrogen peroxide is 3.1 with alismone molar ratio:1.40
10h is stirred to react at DEG C.Catalyst is precipitated with methanol after reaction, reaction solution is extracted 3 times with 5mL ethyl acetate, separation
Go out organic phase.It takes the sodium bicarbonate solution of 2mL 5% to wash organic phase 3 times, then organic phase is washed to neutrality with deionized water.
Water phase is adjusted to alkalescent with 5% sodium bicarbonate solution and is extracted with ethyl acetate, by acetic acid ethyl acetate extract with it is organic
Mutually merge, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The conversion ratio of alismone is
99%, the yield of δ-dodecalactone is 91%.
Embodiment 3
0.80g graphenes are added in three-necked bottle, add 10mL dichloroethanes as solvent, it is in the case where adding ultrasound that its is complete
Full dispersion, is cooled to room temperature.The concentrated sulfuric acid of 3.20g 98wt% is then added as sulfonated reagent, carry out sulphur is stirred at room temperature
Change reaction, reaction time 22h.Ultrasonic Separation after reaction obtains sulfonated graphene after solid product drying.Take above-mentioned system
It obtains sulfonated graphene 0.51g to be placed in three-necked bottle, it is that solvent is completely dispersed that 10mL dichloroethanes, which is added, adds 2.04g
Polyvinyl resin is stirred to react 21h.After the reaction was complete, product is precipitated with water, is filtered, it is dry after washing, obtain sulfonated graphite
Alkene polyethylene catalysts.
In 50mL three-necked flasks, 0.51g 2- methyl cyclohexanones, 5mL dichloroethanes is added, 0.10g sulfonated graphenes gather
Catalyst for ethylene, is added dropwise 40wt% hydrogenperoxide steam generators, and hydrogen peroxide is 2.7 with 2- methyl cyclohexanone molar ratios:1.At 40 DEG C
Under be stirred to react 20h.Catalyst is precipitated with water after reaction, reaction solution is extracted 3 times with 5mL ethyl acetate, has been isolated
Machine phase.It takes the sodium bicarbonate solution of 2mL 5% to wash organic phase 3 times, then organic phase is washed to neutrality with deionized water.With
Water phase is adjusted to alkalescent and is extracted with ethyl acetate by 5% sodium bicarbonate solution, by acetic acid ethyl acetate extract and organic phase
Merge, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The conversion ratio of 2- methyl cyclohexanones is 92%,
The yield of 7- methyl -2- oxepanes is 86%.
Embodiment 4
0.81g graphenes are added in three-necked bottle, adds 10mL ether as solvent, divides it completely in the case where adding ultrasound
It dissipates, is cooled to room temperature.The concentrated sulfuric acid of 2.84g 98wt% is then added as sulfonated reagent, it is anti-that progress sulfonation is stirred at room temperature
It answers, the reaction time is for 24 hours.Ultrasonic Separation after reaction obtains sulfonated graphene after solid product drying.Take above-mentioned obtained sulphur
Graphite alkene 0.52g is placed in three-necked bottle, and it is that solvent is completely dispersed that 10mL ether, which is added, adds 2.05g polypropylene trees
Fat is stirred to react 20h.After the reaction was complete, product is precipitated with acetonitrile, is filtered, it is dry after washing, obtain sulfonated graphene poly- third
Alkene catalyst.
In 50mL three-necked flasks, addition 0.50g cyclopentanone, 5mL ether, 0.05g sulfonated graphene polypropylene catalysts,
45wt% hydrogenperoxide steam generators are added dropwise, hydrogen peroxide is 2.4 with cyclopentanone molar ratio:1.It is stirred to react 15h at 25 DEG C.Reaction
After catalyst is precipitated with acetonitrile, reaction solution with 5mL ethyl acetate extract 3 times, isolate organic phase.Take 2mL's 5%
Sodium bicarbonate solution washs organic phase 3 times, then organic phase is washed to neutrality with deionized water.With 5% sodium bicarbonate solution
Water phase is adjusted to alkalescent and is extracted with ethyl acetate, acetic acid ethyl acetate extract is merged with organic phase, rotary evaporation in vacuo,
Remove solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The conversion ratio of cyclopentanone is that the yield of 64%, δ-ring valerolactones is 45%.
