CN106977709A - A kind of Salen catalyst using CN as axial ligand and its preparation method and application - Google Patents

A kind of Salen catalyst using CN as axial ligand and its preparation method and application Download PDF

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CN106977709A
CN106977709A CN201710285379.9A CN201710285379A CN106977709A CN 106977709 A CN106977709 A CN 106977709A CN 201710285379 A CN201710285379 A CN 201710285379A CN 106977709 A CN106977709 A CN 106977709A
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salen
catalyst
preparation
salen catalyst
metal
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程瑞华
李佳佳
周宇杰
刘柏平
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East China University of Science and Technology
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers

Abstract

The present invention relates to a kind of Salen catalyst using CN as axial ligand and its preparation method and application, preparation process is that (1) synthesizes SalenH2；(2) SalenH2 is synthesized into Salen M with the ethanol solution hybrid reaction of metal M salt；(3) Salen M are synthesized into the Salen catalyst using CN as axial ligand with the aqueous solution hybrid reaction of metal cyanides.Compared with prior art, the present invention is by using the cyano group of strong electron-withdrawing power as axial ligand, and catalyst stabilization is unlikely to deteriorate inactivation, in catalysis carbon dioxide and epoxypropane copolymerization into the generation in the course of reaction of makrolon, being conducive to suppressing cyclic carbonate ester accessory substance；Process window is broadened, under the conditions of high temperature polymerization, and the activity of Salen catalyst is greatly improved.

