CN111100137A - Method for catalytic oxidation of dicyclopentadiene by supported heteropoly acid - Google Patents
Method for catalytic oxidation of dicyclopentadiene by supported heteropoly acid Download PDFInfo
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- CN111100137A CN111100137A CN201811246927.8A CN201811246927A CN111100137A CN 111100137 A CN111100137 A CN 111100137A CN 201811246927 A CN201811246927 A CN 201811246927A CN 111100137 A CN111100137 A CN 111100137A
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- dicyclopentadiene
- reaction
- catalyst
- heteropoly acid
- heteropolyacid
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 title claims abstract description 55
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 10
- 230000003647 oxidation Effects 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000001590 oxidative effect Effects 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 26
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 238000006884 silylation reaction Methods 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000007810 chemical reaction solvent Substances 0.000 claims description 32
- 238000006735 epoxidation reaction Methods 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 13
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 10
- 239000000395 magnesium oxide Substances 0.000 description 10
- 239000012043 crude product Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- -1 benzoyl peroxide dicyclopentadiene Chemical compound 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
- B01J31/124—Silicones or siloxanes or comprising such units
- B01J31/127—Silicones or siloxanes or comprising such units the siloxane units, e.g. silsesquioxane units, being grafted onto other polymers or inorganic supports, e.g. via an organic linker
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for catalyzing and oxidizing dicyclopentadiene by using supported heteropoly acid. The method adopts a process of catalyzing and oxidizing dicyclopentadiene by using supported heteropolyacid, takes dicyclopentadiene as a raw material, hydrogen peroxide as an oxidant, takes nano MgO-supported heteropolyacid or peroxy heteropolyacid which is grafted and modified by a silylation reagent containing quaternary phosphonium salt as a catalyst, and adopts a fixed bed or suspension bed reactor to carry out catalytic oxidation reaction in the presence of a solvent to prepare the dicyclopentadiene dioxide. Compared with the prior art, the method is simple, the catalyst has good heat resistance, stable service life, easy recovery and environmental protection, and the yield of the target product is more than 96%.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for catalyzing and oxidizing dicyclopentadiene by using supported heteropoly acid.
Background
Dicyclopentadiene dioxide was first prepared by h.wieland et al in 1925 from benzoyl peroxide dicyclopentadiene oxide. The production of small scale is carried out in early foreign countries by using relatively cheap peracetic acid as an oxidant. In the sixties of the last century, the Shanghai research institute for synthetic resins began to synthesize dicyclopentadiene dioxide products. In the seventies of the last century, dicyclopentadiene dioxide industrial products, the mark Hy-101 epoxy resin, were also tried out by the Tianjin chemical institute and the Tianjin Dong chemical plant by a pre-fabricated aqueous peracetic acid method, and research was conducted on the application of the resin in the fields of castable, glass laminate, high temperature resistant adhesive, B-stage resin, and the like. 40t/a pilot-scale technical development of synthesizing dicyclopentadiene dioxide by an acetaldehyde oxidation method is completed in 1984 by Shanghai Shi Ming Dynasty chemical Co. Because of adopting the production process of the peroxyacetic acid method, the production yield is low, the cost is high, the danger of the production process is high, the equipment corrosion is serious and the like, and the development and the application of the dicyclopentadiene dioxide product are limited. The Shanghai resin factory, Tianjin Jindong chemical factory and other factories which originally research and develop the dicyclopentadiene dioxide in China only have small-batch production due to the adoption of the peracid method, and the production cost is higher. Dicyclopentadiene dioxide produced by the industrial and industrial company Limited of Changde in Yueyang in Hunan by peroxyacetic acid oxidation method is CDR-0122, and the productivity is less than 100 tons.
Dicyclopentadiene dioxide is usually industrially prepared from dicyclopentadiene (DCPD) through epoxidation reaction by methods such as a peracetic acid method, a halohydrin method, a hydroperoxide catalytic epoxidation method and the like, but the three methods all have the defects at present, such as complex reaction process, serious equipment corrosion, easy generation of by-products by acidic ring opening of epoxide, high discharge of three wastes and the like.