Embodiment 5
0.80g graphenes are added in three-necked bottle, adds 10mL chloroforms as solvent, divides it completely in the case where adding ultrasound
It dissipates, is cooled to room temperature.The concentrated sulfuric acid of 4.00g 98wt% is then added as sulfonated reagent, it is anti-that progress sulfonation is stirred at room temperature
It answers, reaction time 18h.Ultrasonic Separation after reaction obtains sulfonated graphene after solid product drying.Take above-mentioned obtained sulphur
Graphite alkene 0.51g is placed in three-necked bottle, and it is that solvent is completely dispersed that 10mL chloroforms, which are added, adds 2.30g makrolon
Resin is stirred to react 23h.After the reaction was complete, product is precipitated with dimethyl sulfoxide (DMSO), is filtered, it is dry after washing, obtain sulfonation stone
Black alkene polycarbonate catalyst.
In 50mL three-necked flasks, 0.51g cyclohexanone, 5mL chloroforms, 0.10g sulfonated graphene polycarbonate catalysts is added
Agent, is added dropwise 50wt% hydrogenperoxide steam generators, and hydrogen peroxide is 2 with cyclohexanone molar ratio:1.It is stirred to react 20h at 55 DEG C.Instead
Catalyst is precipitated with dimethyl sulfoxide (DMSO) after answering, reaction solution is extracted 3 times with 5mL ethyl acetate, isolates organic phase.It takes
The sodium bicarbonate solution washing organic phase of 2mL 5% 3 times, then organic phase is washed to neutrality with deionized water.With 5% carbonic acid
Water phase is adjusted to alkalescent and is extracted with ethyl acetate by hydrogen sodium solution, acetic acid ethyl acetate extract is merged with organic phase, vacuum
Rotary evaporation removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The conversion ratio of cyclohexanone is the production of 82%, ε-hexamethylene lactones
Rate is 47%.
Embodiment 6
0.81g graphenes are added in three-necked bottle, add 10mL dichloromethane as solvent, it is in the case where adding ultrasound that its is complete
Full dispersion, is cooled to room temperature.The concentrated sulfuric acid of 3.65g 98wt% is then added as sulfonated reagent, carry out sulphur is stirred at room temperature
Change reaction, reaction time 20h.Ultrasonic Separation after reaction obtains sulfonated graphene after solid product drying.Take above-mentioned system
It obtains sulfonated graphene 0.50g to be placed in three-necked bottle, it is that solvent is completely dispersed that 10mL dichloromethane, which is added, adds 2.51g
Corvic is stirred to react for 24 hours.After the reaction was complete, product is precipitated with ethyl alcohol, is filtered, it is dry after washing, obtain sulfonation
Graphene polyvinyl chloride catalyst.
In 50mL three-necked flasks, 0.50g 2- Buddha's warrior attendant alkanones, 5mL dichloromethane, 0.05g sulfonated graphene polychlorostyrene is added
Catalyst for ethylene, is added dropwise 30wt% hydrogenperoxide steam generators, and hydrogen peroxide is 2.5 with 2- Buddha's warrior attendant alkanone molar ratios:1.At 40 DEG C
It is stirred to react 20h.Catalyst is precipitated with ethyl alcohol after reaction, reaction solution is extracted 3 times with 5mL ethyl acetate, has been isolated
Machine phase.It takes the sodium bicarbonate solution of 2mL 5% to wash organic phase 3 times, then organic phase is washed to neutrality with deionized water.With
Water phase is adjusted to alkalescent and is extracted with ethyl acetate by 5% sodium bicarbonate solution, by acetic acid ethyl acetate extract and organic phase
Merge, rotary evaporation in vacuo, removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The conversion ratio of 2- Buddha's warrior attendant alkanones is 71%, ε-
The yield of Buddha's warrior attendant alkanone lactone is 63%
Comparative example
In 50mL three-necked flasks, 0.51g 2- Buddha's warrior attendant alkanones, 5mL dichloromethane, the catalysis of 0.05g Iron trichloride hexahydrates is added
Agent, is added dropwise 30wt% hydrogenperoxide steam generators, and hydrogen peroxide is 2.5 with 2- Buddha's warrior attendant alkanone molar ratios:1.It is stirred to react at 40 DEG C
20h.Catalyst is precipitated with ethyl alcohol after reaction, reaction solution is extracted 3 times with 5mL ethyl acetate, isolates organic phase.It takes
The sodium bicarbonate solution washing organic phase of 2mL 5% 3 times, then organic phase is washed to neutrality with deionized water.With 5% carbonic acid
Water phase is adjusted to alkalescent and is extracted with ethyl acetate by hydrogen sodium solution, acetic acid ethyl acetate extract is merged with organic phase, vacuum
Rotary evaporation removes solvent, promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The conversion ratio of 2- Buddha's warrior attendant alkanones is 39%, ε-Buddha's warrior attendant alkanones
The yield of lactone is 31%.