Description

A kind of Salen catalyst using CN as axial ligand and its preparation method and application
Technical field
The present invention relates to catalyst technical field, and in particular to a kind of Salen catalyst using CN as axial ligand and its Preparation method and application.
Background technology
With the reinforcement of people's environmental consciousness, green low-carbon turns into the theme that people live, and solves problem of environmental pollution It is very urgent.With CO2Based on greenhouse gases trigger Global Temperature rise, sea level rise, the natural calamity such as unusual weather conditions Evil, brings very serious consequence to earth ecology, or even threatens the existence of the mankind, and global industry titanium dioxide at present The discharge capacity of carbon is also continuing to increase, and the environmental problem thus triggered is also with CO in air2The continuation of increasing of content deteriorates, long This will seriously threaten environment for the survival of mankind in the past.Therefore, effective utilize for strengthening carbon dioxide is to solve carbon emission Effective way.Carbon dioxide and epoxides can prepare makrolon with copolymerization, and the reaction synthesizes high score using carbon dioxide Sub- material, atom utilization is high, and the makrolon of generation is biodegradable, instead of the plastics for being difficult to degrade of parts of traditional, has Beneficial to " white pollution " problem of mitigation, it is the focus studied at present, is also CO2Most one of Land use systems of application prospect.
From Inoue in 1969 first using diethyl zinc/aqueous systems be successfully catalyzed carbon dioxide and propylene oxide copolymer with Come, have been developed including diethyl zinc/many Proton Systems, carboxylate metal salt system, double metal cyanide, rare-earth ternary system with And a variety of catalyst system and catalyzings including Salen systems, but currently without a kind of preferably catalyst system and catalyzing capable of being industrialized, these catalysis The problem of system all has not high catalytic activity or not good product property, prepares a kind of high catalytic efficiency, carbon dioxide insertion The catalyst that rate is high, product property is good turns into urgent problem, is also carbon dioxide-base makrolon large-scale application Premise.
Salen is N, the general designation of N '-ethylenebis (salicylic alidehyde imine) class compound, and Salen catalyst system and catalyzings can be efficient Carbon dioxide and propylene oxide copolymer are activated, the makrolon of alternating copolymerization, and product stereoselectivity and region is prepared Selectivity is high, can effectively suppress the generation of polyether segment, but its activity need further raising, especially when polymerization temperature is raised When, the selectivity of the catalyst system and catalyzing drastically declines, and generates the more stable small molecule cyclic carbonate ester of thermodynamics.
, (the Journal of the American Chemical Society, 2005.127 such as Coates in 2003 (31):Salen-Co 10869-10878) is used first(III)(OAc) polymerization of catalysis carbon dioxide and expoxy propane, gentle Reaction condition under obtained selectivity of product be more than carbonate unit content in 99%, polymer and be more than 90%, and study Influence of the R substituent to catalytic efficiency on phenyl ring.Influence result to temperature shows, 25 DEG C be the catalytic reaction optimal temperature Degree, when temperature is below or above this temperature, catalytic activity is reduced, after temperature is higher than 40 DEG C, molecular weight of product reduction, polyethers The content of chain link is significantly raised.Catalytic activity, product are selected in addition, Coates also has studied in detail catalyst axial ligand Property, the influence of regio- and stereo-selectivity, and be prepared for a series of Salen catalyst of axially different parts respectively, catalysis two The result of carbonoxide and propylene oxide copolymer shows that its catalytic activity order is I<Cl<OAc<OBzF5<Br, wherein Salen-Co(III)Br activity is up to TOF=90h-1。
Lv little Bing etc. (Journal of the American Chemical Society, 2006,128,1664-1674) It was found that, although Salen-Co(III)X can be catalyzed carbon dioxide propylene oxide copolymer under 5.5MPa pressure carbon dioxide and obtain High selectivity and more than 80% end to end makrolon, but when reducing pressure carbon dioxide or rise polymerization temperature Wait, catalyst will be reduced to the divalence Co (II) of red, no longer show catalytic activity.By to a series of axially different The catalyst research discovery of part, Salen-Co(III)X catalyst system and catalyzing axial ligands X electronic effect, nucleophilicity and leaving capability And the coordination ability of nucleopilic reagent all significantly affects the regio- and stereo-selectivity of catalytic efficiency, product.By weak energy of leaving away The electrophilic group of power can effectively suppress the formation of cyclic carbonate ester as the axial ligand of Salen catalyst, improve product choosing Selecting property and corresponding selection, with the non-nucleophilic anion with large space steric hindrance and weak leaving capability as co-catalyst, composition Desired catalytic system is catalyzed carbon dioxide and propylene oxide copolymer has excellent catalytic efficiency, higher corresponding selection, head and the tail The structure that connects is more than 95%, and carbonate unit content is more than 99%.
It is the current more extensive catalyst system and catalyzing of research using Cl and Br as the axial ligand of Salen catalyst, but when anti- Temperature is answered to raise, the regio- and stereo-selectivity of polymerizate drastically declines, and polymerisation is an exothermic process, if instead Fuel factor during answering can not spread immediately, and local heating will cause the drastically decline of selectivity and makrolon chain link, So as to influence product property, this is also a principal element for limiting the amplification of Salen systems.
The content of the invention
The purpose of the present invention is exactly to provide a kind of Salen catalyst using CN as axial ligand to solve the above problems And its preparation method and application, change axial ligand on the basis of Salen skeletons, using its electronic effect to activated centre and Steric hindrance effect makes it in the polymerization, is conducive to suppressing the generation of cyclic carbonate, improves the production of polypropylene carbonate Thing selectivity, under high temperature polymerization reaction condition, with higher activity and selectivity.
