CN103143381A - Carbon-nitrogen material immobilized heteropoly acid catalyst and olefin epoxidation synthesis method - Google Patents
Carbon-nitrogen material immobilized heteropoly acid catalyst and olefin epoxidation synthesis method Download PDFInfo
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- CN103143381A CN103143381A CN2013100964426A CN201310096442A CN103143381A CN 103143381 A CN103143381 A CN 103143381A CN 2013100964426 A CN2013100964426 A CN 2013100964426A CN 201310096442 A CN201310096442 A CN 201310096442A CN 103143381 A CN103143381 A CN 103143381A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 14
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims description 20
- 238000006735 epoxidation reaction Methods 0.000 title abstract description 6
- 238000001308 synthesis method Methods 0.000 title 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 22
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- 239000010937 tungsten Substances 0.000 claims description 20
- -1 olefin epoxide Chemical class 0.000 claims description 16
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 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 claims description 8
- UTEIUSUWIZICDO-UHFFFAOYSA-N 6-methylcyclohex-3-ene-1-carboxylic acid Chemical compound CC1CC=CCC1C(O)=O UTEIUSUWIZICDO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- VUSWCWPCANWBFG-UHFFFAOYSA-N cyclohex-3-ene-1-carboxylic acid Chemical compound OC(=O)C1CCC=CC1 VUSWCWPCANWBFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000008282 halocarbons Chemical group 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 2
- 239000004913 cyclooctene Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 54
- 239000000047 product Substances 0.000 description 24
- 230000003647 oxidation Effects 0.000 description 23
- 238000007254 oxidation reaction Methods 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 22
- 238000002390 rotary evaporation Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000012018 catalyst precursor Substances 0.000 description 12
- 150000004702 methyl esters Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SQDHHLGTMQUVSH-UHFFFAOYSA-N [O-2].[Ti+4].C1=CC=CC1.[O-2] Chemical compound [O-2].[Ti+4].C1=CC=CC1.[O-2] SQDHHLGTMQUVSH-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a carbon and nitrogen material immobilized heteropoly acid catalyst and a method for olefin epoxidation synthesis by using the catalyst. Adding the catalyst and the olefin reactant into the organic solvent, adding hydrogen peroxide, and continuously stirring until the reaction is finished. Then separating the solid phase from the liquid phase, removing the organic solvent from the liquid phase to obtain a product, and washing and drying the solid phase catalyst and then recovering the solid phase catalyst. The invention uses hydrogen peroxide as an oxygen source, the catalyst preparation is simple and easy, the epoxidation process flow is simple, the equipment requirement is low, the product yield is high, and the solvent and the catalyst can be recycled.
Description
Technical field
A kind of method that the present invention relates to carbon-nitrogen material solid-carrying heteropolyacid catalyst and utilize the olefin epoxide of this catalyst to be combined to.
Background technology
Recent years, the report of relevant carbon-nitrogen material is more and more, is that environmentally safe meets the Green Chemistry requirement because the essential element that forms carbon-nitrogen material is carbon and nitrogen and a small amount of hydrogen on the one hand; On the other hand, due to the Heat stability is good of carbon-nitrogen material, and show outstanding catalytic performance in a series of reaction.2007, it was raw material with melamine and trichloromethyl silane that bibliographical information (J.Solid.State.Chem.2007,125-133.) is arranged, and made a kind of porous carbon nitrogen material that contains silicon by high-temperature calcination; 2009, Vinu has reported (Angew.Chem.2009,121,8024-8027.) with having carbon-nitrogen material than bigger serface as ester exchange catalyst, and after this carbon-nitrogen material load gold catalyst, can be with benzaldehyde, piperidines and phenylacetylene make corresponding propargyl amine by coupling reaction.2010, Ye reported (J.Phys.Chem.C.2010,114,4100-4105.) tantalic acid is entrained in carbon-nitrogen material as photochemical catalyst, success make hydrogen from methanol solution.2011, Wang reported (J.Am.Chem.Soc., 2011, then 2362-2365.) a kind of carbon-nitrogen material of porous is used for the carried metal palladium, does the phenol hydrogenation reaction with this catalyst.The present invention makes the carbon-nitrogen material solid-carrying heteropolyacid catalyst take melamine and heteropoly acid as raw material by high-temperature calcination, and the epoxy reaction of using this carbon-nitrogen material catalysis of solid supported heteropoly acid catalyst alkene obtains aliphatic epoxy resin.
