CN106238102A - There are the preparation method and applications of chirality Salen catalysis ceramic membrane - Google Patents
There are the preparation method and applications of chirality Salen catalysis ceramic membrane Download PDFInfo
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- CN106238102A CN106238102A CN201610730824.3A CN201610730824A CN106238102A CN 106238102 A CN106238102 A CN 106238102A CN 201610730824 A CN201610730824 A CN 201610730824A CN 106238102 A CN106238102 A CN 106238102A
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- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 239000000919 ceramic Substances 0.000 title claims abstract description 63
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000012530 fluid Substances 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 38
- 239000010935 stainless steel Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 238000001802 infusion Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 239000008187 granular material Substances 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 12
- 230000033228 biological regulation Effects 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 4
- 108090000862 Ion Channels Proteins 0.000 claims description 3
- 102000004310 Ion Channels Human genes 0.000 claims description 3
- 210000002469 basement membrane Anatomy 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- 229950000845 politef Drugs 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- 150000001669 calcium Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000007265 chloromethylation reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- -1 amino alcohol compounds Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- ZJBAHYJKBANYHJ-UHFFFAOYSA-N cobalt(3+);hydrate Chemical compound O.[Co+3] ZJBAHYJKBANYHJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 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
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000003987 high-resolution gas chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2475—Membrane reactors
-
- B01J35/59—
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- 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
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/40—Non-coordinating groups comprising nitrogen
Abstract
The present invention relates to a kind of preparation method and applications with chirality Salen catalysis ceramic membrane, belong to chiral catalysis field and technical field of membrane.By graft modification the immobilized Nano-meter SiO_2 having Salen catalyst2Particles filled in ceramic membrane, i.e. obtain that there is chirality Salen catalysis ceramic membrane.Reactor includes: infusion pump, material fluid bath, flow control valve, inlet, liquid outlet, sample tap, air inlet, air vent, stainless steel reaction container and rubber gasket etc..Present invention achieves nano-particle be grafted immobilized Salen catalyst and be filled into ceramic membrane, it is configured to ceramic membrane reactor, improve the immobilized rate of Salen catalyst, when carrying out asymmetric catalysis, improve conversion ratio and the ee value of reaction, and simplify the recycling process of catalyst, provide possibility for continuous prodution.
Description
Technical field
The present invention relates to a kind of preparation method and applications with chirality Salen catalysis ceramic membrane, belong to chirality
Catalytic field and technical field of membrane.
Background technology
Asymmetric catalysis can provide weight for the synthesis of many natural product, optical material, optics drugs etc.
The intermediate wanted, as having optically active epoxide, chiral alcohol or chiral amino alcohol compounds.Chirality Salen is catalyzed
Agent is the outstanding catalyst of asymmetric catalysis, such as, at aromatic alcohol kinetic resolution, Asymmetric catalytic epoxidation, azepine
In the reactions such as Cyclopropanated and epoxide hydrolytic kinetic resolution, the hands such as Salen-Mn, Salen-Co and Salen-Cr
Property Salen catalyst all presents good asymmetric induction effect.The research and development of Salen catalyst at scientific research field and
Wide application prospect is suffered from commercial production.
But Salen catalyst synthesis cost is high, and it is difficult to from reaction system separate, is not easily recycled and circulates profit
With.Along with the development of research, the recycling of Salen catalyst improves utilization ratio, reduces catalysis cost, gradually causes
The extensive concern of people.Carrying out catalyst immobilized is one of effective ways realizing this approach.
The carrier of immobilized Salen catalyst is broadly divided into organic carrier and inorganic carrier two class.Inorganic carrier is because of possessing
Learn good stability, the characteristics such as mechanical strength is high and receive much concern.Wherein using more inorganic carrier is kieselguhr, zeolite and point
Sub-sieves etc., carry out chemistry by active group such as carboxyl, amino and the hydroxyl introduced on carrier with the functional group on catalyst
It is immobilized that reaction realizes chamical binding.But these reaction systems still suffer from some problems: the most immobilized heterogeneous catalysis obtained
Remain a need for being separated from reaction system by modes such as filtrations, especially for some ultrafine dusts, may also need to use film
The technology such as separation separate and recover, and running cost is high；The most still can not realize continuous reaction；3. carrier can not evenly spread to
In reaction system so that catalyst contacts abundant not with reactant, affects mass transfer.The present invention fills immobilized by ceramic membrane
Salen catalyst, can not only effectively solve the problems referred to above, and can improve immobilized rate and the conversion of reaction of Salen catalyst
Rate and ee value (enantiomeric excess value).