Because of the excellent performance of dicyclopentadiene dioxide, dicyclopentadiene dioxide is widely used in the key technical fields of military industry, aviation, aerospace and the like abroad. Compared with bisphenol A series epoxy resin, dicyclopentadiene dioxide is expected to become a new generation of epoxy resin product with important influence in high-end fields of electric appliances and the like, so that the improvement and improvement of the synthesis process of dicyclopentadiene dioxide increasingly becomes the research focus in the field.
The heteropoly acid catalyst is paid much attention in the research field of olefin epoxidation reaction at present, the quaternary ammonium salt type phosphotungstic heteropoly acid compound catalyst system disclosed by Venturi and Ishii has the conversion rate of more than 95 percent when being used for most olefin epoxidation reactions such as 1-octene, cyclohexene, styrene and the like, and the epoxide selectivity is 80 percent, but the defects of difficult catalyst recovery, less repeated use frequency and the like generally exist. The heteropoly acid is loaded on the surface of the silicon dioxide by an immersion method and a sol-gel method, although the problem of catalyst recovery can be solved, the solution of the heteropoly acid falls off from the surface of a catalyst carrier in the reaction process, the service life of the catalyst is short, the catalyst is generally reused for 5-6 times, the activity of the catalyst is obviously reduced, and the heteropoly acid can not be used for an industrial generation device.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing dicyclopentadiene dioxide by catalyzing and oxidizing dicyclopentadiene with supported heteropolyacid. The method adopts a supported heteropolyacid catalytic oxidation dicyclopentadiene reaction process, takes dicyclopentadiene as a raw material, hydrogen peroxide as an oxidant, takes nano MgO supported heteropolyacid or peroxy heteropolyacid which is grafted and modified by a silylation reagent containing quaternary phosphonium salt as a catalyst, and adopts a fixed bed or suspension bed reactor to carry out catalytic oxidation reaction in the presence of a solvent to prepare the dicyclopentadiene dioxide. Specifically, the method comprises the following steps:
(1) raw materials and equipment: dicyclopentadiene is adopted as a raw material, hydrogen peroxide is adopted as an oxidant, nano MgO-loaded heteropoly acid or peroxy heteropoly acid subjected to graft modification treatment by a silylation reagent containing quaternary phosphonium salt is adopted as a catalyst, a reaction solvent adopted is any one or any combination of methanol, ethanol, n-propanol, isopropanol, tert-butanol, acetone, butanone, isobutyl ketone, pentanone, cyclopentanone, heptanone, acetonitrile, 1, 2-dichloroethane, chloroform, toluene, methyl acetate or ethyl acetate and butyl acetate, and a suspension bed reactor or a fixed bed reactor is adopted as reaction equipment;
wherein, the weight percentage of the hydrogen peroxide used in the epoxidation reaction is 30-70%, preferably 50-70%, the weight percentage of the heteropoly acid or the peroxy heteropoly acid in the catalyst is 1.8-47.0%, and the dicyclopentadiene and the H2O2The molar ratio of the dicyclopentadiene to the reaction solvent is 1: 2-1: 4, the volume ratio of the dicyclopentadiene to the reaction solvent is 1: 1-1: 6, and for a suspension bed reactor, the amount of the catalyst is 0.5-30% of the weight of the dicyclopentadiene;
(2) adding the raw materials, the oxidant, the catalyst and the reaction solvent in the step (1) into a reaction device to perform an epoxidation reaction, wherein the epoxidation reaction temperature is 30-80 ℃, and the reaction pressure is 0.1-6.0 MPa; for a fixed bed reactor, the total reaction material feeding volume airspeed is 0.1-2.2 h-1(ii) a For the suspension bed reactor, the reaction time is 6-18 h; separating the solvent after the reactant leaves the reactor to obtain the crude dicyclopentadiene dioxide.