Epoxy resin is a kind of important thermosetting resin kind, and it is widely used in the industrial circles such as chemical industry, light industry, water conservancy, traffic, machinery, electronics, household electrical appliances, automobile and space flight and aviation.And as epoxy resin of new generation, aliphatic diepoxides has Heat stability is good, and weatherability is high, and electrical insulation capability is excellent, ultraviolet resistance and electron-irradiation resisting performance and be suitable for outdoor use, and can be widely used on the electronic products such as anti-ultraviolet paint and LED.At present industrial main acid oxidation and the synthetic olefin epoxide compound of catalytic oxidation of adopting.Cross acid oxidation and adopt the Peracetic acid of high concentration to make oxidant, have in process of production very large potential safety hazard, and produce in process of production a large amount of acetic acid, cause the separation of products difficulty, so the method can't realize large-scale production at home.And catalytic oxidation to adopt the metallic compound with oxidisability be catalyst, and take hydrogen peroxide or alkyl peroxide as oxygen source, come synthctic fat family epoxide.Nineteen eighty-three, the phase transfer catalyst of using sodium tungstate and phosphoric acid etc. to synthesize of Venturello report is take hydrogen peroxide as oxygen source, this system is water-oily two-phase reaction system, and straight chain end alkene is had epoxidation catalytic activity (J.Org.Chem., 1983 preferably, 48,3831-3833.).1988, Ishii improved Venturello, but not change of active material (J.Org.Chem., 1988,53,3587-3593.).Calendar year 2001, the reaction-controlled phase transfer catalysis system of Xi Zuwei, well solved the recovery of homogeneous catalyst problem (Journal of Molecular Catalysis., 2001,2,113-118.).2008, publication number was to have proposed the catalysis epoxidation technique that the recyclable circulation of a kind of catalyst is use in the patent of invention of CN101143919, and still, this technique exists that catalyst is difficult to reclaim and residual problem in product.
Summary of the invention
The objective of the invention is to provide in order to improve the deficiencies in the prior art a kind of carbon-nitrogen material solid-carrying heteropolyacid catalyst, another object of the present invention also provides the catalyzing expoxidation of olefines compound synthetic method, the catalyst that makes by the present invention can circulate and repeatedly use, and can be used for carrying out the large-scale production of safety olefin epoxide compound.
Technical scheme of the present invention is: a kind of carbon-nitrogen material solid-carrying heteropolyacid catalyst, prepared by following methods, its concrete steps are as follows: heteropoly acid and melamine are dissolved into respectively in the hot water of 50 ℃～60 ℃, then the mol ratio by heteropoly acid and melamine is 1:(1～4) heteropoly acid solution is joined in melamine solution, through stirring, filter, oven dry, obtain the white solid powder, then the high-temperature calcination under atmosphere of inert gases of this pressed powder is made its curing, namely get the carbon-nitrogen material solid-carrying heteropolyacid catalyst.
Preferred described heteropoly acid is H
3PW
12O
40, H
4SiW
12O
40Or H
4PW
11VO
40The temperature of preferred described high-temperature calcination is 350 ℃～450 ℃, and the heating rate scope is 5 ℃/minutes～10 ℃/minutes; Calcination time is 4 hours～6 hours.
The method that the present invention also provides the olefin epoxide that utilizes above-mentioned carbon-nitrogen material solid-carrying heteropolyacid catalyst to be combined to, its concrete steps are: catalyst and olefin substrate are joined in organic solvent, and add hydrogen peroxide, constantly stir under heating until reaction finishes; Then with the solid-liquid two-phase separately, liquid phase is removed organic solvent and is obtained product, and solid-phase catalyst reclaims after washing drying.
The mole that preferred described catalyst amount is tungsten in catalyst is 3.2～10% of olefin substrate mole.
The mass concentration scope of preferred described hydrogen peroxide is 20%～50%, and the mol ratio of hydrogen peroxide and olefin substrate is 2～3:1.
Preferred heating-up temperature is 70～80 ℃, and the reaction time is 6～8h.
In the selection of solvent, nitrile, halogenated hydrocarbons, ester, ketone, aromatic hydrocarbon, the organic solvents such as alcohol all can be used as synthesis reaction solvent of the present invention, and preferred described solvent is halogenated hydrocarbons, nitrile, ester or ketone; More preferably solvent is a kind of in acetonitrile, dichloroethanes, chloroform, ethyl acetate, toluene, methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, acetone, butanone etc.; Most preferably acetonitrile, dichloroethanes, chloroform and ethyl acetate.