Summary of the invention
The invention aims to solve that the low reaction caused of immobilized rate in prior art is insufficient and conversion ratio and ee
It is worth low problem, it is provided that a kind of preparation method and applications with chirality Salen catalysis ceramic membrane.
The present invention is achieved through the following technical solutions.
A kind of preparation method with chirality Salen catalysis ceramic membrane, specifically comprises the following steps that
Step one, Nano-meter SiO_22The graft modification of granule
By Nano-meter SiO_22Even particulate dispersion, in solvent, adds silane coupler, is heated to reflux under protection gas effect,
Reaction is evaporated after terminating and obtains being dried granule, stand-by.Described SiO2It is 10:1～1:10 with the mass ratio of silane coupler；
Step 2, Nano-meter SiO_22Granule immobilized Salen catalyst
By the dry even particulate dispersion of step one gained in solvent, add Salen catalyst, be passed through protection gas heating
Backflow, is evaporated the SiO obtaining immobilized Salen catalyst2Granule.The dry granule of step one gained and the matter of Salen catalyst
Amount ratio is 40:1～4:1；
Step 3, Nano-meter SiO_22Particles filled ceramic membrane
The SiO of the immobilized Salen catalyst that step 2 is obtained2Even particulate dispersion, obtains dispersion；Bottom is sealed
Mouth top connects in the ceramic membrane immersed systems of vacuum pump, makes the SiO of immobilized Salen catalyst by the way of evacuation2
Particles filled in ceramic membrane；Fill complete, take out ceramic membrane and with solvent clean for several times, dry, i.e. obtain that there is chirality
Salen catalysis ceramic membrane.
Described silane coupler is the silane coupler containing amino or sulfydryl.
The application of a kind of preparation method with chirality Salen catalysis ceramic membrane, will have chirality Salen catalysis merit
Energy ceramic membrane is put in reactor and is reacted as catalyst；
Described reactor includes: stainless steel reactor upper cover, stainless steel reactor cylinder body, stainless steel reactor lower cover, material
Liquid bath and infusion pump；Stainless steel reactor cylinder body is the two ends hollow circular cylinders with convex, stainless steel reactor cylinder body and pottery
The height of porcelain film is identical；Two through holes are offered on the sidewall of stainless steel reactor cylinder body；Stainless steel reactor upper cover and rustless steel
Cover under reactor and respectively offer 5 holes；Ceramic membrane is put in stainless steel reactor cylinder body and is put rubber gasket, stainless
Steel reactor upper cover and stainless steel reactor lower cover lid close and are connected by screw；Material fluid bath is sealing device, and top cover is offered
There are 6 mouths, respectively material fluid bath liquid outlet, the first material fluid bath inlet, the second material fluid bath inlet, material fluid bath air inlet, material
Liquid bath air vent, material fluid bath sample tap；Second material fluid bath inlet and reactor upper cover liquid outlet are connected by pipeline；First material
Liquid bath inlet and reactor cylinder body liquid outlet are connected by pipeline, and pipeline is provided with flow control valve；Material fluid bath liquid outlet
Connected by pipeline with reactor cylinder body inlet, pipeline is provided with infusion pump；Reactor lower cover exhaust close.
Work process: in material fluid bath, feed liquid is entered not from reactor cylinder body inlet by infusion pump by material fluid bath liquid outlet
In rust steel reactor cylinder body, close reactor lower cover air vent, flow through stainless steel reactor cylinder by regulation flow control valve
In the feed liquid in gap penetrates film entrance membrane channels between body and ceramic membrane, and flowed out through second by reactor upper cover liquid outlet
Material fluid bath inlet is circulated back in material fluid bath, regulation infusion pump and regulation flow control valve to control flow, during reaction from
Material fluid bath sample tap samples and passes through gas chromatogram tracing detection.
Described infusion pump is the pump of controllable flow rate, is preferably: peristaltic pump, syringe pump.
Described material fluid bath material is preferably: glass, politef, rustless steel.