Further, the silylation reagent containing quaternary phosphonium salt for the nano MgO surface graft modification treatment described in the step (1) has any one of the following two chemical formulas:
RmSi(OR)3-m(CH2)nP+R1R2R3X-(1)
RmSiX3-m(CH2)nP+R1R2R3X-(2)
wherein P, O, Si in chemical formulas (1) and (2) respectively represent phosphorus, oxygen and silicon; x represents halogen, and any one of F, Cl, Br and I elements is selected, preferably Cl; m represents the number of alkyl groups bonded to the silicon atom, and is an integer of 0 to 2; n represents the number of methylene groups connected between silicon and phosphorus atoms, and is an integer of 1-18, preferably 1-3; r, R1、R2、R3The alkyl group is preferably any one of methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, tetradecyl, hexadecyl and octadecyl.
Further, the heteropoly acid in the step (1) is a heteropoly acid with a Keggin structure, and preferably any one of dodecaphosphotungstic acid, dodecasilicotungstic acid, dodecasilicomolybdic acid and dodecaphosphomolybdic acid.
The invention has the advantages that: (1) compared with the prior art, the method has simple operation and simple and convenient separation of the product and the catalyst; (2) the catalyst has the advantages of good heat resistance, high reaction activity, stable service life, easy recovery and environment-friendly reaction product; (3) the yield of the target product is more than 96 percent; (4) the method is not only suitable for the reaction of preparing the dicyclopentadiene dioxide by oxidizing the dicyclopentadiene, but also widely suitable for the epoxidation reaction of various olefins, and has good industrial application prospect.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
In examples 1 to 6, the silylation reagent used for modifying the nano-magnesia has the molecular structural formulas (1) to (6):
the yield of the reaction product in examples 1 to 6 is defined as follows:
example 1
(1) Raw materials and equipment: dicyclopentadiene is adopted as a raw material, hydrogen peroxide is adopted as an oxidant, nano MgO-loaded dodecaphosphotungstic heteropoly acid which is subjected to graft modification treatment by a silylation reagent containing quaternary phosphonium salt is adopted as a catalyst, a reaction solvent is methanol, and a suspension bed reactor is adopted as reaction equipment;
wherein the weight percentage of the hydrogen peroxide used in the epoxidation reaction is 30 percent, the weight percentage of the heteropoly acid in the catalyst is 1.8 percent, and the dicyclopentadiene and the H2O2The molar ratio of the dicyclopentadiene to the reaction solvent is 1:2, the volume ratio of the dicyclopentadiene to the reaction solvent is 1:1, and the dosage of the catalyst is 0.5 percent of the mass of the dicyclopentadiene;
(2) adding the raw materials, the oxidant, the catalyst and the reaction solvent in the step (1) into a suspension bed reaction device for epoxidation reaction, wherein the epoxidation reaction temperature is 30 ℃, the reaction pressure is 0.1MPa, and the reaction time is 18h to obtain a dicyclopentadiene dioxide crude product
In this example, the yield of the target product was 97.5%.
Example 2
(1) Raw materials and equipment: dicyclopentadiene is adopted as a raw material, hydrogen peroxide is adopted as an oxidant, nano MgO-loaded dodecasilicotungstic heteropoly acid subjected to graft modification treatment by a silylation reagent containing quaternary phosphonium salt is adopted as a catalyst, a reaction solvent is ethanol, and a fixed bed reactor is adopted as reaction equipment;
wherein the weight percentage of the hydrogen peroxide used in the epoxidation reaction is 70 percent, the weight percentage of the heteropoly acid in the catalyst is 47.0 percent, and the dicyclopentadiene and the H2O2The molar ratio of the dicyclopentadiene to the reaction solvent is 1:4, and the volume ratio of the dicyclopentadiene to the reaction solvent is 1: 6;
(2) adding the raw materials, the oxidant, the catalyst and the reaction solvent in the step (1) into a fixed bed reactor for epoxidation reaction, wherein the feeding volume airspeed of the total reaction materials is 2.2h-1And the epoxidation reaction temperature is 80 ℃, and the reaction pressure is 6.0MPa, so that the dicyclopentadiene dioxide crude product is obtained.
In this example, the yield of the objective product was 97.7%.