Above-mentioned alkene comprises general alkene structures compound, be specially adapted to have the bicyclic alkene compound of following architectural feature, because the dicyclo oxidation of diolefin compound has important industrial application value, a series of test results of the present invention are based on the corresponding diepoxides of the cited diolefin substrate of table 1 and generation:
Table 1
Preferred described olefin substrate is cyclohexene, cyclo-octene, dicyclopentadiene, 3-cyclohexenecarboxylic acid-3 ,-cyclohexene methyl esters or 6-methyl-3-cyclohexenecarboxylic acid-6 ,-methyl-3 ,-cyclohexene methyl esters.
In the present invention, the recovery of catalysts and solvents is after system reacts completely, and the system for the treatment of is cooled to room temperature, by filtering, solid and liquid is separated, and liquid is collected organic phase by standing, obtains organic solvent by decompression distillation, and obtains corresponding epoxy product; The solid that filtration obtains after washing, drying, constant weight, is reused for synthetic epoxy resin according to top described process conditions.Reclaim the catalyst that uses and still keep well selective.
Beneficial effect:
The raw material that in the present invention, synthetic catalyst uses cheaply is easy to get, and the preparation method is simple, safety, and catalyst activity is high, the most important thing is that the catalyst in the present invention can be repeatedly used, and keeps high activity, high selectivity.The catalyst that synthesizes by the present invention can not only reduce synthetic cost, and catalyst life is extended, and compares with homogeneous catalyst in the past, and cost performance is higher.In the today of advocating Green Chemistry, a kind of like this catalyst is to be fit to large-scale industrialization fully produce.
All epoxidation reactions in the present invention are all take commercially available hydrogen peroxide as oxygen source, and method different from the past is used dangerous, explosive Peracetic Acid.The hydrogen peroxide low price, the source is wide, and less water is arranged in production process, has avoided the decomposition of product.Compared with prior art, the present invention also has an advantage, adopts production technology of the present invention, need not to make production technology convenient, succinct by adding buffer to regulate the pH value.
On the basis of foregoing, according to ordinary skill knowledge and the customary means of this area, not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite, can also make modification, replacement or the change of various ways.
Below the specific embodiment by form of implementation, foregoing of the present invention is described in further detail again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to category of the present invention.
The specific embodiment
Synthesizing of embodiment 1 catalyst A
288mL is dissolved with 28.8 grams (10mmol) H
3PW
12O
4050 ℃ of hydrothermal solutions, join in the situation that constantly stir 50 ℃ of hot water that 126mL is dissolved with 1.26 grams (10mmol) melamine, continue vigorous stirring 24h, fully after reaction, make reactant mixture cooling, filter, filter cake is successively through washing, after ethanol was washed, vacuum drying obtained catalyst precursor [C to constant weight
3H
6N
6H
3] PW
12O
40
Take the catalyst precursor that 20 grams make above, fully grind in mortar, grind to form very thin powder, ground powder solid is joined in silica ware, then be placed in the temperature programming stove, calcine under atmosphere of inert gases.Heating rate is controlled at 5 ℃/minutes, and target temperature is arranged on 350 ℃, and continuing calcination time under 350 ℃ is 4h, and temperature fall time is controlled to be 1h, obtains black catalyst A pressed powder.
Implement the synthetic of 2 catalyst B
288mL is dissolved with 28.8 grams (10mmol) H
3PW
12O
4060 ℃ of hydrothermal solutions, join in the situation that constantly stir 60 ℃ of hot water that 200mL is dissolved with 3.78 grams (30mmol) melamine, continue vigorous stirring 24h, fully after reaction, make reactant mixture cooling, filter, filter cake is successively through washing, after ethanol was washed, vacuum drying made catalyst precursor [C to constant weight
3H
6N
6H] [PW
12O
40]
1/3
Take the catalyst precursor that 20 grams make above, fully grind in mortar, grind to form very thin powder, ground powder solid is joined in silica ware, then be placed in the temperature programming stove, calcine under atmosphere of inert gases.Heating rate is controlled at 10 ℃/minutes, and target temperature is arranged on 400 ℃, and continuing calcination time under 400 ℃ is 5h, and temperature fall time is controlled to be 1.5h, obtains black catalyst B pressed powder.