Described ceramic membrane is the immobilized film having chiral salen catalysts.Basement membrane is inorganic oxide zirconium, titanium oxide or oxidation
Aluminum ceramic membrane.
Beneficial effect
(1) problem solving catalyst recycling difficulty:
By immobilized in Nano-meter SiO_2 for the grafting of Salen catalyst2Granule is also filled into ceramic membrane, reaction terminate directly by film with
Reactant liquor separates and i.e. can reach the purpose reclaiming catalyst, and by the immobilized stream that substantially avoided catalyst of chamical binding method
Lose；
(2) it is that continuous prodution provides possibility:
After ceramic membrane fills immobilized Salen catalyst, it is fixed in ceramic membrane reactor, can be continually used for repeatedly
Asymmetric catalytic epoxidation reacts, and provides possibility for continuous prodution；
(3) problem that immobilized rear catalyst is insufficient contact with reaction substrate is solved:
Reactant liquor squeezes into stainless steel reactor by infusion pump, by valve regulated, makes feed liquid penetrate through supporting layer
Film side, thus reached the purpose that reaction substrate is fully contacted with catalyst.And in course of reaction feed liquid can reactor with
Constantly circulate between material fluid bath, increase the probability that unreacted substrate contacts with catalyst；
(4) purpose of tracing detection at any time has been reached:
The sample tap that material fluid bath is provided with, can realize sampling at any time and carry out situation with tracing detection reaction；
(5) asymmetric catalysis carried out with this chirality Salen catalysis membrane reactor, can reach preferably catalysis
Effect.
Accompanying drawing explanation
Fig. 1 is the structure chart of chirality Salen catalysis ceramic membrane reactor of the present invention；
Wherein, 1 stainless steel reactor upper cover, 2 stainless steel reactor cylinder bodies, 3 stainless steel reactor lower covers, 4
Ceramic membrane, 5 rubber gaskets, 6 material fluid baths, 7 infusion pump, 8 flow control valves, 101 reactor upper covers go out liquid
Mouth, 201 reactor cylinder body liquid outlets, 202 reactor cylinder body inlets, 301 reactor lower cover air vents, 601 material
Liquid bath liquid outlet, 602 first material fluid bath inlets, 603 second material fluid bath inlets, 604 material fluid bath air inlets,
605 material fluid bath air vents, 606 material fluid bath sample taps.
Fig. 2 is the route map that ceramic membrane basement membrane of the present invention fills immobilized chiral salen catalysts.
Detailed description of the invention
The invention will be further described with embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of preparation method with chirality Salen catalysis ceramic membrane, as in figure 2 it is shown, specifically comprise the following steps that
Step one, mono-CH2The synthesis of Cl-Salen-Mn (III) catalyst:
By 2-TBP synthesis 3-tert-butyl group salicylide (product 1), 3-tert-butyl group salicylide chloromethylation is synthesized
The 3-tert-butyl group-5-chloromethyl salicylaldehyde (product 2)；3,5-di-t-butyl water is synthesized through Duff by 2,4-DI-tert-butylphenol compounds
Poplar aldehyde (product 3), product 3 and (1R, 2R)-(-) reaction of-cyclohexanediamine prepares (R, R)-N-3,5-di-tert-butyl salicylaldehyde-1,
2-cyclohexanediamine (product 4)；Product 4 and product 2 react (R, R)-N-(3,5-di-tert-butyl salicylaldehyde)-N-(3 '-tertiary fourth
Base-5 '-chloromethyl salicylaldehyde)-1,2-cyclohexanediamine (product 5), product 5 and Mn (OAc)2.4H2O back flow reaction prepare (R, R)-
N-(3,5-di-tert-butyl salicylaldehyde)-N-(3 '-tert-butyl group-5 '-chloromethyl salicylaldehyde)-1,2-cyclohexanediamine conjunction manganese (II) (product
Thing 6), product 6 obtain after air oxidation (R, R)-N-(3,5-di-tert-butyl salicylaldehyde)-N-(3 '-tert-butyl group-5 '-chloromethyl
Salicylide)-1,2-cyclohexanediamine manganese chloride (III) (mono-CH2Cl-Salen-Mn(Ⅲ))。
Step 2, Nano-meter SiO_22The graft modification of granule:
By 5.0g Nano-meter SiO_22Granule adds in 300mL toluene (the most plus hydrogenated calcium removes water), uses super after stirring 2 hours
Sound disperses 0.5 hour, adds the APTES (APTES) of 4.4mL, at N2110 DEG C it are heated under effect
Refluxing 36 hours, granule is evaporated after terminating by reaction, stand-by.