Claims (7)
1. sulfonated graphene resin type catalyst is in the Baeyer-Villiger oxidation reactions using hydrogen peroxide as oxidant
Application, the sulfonated graphene resin type catalyst be sulfonated graphene and resin compound, the resin is solid
The hydrophobic resin of body.
2. application according to claim 1, which is characterized in that sulfonated graphene resin type catalyst is in Baeyer-
Application process in Villiger oxidation reactions, includes the following steps：Ketone is dissolved in organic solvent first, peroxide is then added
Change hydrogen solution and sulfonated graphene resin type catalyst, be stirred to react completely, polar solvent is added after reaction by catalyst
It is precipitated, the mixed liquor after catalyst is precipitated and is centrifuged to obtain supernatant, last supernatant is washed, extracts, is obtained after distillation
To esters product.
3. application according to claim 2, which is characterized in that the sulfonated graphene resin type catalyst passes through following
It is prepared by step：Graphene is dissolved in organic solvent, sulfonating reaction is carried out at room temperature after the concentrated sulfuric acid is added, after reaction centrifugation point
From, it is dried to obtain sulfonated graphene, then sulfonated graphene and resin are dissolved in organic solvent, after ultrasonic disperse is uniform, analysis
Go out, filter, being drying to obtain sulfonated graphene resin type catalyst.
4. application according to claim 3, which is characterized in that the resin be selected from polystyrene resin, ABS resin,
One kind in polyvinyl resin, acrylic resin, polycarbonate resin and Corvic.
5. application according to claim 3, which is characterized in that the mass ratio of the graphene and the concentrated sulfuric acid is 1:3.5
~5, the sulfonating reaction time is 18~for 24 hours, the molar ratio of sulfonated graphene and resin is 1:4~5, ultrasonic time is 20~25h.
6. application according to claim 2 or 3, which is characterized in that the organic solvent is selected from dichloromethane, acetic acid second
One kind in ester, dichloroethanes, ether and chloroform.
7. application according to claim 2, which is characterized in that the ketone be selected from 2- Buddha's warrior attendants alkanone, alismone,
One kind in 2- methyl cyclohexanones, cyclopentanone and cyclohexanone, the polar solvent are selected from ethyl alcohol, methanol, water, acetonitrile and diformazan
One kind in base sulfoxide, the quality of the sulfonated graphene resin type catalyst are the 10%~20% of ketone, and reaction temperature is
25~55 DEG C, the reaction time is 10~20h, and the mass fraction of the hydrogenperoxide steam generator is 30%~50%, the mistake
The molar ratio of hydrogen oxide and ketone is 2~3.5:1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5808115A (en) * | 1996-03-08 | 1998-09-15 | University Of Georgia Research Foundation | Carbodiimide-promoted epoxidation of olefins |
| CN101811948A (en) * | 2010-03-22 | 2010-08-25 | 滕州市悟通香料有限责任公司 | Method for synthesizing pentanone-2 through Bayer-Vlieger oxidation reaction |
| CN103846103A (en) * | 2014-03-28 | 2014-06-11 | 南京理工大学 | Silica gel loaded type catalyst and application of catalyst in Baeyer-Villiger reaction |
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| JP4115828B2 (en) * | 2002-12-26 | 2008-07-09 | 花王株式会社 | Preparation of 2- (alkylidene) cycloalkanone |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5808115A (en) * | 1996-03-08 | 1998-09-15 | University Of Georgia Research Foundation | Carbodiimide-promoted epoxidation of olefins |
| CN101811948A (en) * | 2010-03-22 | 2010-08-25 | 滕州市悟通香料有限责任公司 | Method for synthesizing pentanone-2 through Bayer-Vlieger oxidation reaction |
| CN103846103A (en) * | 2014-03-28 | 2014-06-11 | 南京理工大学 | Silica gel loaded type catalyst and application of catalyst in Baeyer-Villiger reaction |
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