Implement the synthetic of 3 catalyst C
300mL is dissolved with 28.8 grams (10mmol) H
4SiW
12O
4055 ℃ of aqueous solution, add during 150mL is dissolved with 55 ℃ of hot water of 1.67 grams (13.3mmol) melamine in the situation that constantly stir, continue vigorous stirring 24h, fully after reaction, make reactant mixture cooling, filter, filter cake is successively through washing, after ethanol was washed, vacuum drying made catalyst precursor [C to constant weight
3H
6N
6H
3] [SiW
12O
40]
3/4
Take the catalyst precursor that 20 grams make above, fully grind in mortar, grind to form very thin powder, ground powder solid is joined in silica ware, then be placed in the temperature programming stove, calcine under atmosphere of inert gases.Heating rate is controlled at 5 ℃/minutes, and target temperature is arranged on 350 ℃, and lasting calcination time is 4h, and temperature fall time is controlled to be 1h, obtains black catalyst C pressed powder.
Implement the synthetic of 4 catalyst D
300mL is dissolved with 28.8 grams (10mmol) H
4SiW
12O
4060 ℃ of aqueous solution, join in the situation that constantly stir 60 ℃ of hot water that 250mL is dissolved with 4.9 grams (40mmol) melamine, continue vigorous stirring 24h, fully after reaction, make reactant mixture cooling, filter, filter cake is successively through washing, after ethanol was washed, vacuum drying made catalyst precursor [C to constant weight
3H
6N
6H] [SiW
12O
40]
1/4
Take the catalyst precursor that 20 grams make above, fully grind in mortar, grind to form very thin powder, ground powder solid is joined in silica ware, then be placed in the temperature programming stove, calcine under atmosphere of inert gases.Heating rate is controlled at 10 ℃/minutes, and target temperature is arranged on 450 ℃, and lasting calcination time is 6h, and temperature fall time is controlled to be 2h, obtains black catalyst D pressed powder.
Implement the synthetic of 5 catalyst E
310mL is dissolved with 31 grams (10mmol) H
4PW
11VO
455 ℃ of hydrothermal solutions, join in the situation that constantly stir 55 ℃ of hot water that 150mL is dissolved with 1.67 grams (13.3mmol) melamine, continue vigorous stirring 24h, fully after reaction, make reactant mixture cooling, filter, filter cake is successively through washing, after ethanol was washed, vacuum drying made catalyst precursor [C to constant weight
3H
6N
6H
3] [PW
11VO
4]
3/4
Take the catalyst precursor that 20 grams make above, fully grind in mortar, grind to form very thin powder, ground powder solid is joined in silica ware, then be placed in the temperature programming stove, calcine under atmosphere of inert gases.Heating rate is controlled at 10 ℃/minutes, and target temperature is arranged on 450 ℃, and lasting calcination time is 4h, and temperature fall time is controlled to be 2h, obtains black catalyst E pressed powder.
Implement the synthetic of 6 catalyst F
310mL is dissolved with 31 grams (10mmol) H
4PW
11VO
460 ℃ of hydrothermal solutions, join in the situation that constantly stir 60 ℃ of hot water that 250mL is dissolved with 4.9 grams (40mmol) melamine, continue vigorous stirring 24h, fully after reaction, make reactant mixture cooling, filter, filter cake is successively through washing, after ethanol was washed, vacuum drying made catalyst precursor [C to constant weight
3H
6N
6H] [PW
11VO
4]
1/4
Take the catalyst precursor that 20 grams make above, fully grind in mortar, grind to form very thin powder, ground powder solid is joined in silica ware, then be placed in the temperature programming stove, calcine under the atmosphere of nitrogen.Heating rate is controlled at 10 ℃/minutes, and target temperature is set to 450 ℃, and lasting calcination time is 6h, and temperature fall time is controlled to be 2h, obtains black catalyst F pressed powder.
Implement 7122 catalytic oxidations synthetic
66 grams (0.5mol) dicyclopentadiene and 5 gram catalyst A (amount of tungsten is 0.02mol) are joined in 100 gram acetonitriles, splash into 165mL20%(1.1mol under 80 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtains product titanium dioxide cyclopentadiene 76 grams, productive rate 94%.