Step 3, Nano-meter SiO_22The immobilized mono-CH of granule2Cl-Salen-Mn (III) catalyst:
Take the Nano-meter SiO_2 after 4.0g grafting2Even particulate dispersion, in 240mL toluene (the most plus hydrogenated calcium removes water), adds
Enter 0.3g mono-CH2Cl-Salen-Mn (III) catalyst, at N2Being heated to 110 DEG C under effect to reflux 24 hours, reaction terminates
After granule is evaporated, stand-by.
Step 4, Nano-meter SiO_22Particles filled ceramic membrane
Take the immobilized mono-CH of 2.0g2SiO after Cl-Salen-Mn (III) catalyst2Even particulate dispersion is in 250mL ethanol
In, bottom is sealed in the ceramic membrane immersed systems that top connects vacuum pump, persistently fill by the way of evacuation 5 hours
After, collect reactant liquor and with ethanol (200mL × 3) cleaning ceramic film, dry.
The application of a kind of preparation method with chirality Salen catalysis ceramic membrane, will have chirality Salen catalysis merit
Reactor can be put into as the cinnamic asymmetric epoxidation reaction of catalyst by ceramic membrane.First reactor is placed in cooling
Reactive bath technique is cooled to 0 DEG C, successively in material fluid bath add 4mmol styrene, 20mmol N-methyl morpholine oxide (NMO),
1mmol metachloroperbenzoic acid (m-CPBA), 0.1g toluene and 55mL dichloromethane, stir, and opens infusion pump, regulation stream
Control valve, is circulated reaction.
Described reactor, as it is shown in figure 1, include: stainless steel reactor upper cover 1, stainless steel reactor cylinder body 2, rustless steel
Reactor lower cover 3, material fluid bath 6 and infusion pump 7；Stainless steel reactor cylinder body 2 is the two ends hollow circular cylinders with convex, stainless
Steel reactor cylinder body 2 is identical with the height of ceramic membrane 4；Two through holes are offered on the sidewall of stainless steel reactor cylinder body 2；Rustless steel
5 holes are respectively offered on reactor upper cover 1 and stainless steel reactor lower cover 3；Ceramic membrane 4 is put in stainless steel reactor cylinder body 2
And putting rubber gasket 5, stainless steel reactor upper cover 1 and stainless steel reactor lower cover 3 lid close and are connected by screw；Material
Liquid bath 6 is sealing device, and top cover offers 6 mouths, respectively material fluid bath liquid outlet the 601, first material fluid bath inlet 602,
Second material fluid bath inlet 603, material fluid bath air inlet 604, material fluid bath air vent 605, material fluid bath sample tap 606；Second feed liquid
Groove inlet 603 and reactor upper cover liquid outlet 101 are connected by pipeline；First material fluid bath inlet 602 and reactor cylinder body
Liquid outlet 201 is connected by pipeline, and pipeline is provided with flow control valve 8；Material fluid bath liquid outlet 601 and reactor cylinder body feed liquor
Mouth 202 is connected by pipeline, and pipeline is provided with infusion pump 7；Reactor lower cover air vent 301 cuts out.
Work process: in material fluid bath 6, feed liquid is passed through infusion pump 7 from reactor cylinder body inlet by material fluid bath liquid outlet 601
202 enter in stainless steel reactor cylinder body 2, close reactor lower cover air vent 301, are flowed through by regulation flow control valve 8
In between stainless steel reactor cylinder body 2 and ceramic membrane 4, the feed liquid in gap penetrates film entrance membrane channels, and gone out by reactor upper cover
Liquid mouth 101 flows out through the second material fluid bath inlet 603 and is circulated back in material fluid bath 6, regulation infusion pump 7 and flow control valve 8
To control flow, sample from material fluid bath sample tap 606 during reaction.
Course of reaction extracted sample every 1 hour from sample tap, was tracked detection with high resolution gas chromatography.React 8 little
Time ee value can reach 42.3%, corresponding cinnamic conversion ratio is 35.1%.Reaction equation is shown in formula (1-1), marks configuration
Material be target compound.