Example 3
(1) Raw materials and equipment: dicyclopentadiene is adopted as a raw material, hydrogen peroxide is adopted as an oxidant, nano MgO-loaded dodecaphosphomolybdic heteropoly acid subjected to graft modification treatment by a silylation reagent containing quaternary phosphonium salt is adopted as a catalyst, a reaction solvent is acetone, and a suspension bed reactor is adopted as reaction equipment;
wherein the weight percentage of the hydrogen peroxide used in the epoxidation reaction is 40 percent, the weight percentage of the heteropoly acid in the catalyst is 10 percent, and the dicyclopentadiene and the H2O2The molar ratio of the dicyclopentadiene to the reaction solvent is 1:3, the volume ratio of the dicyclopentadiene to the reaction solvent is 1:2, and the dosage of the catalyst is 5 percent of the mass of the dicyclopentadiene;
(2) and (2) adding the raw materials, the oxidant, the catalyst and the reaction solvent in the step (1) into a reaction device to perform epoxidation reaction, wherein the epoxidation reaction temperature is 40 ℃, the reaction pressure is 0.8MPa, and the reaction time is 8 hours, so as to obtain a dicyclopentadiene dioxide crude product.
In this example, the yield of the target product was 97.1%.
Example 4
(1) Raw materials and equipment: dicyclopentadiene is adopted as a raw material, hydrogen peroxide is adopted as an oxidant, nano MgO-loaded dodecasilicomolybdic heteropoly acid subjected to graft modification treatment by a silylation reagent containing quaternary phosphonium salt is adopted as a catalyst, a reaction solvent is ethyl acetate, and a fixed bed reactor is adopted as reaction equipment;
wherein the weight percentage of the hydrogen peroxide used in the epoxidation reaction is 50 percent, the weight percentage of the heteropoly acid in the catalyst is 20 percent, and the dicyclopentadiene and the H2O2The molar ratio of the dicyclopentadiene to the reaction solvent is 1:4, and the volume ratio of the dicyclopentadiene to the reaction solvent is 1: 3;
(2) adding the raw materials, the oxidant, the catalyst and the reaction solvent in the step (1) into a reaction device for epoxidation reaction, wherein the total reaction material feeding volume airspeed is 1.5h-1And the epoxidation reaction temperature is 50 ℃, and the reaction pressure is 2MPa, so that the dicyclopentadiene dioxide crude product is obtained.
In this example, the yield of the target product was 96.4%.
Example 5
(1) Raw materials and equipment: dicyclopentadiene is adopted as a raw material, hydrogen peroxide is adopted as an oxidant, nano MgO-loaded peroxy phosphotungstic heteropoly acid subjected to graft modification treatment by a silylation reagent containing quaternary phosphonium salt is adopted as a catalyst, a reaction solvent is toluene, and a suspension bed reactor is adopted as reaction equipment;
wherein the weight percentage of the hydrogen peroxide used in the epoxidation reaction is 60 percent, the weight percentage of the peroxy heteropoly acid in the catalyst is 30 percent, and the dicyclopentadiene and the H2O2The molar ratio of the dicyclopentadiene to the reaction solvent is 1:2, the volume ratio of the dicyclopentadiene to the reaction solvent is 1:5, and the dosage of the catalyst is 20 percent of the mass of the dicyclopentadiene;
(2) and (2) adding the raw materials, the oxidant, the catalyst and the reaction solvent in the step (1) into a reaction device to perform epoxidation reaction, wherein the epoxidation reaction temperature is 70 ℃, the reaction pressure is 4MPa, and the reaction time is 12 hours, so as to obtain a dicyclopentadiene dioxide crude product.
In this example, the yield of the target product was 96.3%.
Example 6
(1) Raw materials and equipment: dicyclopentadiene is adopted as a raw material, hydrogen peroxide is adopted as an oxidant, nano MgO-loaded dodecaphosphotungstic heteropoly acid subjected to graft modification treatment by a silylation reagent containing quaternary phosphonium salt is adopted as a catalyst, a reaction solvent is a mixture of methanol and ethanol with the same amount, and a fixed bed reactor is adopted as reaction equipment;
wherein the weight percentage of the hydrogen peroxide used in the epoxidation reaction is 50 percent, the weight percentage of the heteropoly acid in the catalyst is 40 percent, and the dicyclopentadiene and the H2O2The molar ratio of the dicyclopentadiene to the reaction solvent is 1:4, and the volume ratio of the dicyclopentadiene to the reaction solvent is 1: 5;
(2) adding the raw materials, the oxidant, the catalyst and the reaction solvent in the step (1) into fixed bed reaction equipment for epoxidation reaction, wherein the total reaction material feeding volume airspeed is 2.0h-1The epoxidation reaction temperature is 75 ℃, the reaction pressure is 5.0MPa, and the product is obtainedAnd (3) crude dicyclopentadiene dioxide.