Implement 8122 catalytic oxidations synthetic
66 grams (0.5mol) dicyclopentadiene and 5 gram catalyst B (amount of tungsten is 0.018mol) are joined in 100 gram acetonitriles, splash into 165mL20%(1.1mol under 80 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtains product titanium dioxide cyclopentadiene 72 grams, productive rate 88%.
Implement 9122 catalytic oxidations synthetic
Be 0.018mol with the amount of 66 grams (0.5mol) dicyclopentadiene and 5 gram catalyst C(tungsten) join in 100 gram acetonitriles, splash into 110mL30%(1.1mol under 75 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtains product titanium dioxide cyclopentadiene 70 grams, productive rate 85%.Implement 10122 catalytic oxidations synthetic
Be 0.016mol with the amount of 66 grams (0.5mol) dicyclopentadiene and 5 gram catalyst D(tungsten) join in 100 gram acetonitriles, splash into 150mL30%(1.5mol under 75 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtains product titanium dioxide cyclopentadiene 65 grams, productive rate 79%.
Implement 11122 catalytic oxidations synthetic
Be 0.05mol with the amount of 66 grams (0.5mol) dicyclopentadiene and 15 gram catalyst E(tungsten) join in 100 gram acetonitriles, splash into 63mL50%(1.05mol under 70 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtains product titanium dioxide cyclopentadiene 78 grams, productive rate 95%.
Implement 12122 catalytic oxidations synthetic
Be 0.045mol with the amount of 66 grams (0.5mol) dicyclopentadiene and 15 gram catalyst F(tungsten) join in 100 gram acetonitriles, splash into 63mL50%(1.05mol under 70 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtains product titanium dioxide cyclopentadiene 76 grams, productive rate 94%.
Implement the 13CER-4221 catalytic oxidation synthetic
With 110 grams (0.5mol) 3-cyclohexenecarboxylic acid-3 ,-cyclohexene methyl esters and 5 gram catalyst A (amount of tungsten is 0.02mol) join in 100 gram acetonitriles, splash into 165mL20%(1.1mol under 80 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtain product 3,4-epoxy-hexahydrobenzoid acid-3,, 4,-epoxycyclohexyl methyl esters 115 grams, productive rate 81%.
Implement the 14CER-4221 catalytic oxidation synthetic
With 110 grams (0.5mol) 3-cyclohexenecarboxylic acid-3 ,-cyclohexene methyl esters and 5 gram catalyst B (amount of tungsten is 0.018mol) join in 100 gram acetonitriles, splash into 165mL20%(1.1mol under 80 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtain product 3,4-epoxy-hexahydrobenzoid acid-3,, 4,-epoxycyclohexyl methyl esters 105 grams, productive rate 74%.
Implement the 15CER-4221 catalytic oxidation synthetic
With 110 grams (0.5mol) 3-cyclohexenecarboxylic acid-3, the amount of-cyclohexene methyl esters and 5 gram catalyst C(tungsten is 0.018mol) join in 100 gram acetonitriles, splash into 110mL30%(1.1mol under 75 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtain product 3,4-epoxy-hexahydrobenzoid acid-3,, 4,-epoxycyclohexyl methyl esters 104 grams, productive rate 73%.
Implement the 16CER-4221 catalytic oxidation synthetic
With 110 grams (0.5mol) 3-cyclohexenecarboxylic acid-3, the amount of-cyclohexene methyl esters and 5 gram catalyst D(tungsten is 0.016mol) join in 100 gram acetonitriles, splash into 150mL30%(1.5mol under 75 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtain product 3,4-epoxy-hexahydrobenzoid acid-3,, 4,-epoxycyclohexyl methyl esters 103 grams, productive rate 72%.
Implement the 17CER-4221 catalytic oxidation synthetic
With 110 grams (0.5mol) 3-cyclohexenecarboxylic acid-3, the amount of-cyclohexene methyl esters and 15 gram catalyst E(tungsten is 0.05mol) join in 100 gram acetonitriles, splash into 63mL50%(1.05mol under 70 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtain product 3,4-epoxy-hexahydrobenzoid acid-3,, 4,-epoxycyclohexyl methyl esters 130 grams, productive rate 91%.