Embodiment 2
A kind of preparation method with chirality Salen catalysis ceramic membrane, specifically comprises the following steps that
Step one, mono-CH2The synthesis of Cl-Salen-Co (III) catalyst:
By 2-TBP synthesis 3-tert-butyl group salicylide (product 1), 3-tert-butyl group salicylide chloromethylation is synthesized
The 3-tert-butyl group-5-chloromethyl salicylaldehyde (product 2)；3,5-di-t-butyl water is synthesized through Duff by 2,4-DI-tert-butylphenol compounds
Poplar aldehyde (product 3), product 3 and (1R, 2R)-(-) reaction of-cyclohexanediamine prepares (R, R)-N-3,5-di-tert-butyl salicylaldehyde-1,
2-cyclohexanediamine (product 4)；Product 4 and product 2 react (R, R)-N-(3,5-di-tert-butyl salicylaldehyde)-N-(3 '-tertiary fourth
Base-5 '-chloromethyl salicylaldehyde)-1,2-cyclohexanediamine (product 5), product 5 and Co (OAc)2.4H2O back flow reaction prepare (R, R)-
N-(3,5-di-tert-butyl salicylaldehyde)-N-(3 '-tert-butyl group-5 '-chloromethyl salicylaldehyde)-1,2-cyclohexanediamine conjunction cobalt (II) (product
Thing 6), product 6 obtain after air oxidation (R, R)-N-(3,5-di-tert-butyl salicylaldehyde)-N-(3 '-tert-butyl group-5 '-chloromethyl
Salicylide)-1,2-cyclohexanediamine acetic acid conjunction cobalt (III) hydrate (mono-CH2Cl-Salen-Co(Ⅲ))。
Step 2, Nano-meter SiO_22The graft modification of granule:
By 5.0g Nano-meter SiO_22Granule adds in 300mL toluene (the most plus hydrogenated calcium removes water), uses super after stirring 2 hours
Sound disperses 0.5 hour, adds the APTES (APTES) of 4.4mL, at N2110 DEG C it are heated under effect
Refluxing 36 hours, granule is evaporated after terminating by reaction, stand-by.
Step 3, Nano-meter SiO_22The immobilized mono-CH of granule2Cl-Salen-Co (III) catalyst:
Take the Nano-meter SiO_2 after 4.0g grafting2Even particulate dispersion, in 240mL toluene (the most plus hydrogenated calcium removes water), adds
Enter 0.3g mono-CH2Cl-Salen-Co (III) catalyst, at N2Being heated to 110 DEG C under effect to reflux 24 hours, reaction terminates
After granule is evaporated, stand-by.
Step 4, Nano-meter SiO_22Particles filled ceramic membrane
Take the immobilized mono-CH of 2.0g2SiO after Cl-Salen-Co (III) catalyst2Even particulate dispersion is in 250mL ethanol
In, bottom is sealed in the ceramic membrane immersed systems that top connects vacuum pump, persistently fill by the way of evacuation 5 hours
After, collect reactant liquor and with ethanol (200mL × 3) cleaning ceramic film, dry.
The application of a kind of preparation method with chirality Salen catalysis ceramic membrane, will have chirality Salen catalysis merit
Energy ceramic membrane is put into reactor and is carried out epoxychloropropane hydrolytic kinetic resolution experiment as catalyst.Accurately measure 25ml epoxy
Chloropropane, 25ml oxolane, 0.8000g hexone, 3.75mL deionized water, by the mixing of this catalyst system and catalyzing all
Even, open infusion pump, regulate flow control valve, be circulated reaction, and periodically extract sample from sample tap, with efficient gas phase color
Spectrum is tracked detection.Reaction equation is shown in formula (1-2).