In this example, the yield of the target product was 96.9%.
Claims (6)
1. A method for catalyzing and oxidizing dicyclopentadiene by using supported heteropolyacid is characterized by comprising the following steps:
(1) raw materials and equipment: dicyclopentadiene is used as a raw material, hydrogen peroxide is used as an oxidant, nano MgO-loaded heteropoly acid or peroxy heteropoly acid subjected to graft modification by a silylation reagent containing quaternary phosphonium salt is used as a catalyst, a reaction solvent is any one or any combination of methanol, ethanol, n-propanol, isopropanol, tert-butanol, acetone, butanone, isobutyl ketone, pentanone, cyclopentanone, heptanone, acetonitrile, 1, 2-dichloroethane, chloroform, toluene, methyl acetate or ethyl acetate and butyl acetate, and a suspension bed reactor or a fixed bed reactor is used as reaction equipment;
wherein the weight percentage of the hydrogen peroxide used in the epoxidation reaction is 30-70%, the weight percentage of the heteropoly acid or the peroxy heteropoly acid in the catalyst is 1.8-47.0%, and the dicyclopentadiene and the H2O2The molar ratio of the dicyclopentadiene to the reaction solvent is 1: 2-1: 4, the volume ratio of the dicyclopentadiene to the reaction solvent is 1: 1-1: 6, and for a suspension bed reactor, the amount of the catalyst is 0.5-30% of the weight of the dicyclopentadiene;
(2) adding the raw materials, the oxidant, the catalyst and the reaction solvent in the step (1) into a reaction device to perform an epoxidation reaction, wherein the epoxidation reaction temperature is 30-80 ℃, and the reaction pressure is 0.1-6.0 MPa; for a fixed bed reactor, the total reaction material feeding volume airspeed is 0.1-2.2 h-1(ii) a For the suspension bed reactor, the reaction time is 6-18 h; separating the solvent after the reactant leaves the reactor to obtain the crude dicyclopentadiene dioxide.
2. The method for catalytic oxidation of dicyclopentadiene by supported heteropolyacid according to claim 1, wherein the silylation agent containing quaternary phosphonium salt for nano-MgO surface graft modification treatment has any one of the following two chemical formulas:
RmSi(OR)3-m(CH2)nP+R1R2R3X-(1)
RmSiX3-m(CH2)nP+R1R2R3X-(2)
wherein P, O, Si in chemical formulas (1) and (2) respectively represent phosphorus, oxygen and silicon; x represents halogen, and any one of F, Cl, Br and I elements is selected; m represents the number of alkyl groups bonded to the silicon atom, and is an integer of 0 to 2; n represents the number of methylene groups connected between silicon and phosphorus atoms, and is an integer of 1-18; r, R1、R2、R3Selected from alkyl with 1-18 carbon atoms, phenyl or benzyl.
3. The method for catalytic oxidation of dicyclopentadiene with a supported heteropolyacid according to claim 2, wherein X in the formulae (1) and (2) is Cl; n is an integer of 1-3; r, R1、R2、R3The alkyl group having 1 to 18 carbon atoms is any one of methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl.
4. The method for catalyzing and oxidizing dicyclopentadiene by using the supported heteropolyacid as claimed in claim 1, wherein the heteropolyacid is a heteropolyacid having a Keggin structure.
5. The method for catalytic oxidation of dicyclopentadiene by the supported heteropolyacid according to claim 4, wherein the heteropolyacid is any one of dodecaphosphotungstic acid, dodecasilicotungstic acid, dodecasilicomolybdic acid and dodecaphosphomolybdic acid.
6. The method for catalytic oxidation of dicyclopentadiene with supported heteropolyacid according to claim 1, wherein the mass percentage of hydrogen peroxide used in the epoxidation reaction is 50% to 70%.
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