Implement the 18CER-4221 catalytic oxidation synthetic
With 110 grams (0.5mol) 3-cyclohexenecarboxylic acid-3, the amount of-cyclohexene methyl esters and 15 gram catalyst F(tungsten is 0.045mol) join in 100 gram acetonitriles, splash into 63mL50%(1.05mol under 70 ℃) hydrogen peroxide, reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtain product 3,4-epoxy-hexahydrobenzoid acid-3,, 4,-epoxycyclohexyl methyl esters 125 grams, productive rate 88%.
Implement the 19Unox201 catalytic oxidation synthetic
With 125 grams (0.5mol) 6-methyl-3-cyclohexenecarboxylic acid-6 ,-methyl-3 ,-cyclohexene methyl esters and 5 gram catalyst A (amount of tungsten is 0.02mol) join in 100 gram acetonitriles, splash into 165mL20%(1.1mol under 80 ℃) hydrogen peroxide, the reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtains product 4,5-epoxy-2-methylcyclohexyl formic acid-4,, 5 ,-epoxy-2,-methylcyclohexyl methyl esters 124 grams, productive rate 78%.
Implement the 20Unox201 catalytic oxidation synthetic
With 125 grams (0.5mol) 6-methyl-3-cyclohexenecarboxylic acid-6 ,-methyl-3 ,-cyclohexene methyl esters and 5 gram catalyst B (amount of tungsten is 0.018mol) join in 100 gram acetonitriles, splash into 165mL20%(1.1mol under 80 ℃) hydrogen peroxide, the reaction 7h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtains product 4,5-epoxy-2-methylcyclohexyl formic acid-4,, 5 ,-epoxy-2,-methylcyclohexyl methyl esters 115 grams, productive rate 73%.
Implement the 21Unox201 catalytic oxidation synthetic
With 125 grams (0.5mol) 6-methyl-3-cyclohexenecarboxylic acid-6 ,-methyl-3, the amount of-cyclohexene methyl esters and 5 gram catalyst C(tungsten is 0.018mol) join in 100 gram acetonitriles, splash into 110mL30%(1.1mol under 75 ℃) hydrogen peroxide, the reaction 6h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtains product 4,5-epoxy-2-methylcyclohexyl formic acid-4,, 5 ,-epoxy-2,-methylcyclohexyl methyl esters 113 grams, productive rate 72%.
Implement the 22Unox201 catalytic oxidation synthetic
With 125 grams (0.5mol) 6-methyl-3-cyclohexenecarboxylic acid-6 ,-methyl-3, the amount of-cyclohexene methyl esters and 5 gram catalyst D(tungsten is 0.016mol) join in 100 gram chloroforms, splash into 150mL30%(1.5mol under 75 ℃) hydrogen peroxide, the reaction 8h, be cooled to room temperature, filter, rotary evaporation steams chloroform, obtains product 4,5-epoxy-2-methylcyclohexyl formic acid-4,, 5 ,-epoxy-2,-methylcyclohexyl methyl esters 110 grams, productive rate 70%.
Implement the 23Unox201 catalytic oxidation synthetic
With 125 grams (0.5mol) 6-methyl-3-cyclohexenecarboxylic acid-6 ,-methyl-3, the amount of-cyclohexene methyl esters and 15 gram catalyst E(tungsten is 0.05mol) join in 100 gram acetonitriles, splash into 63mL50%(1.05mol under 70 ℃) hydrogen peroxide, the reaction 8h, be cooled to room temperature, filter, rotary evaporation steams acetonitrile, obtains product 4,5-epoxy-2-methylcyclohexyl formic acid-4,, 5 ,-epoxy-2,-methylcyclohexyl methyl esters 147 grams, productive rate 94%.
Implement the 24Unox201 catalytic oxidation synthetic
With 125 grams (0.5mol) 6-methyl-3-cyclohexenecarboxylic acid-6 ,-methyl-3, the amount of-cyclohexene methyl esters and 5 gram catalyst F(tungsten is 0.045mol) join in 100 gram dichloroethanes, splash into 63mL50%(1.05mol under 70 ℃) hydrogen peroxide, the reaction 7h, be cooled to room temperature, filter, rotary evaporation steams dichloroethanes, obtains product 4,5-epoxy-2-methylcyclohexyl formic acid-4,, 5 ,-epoxy-2,-methylcyclohexyl methyl esters 135 grams, productive rate 86%.