Claims (8)
1. there is a preparation method for chirality Salen catalysis ceramic membrane, specifically comprise the following steps that
Step one, Nano-meter SiO_22The graft modification of granule
By Nano-meter SiO_22Even particulate dispersion, in solvent, adds silane coupler, is heated to reflux, reaction under protection gas effect
It is evaporated after end and obtains being dried granule, stand-by；Described SiO2It is 10:1～1:10 with the mass ratio of silane coupler；
Step 2, Nano-meter SiO_22Granule immobilized Salen catalyst
By the dry even particulate dispersion of step one gained in solvent, add Salen catalyst, be passed through protection gas and heat back
Stream, is evaporated the SiO obtaining immobilized Salen catalyst2Granule；The dry granule of step one gained and the quality of Salen catalyst
Ratio is 40:1～4:1；
Step 3, Nano-meter SiO_22Particles filled ceramic membrane
The SiO of the immobilized Salen catalyst that step 2 is obtained2Even particulate dispersion, obtains dispersion；By sealing top, bottom
End connects in the ceramic membrane immersed systems of vacuum pump, makes the SiO of immobilized Salen catalyst by the way of evacuation2Granule
It is filled in ceramic membrane；Fill complete, take out ceramic membrane and with solvent clean for several times, dry, i.e. obtain that there is chirality Salen and urge
Change function ceramic membrane.
2. there is an application for the preparation method of chirality Salen catalysis ceramic membrane, will have chirality Salen catalysis
Ceramic membrane is put in reactor and is reacted as catalyst；
Described reactor includes: stainless steel reactor upper cover (1), stainless steel reactor cylinder body (2), stainless steel reactor lower cover
(3), material fluid bath (6) and infusion pump (7)；Stainless steel reactor cylinder body (2) is the two ends hollow circular cylinders with convex, rustless steel
Reactor cylinder body (2) is identical with the height of ceramic membrane (4)；Two through holes are offered on the sidewall of stainless steel reactor cylinder body (2)；No
5 holes are respectively offered on rust steel reactor upper cover (1) and stainless steel reactor lower cover (3)；Ceramic membrane (4) is put into stainless steel reaction
In device cylinder body (2) and put rubber gasket (5), stainless steel reactor upper cover (1) and stainless steel reactor lower cover (3) lid close
And be connected by screw；Material fluid bath (6) is sealing device, and top cover offers 6 mouths, respectively material fluid bath liquid outlet (601),
First material fluid bath inlet (602), the second material fluid bath inlet (603), material fluid bath air inlet (604), material fluid bath air vent
(605), material fluid bath sample tap (606)；Second material fluid bath inlet (603) and reactor upper cover liquid outlet (101) pass through pipeline
Connect；First material fluid bath inlet (602) and reactor cylinder body liquid outlet (201) are connected by pipeline, and pipeline is provided with stream
Adjustable valve (8)；Material fluid bath liquid outlet (601) and reactor cylinder body inlet (202) are connected by pipeline, and pipeline is provided with
Infusion pump (7)；Reactor lower cover air vent (301) is closed.
A kind of preparation method with chirality Salen catalysis ceramic membrane, it is characterised in that:
Described silane coupler is the silane coupler containing amino or sulfydryl.
A kind of application of the preparation method with chirality Salen catalysis ceramic membrane, its feature
Be: described in there is chirality Salen catalysis ceramic membrane put into the process that reactor carries out being catalyzed and be: material fluid bath (6) is expected
Liquid is entered stainless steel reactor cylinder body by infusion pump (7) from reactor cylinder body inlet (202) by material fluid bath liquid outlet (601)
(2) in, close reactor lower cover air vent (301), flow through stainless steel reactor cylinder body by regulation flow control valve (8)
(2) feed liquid in gap penetrates film and enters in membrane channels and between ceramic membrane (4), and is flowed by reactor upper cover liquid outlet (101)
Go out and be circulated back in material fluid bath (6) by the second material fluid bath inlet (603), regulation infusion pump (7) and regulation flow control valve
(8) to control flow, sample from material fluid bath sample tap (606) during reaction and pass through gas chromatogram tracing detection.
5. the application of a kind of preparation method with chirality Salen catalysis ceramic membrane as described in claim 2 or 4, its
It is characterised by: described infusion pump is the pump of controllable flow rate.
A kind of application of the preparation method with chirality Salen catalysis ceramic membrane, its feature
It is: described infusion pump is peristaltic pump or syringe pump.
7. the application of a kind of preparation method with chirality Salen catalysis ceramic membrane as described in claim 2 or 4, its
It is characterised by: described material fluid bath material is: glass, politef or rustless steel.
8. the application of a kind of preparation method with chirality Salen catalysis ceramic membrane as described in claim 2 or 4, its
It is characterised by: described ceramic membrane is the immobilized film having chiral salen catalysts；Basement membrane is inorganic oxide zirconium, titanium oxide or oxygen
Change aluminum ceramic membrane.
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