Claims (9)
1. carbon-nitrogen material solid-carrying heteropolyacid catalyst, prepared by following methods, its concrete steps are as follows: heteropoly acid and melamine are dissolved into respectively in the hot water of 50 ℃～60 ℃, then the mol ratio by heteropoly acid and melamine is 1:(1～4) heteropoly acid solution is joined in melamine solution, through stirring, filter, oven dry, obtain the white solid powder, then the high-temperature calcination under atmosphere of inert gases of this pressed powder is made its curing, namely get the carbon-nitrogen material solid-carrying heteropolyacid catalyst.
2. catalyst according to claim 1, is characterized in that described heteropoly acid is H
3PW
12O
40, H
4SiW
12O
40Or H
4PW
11VO
40
3. catalyst according to claim 1, the temperature that it is characterized in that described high-temperature calcination is 350 ℃～450 ℃, the heating rate scope is 5 ℃/minutes～10 ℃/minutes; Calcination time is 4 hours～6 hours.
4. method that the olefin epoxide that utilizes carbon-nitrogen material solid-carrying heteropolyacid catalyst as claimed in claim 1 is combined to, its concrete steps are: catalyst and olefin substrate are joined in organic solvent, and add hydrogen peroxide, constantly stir under heating until reaction finishes; Then with the solid-liquid two-phase separately, liquid phase is removed organic solvent and is obtained product, and solid-phase catalyst reclaims after washing drying.
5. method according to claim 4, is characterized in that described olefin substrate is cyclohexene, cyclo-octene, dicyclopentadiene, 3-cyclohexenecarboxylic acid-3 ,-cyclohexene methyl esters or 6-methyl-3-cyclohexenecarboxylic acid-6 ,-methyl-3 ,-cyclohexene methyl esters.
6. method according to claim 4 is characterized in that described catalyst amount is take the mole of tungsten as 3.2～10% of olefin substrate mole in catalyst.
7. method according to claim 4, the mass concentration scope that it is characterized in that described hydrogen peroxide is 20%～50%, the mol ratio of hydrogen peroxide and olefin substrate is 2～3:1.
8. method according to claim 4, is characterized in that heating-up temperature is 70～80 ℃, and the reaction time is 6～8h.
9. method according to claim 4, is characterized in that described solvent is halogenated hydrocarbons, nitrile, ester or ketone.
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| US20160177023A1 (en) * | 2014-12-17 | 2016-06-23 | Chang Chun Plastics Co., Ltd. | Continuous process of olefinic epoxidation by supported heteropoly acid |
| CN106984355A (en) * | 2017-05-25 | 2017-07-28 | 上海应用技术大学 | A kind of HPW/g C3N4 composites and its preparation method and application |
| CN109126890A (en) * | 2018-08-23 | 2019-01-04 | 江苏扬农化工集团有限公司 | A kind of preparation method of the olefin epoxidation catalysts of Polyaniline-Supported heteropoly acid |
| CN110120539A (en) * | 2019-05-05 | 2019-08-13 | 华北电力大学 | A kind of preparation method and application of modified heteropoly acid nano material |
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| US20160177023A1 (en) * | 2014-12-17 | 2016-06-23 | Chang Chun Plastics Co., Ltd. | Continuous process of olefinic epoxidation by supported heteropoly acid |
| JP2016153388A (en) * | 2014-12-17 | 2016-08-25 | 長春人造樹脂廠股▲分▼有限公司 | Continuous epoxidation method of olefin by carrier heteropolyacid |
| CN104525262A (en) * | 2014-12-29 | 2015-04-22 | 辽宁石油化工大学 | Preparation method of phosphotungstic acid and carbon nitride composite photocatalyst |
| CN105504350A (en) * | 2015-12-23 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | Polyoxometalate based flame retardant synergists and application thereof |
| CN106984355A (en) * | 2017-05-25 | 2017-07-28 | 上海应用技术大学 | A kind of HPW/g C3N4 composites and its preparation method and application |
| CN109126890A (en) * | 2018-08-23 | 2019-01-04 | 江苏扬农化工集团有限公司 | A kind of preparation method of the olefin epoxidation catalysts of Polyaniline-Supported heteropoly acid |
| CN109126890B (en) * | 2018-08-23 | 2021-06-25 | 江苏扬农化工集团有限公司 | Preparation method of olefin epoxidation catalyst of polyaniline-loaded heteropoly acid |
| CN110120539A (en) * | 2019-05-05 | 2019-08-13 | 华北电力大学 | A kind of preparation method and application of modified heteropoly acid nano material |
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