The purpose of the present invention is achieved through the following technical solutions：
A kind of Salen catalyst using CN as axial ligand, molecular structural formula is：
Wherein,
M=Cr, Co, Zn, Ni, Mn, Fe or Al；
R1/R2=H or (1R, 2R)-trans- (CH2)4；
R3/R4=H, Cl, Br or t-Bu.
Work as R1/R2During=H, the molecular structural formula of the catalyst is：
Work as R1/R2=(1R, 2R)-trans- (CH2)4When, the molecular structural formula of the catalyst is：
The preparation method of described Salen catalyst, specifically includes following steps：
(1) SalenH2 is synthesized；
(2) SalenH2 is synthesized into Salen-M with the ethanol solution hybrid reaction of metal M salt；
(3) the Salen-M Salen synthesized with the aqueous solution hybrid reaction of metal cyanides using CN as axial ligand are catalyzed Agent.
Step (1), (2) are made by this area conventional meanses, wherein, SalenH2 can pass through cyclohexanediamine or ethylenediamine Obtained with the reaction of 3,5- di-tert-butyl salicylaldehydes.
Using, it is necessary to split cyclohexanediamine, cyclohexanediamine and acetic acid successively are added into L- (+) tartaric acid during cyclohexanediamine Stirred with the mixed liquor of distilled water, obtain (R, R) -1,2- cyclohexanediamine list-(+) tartrate；By (R, R) -1,2- hexamethylenes Diamines list-(+) tartrate and potassium carbonate, distilled water, ethanol mixed dissolution, the ethanol for adding 3,5- di-tert-butyl salicylaldehydes are molten Liquid is stirred, and obtains SalenH2；
During using ethylenediamine, in the ethanol solution that the ethanol solution of ethylenediamine is added drop-wise to 3,5- di-tert-butyl salicylaldehydes, Reaction temperature is at 60 DEG C or so, and the reaction time is 4-6 hours, and room temperature is cooled to afterwards, is stood overnight, and filters, obtains SalenH2。
Described metal M salt is selected from zinc acetate, nickel acetate, manganese acetate, manganese nitrate, ferrous sulfate, ferric sulfate, protochloride Iron, cobalt chloride, thiocyanation cobalt, cobalt acetate, chromium chloride, chromium acetate or aluminium chloride.
Under nitrogen protection, by SalenH2 and dichloromethane mixed dissolution, the second of metal M salt is added dropwise in step (2) at room temperature Alcoholic solution is simultaneously stirred, cold filtration, methanol washing, 40 DEG C of vacuum drying, and metal M salt and SalenH2 mol ratio are 1:0.5- 2, preferably 1:1.2.
Metal cyanides described in step (3) is selected from the high cobalt acid of the sour potassium of the high cobalt of six cyano group, six cyano group potassium ferrates, six cyano group The sour potassium of calcium, four cyano nickel, the high cobalt acid lithium of six cyano group, six cyano group high chromic acid content potassium, six cyano group high chromic acid content calcium or six cyano group high chromic acid content lithiums. Concretely comprise the following steps：P-methyl benzenesulfonic acid is dissolved in acetone, Salen-M is dissolved in dichloromethane, then both are mixed, oxygen is passed through Gas, 50-70min being stirred at room temperature, vacuum extracts organic solvent, then washing suction filtration with n-hexane, solid product is obtained after drying And dichloromethane is dissolved in, it is added to metal cyanides saturated aqueous solution and shakes, uses anhydrous Na2SO4Water removal, vacuum extract dichloro Methane, then washed with n-hexane, precipitation, 40 DEG C of vacuum drying is collected by filtration.Preferably, described toluene sulfonic acide and acetone Match as 1g:The proportioning of 70-80mL, Salen-M and dichloromethane is 1g:30-35mL, described solid product and dichloromethane Proportioning be 1g:40-60mL.
Described Salen catalyst is used to be catalyzed carbon dioxide and epoxides copolyreaction prepares makrolon.
The mol ratio of described epoxides and Salen catalyst is 200-10000:1, described Salen catalyst with The mol ratio of co-catalyst is 1:0-2, pressure is 1-10MPa during reaction, and reaction temperature is 15-100 DEG C.
Cyano group (CN) of the invention by using strong electron-withdrawing power is as axial ligand, because cyano group has strong electrophilic energy Power, and cyano group has stronger complexing power with heavy metal ion, the catalyst is relatively stablized, and is unlikely to deteriorate inactivation, reduces center The cloud density of metal simultaneously improves its electron deficient, is being catalyzed carbon dioxide and epoxypropane copolymerization into makrolon In course of reaction, be conducive to suppressing the generation of cyclic carbonate ester, under the conditions of high temperature polymerization, activity is greatly enhanced, and gathers The selectivity and makrolon content for closing product are very high, and its activity may be up to 378.59h-1, selectivity is 94%, carbonic ester list First content is 99%, and number-average molecular weight is in 17.7kg/mol, and molecular weight distribution is 1.01, and can improve polymer areas selection Property, headtotail part in polycarbonate chain is up to 95%.
Brief description of the drawings
Fig. 1 is the infrared spectrum using catalyst preparation makrolon of the present invention；
Fig. 2 is using catalyst preparation makrolon of the present invention1H NMR nuclear magnetic spectrograms；
Fig. 3 is catalyst SalenCo(III)CN IR Characterization figure；
Fig. 4 is catalyst SalenCo(III)CN and SalenH2, SalenCo(III)CN IR Characterization figure.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of SalenCo(III)CN catalyst, during preparation, first splits cyclohexanediamine, then by the 2mol tertiary fourths of 3,5- bis- Cyclohexanediamine after base salicylide is split with 1mol synthesizes salicylic alidehyde imine, then mixes metal center with the reaction of acetic anhydride cobalt, Finally by SalenCo(II)It is oxidized to trivalent and mixes axial ligand CN, concretely comprises the following steps：
(1) fractionation of cyclohexanediamine：500mL three-necked flasks are fixed in oil bath pan, pacified respectively at its three openings Mechanical agitator, constant pressure funnel and spherical reflux condensing tube are loaded onto, connects and leads to condensed water after pipeline, by 37.5g L- (+) tartaric acid and 100mL distilled water are added in flask, open mechanical agitator, and oil bath pan sets temperature to be 70 DEG C, measured 66.6mL is poured into constant pressure funnel along trans-ortho-cyclohexanediamine, is slowly added dropwise into above-mentioned solution, after completion of dropping, by oil Bath temperature setting is 90 DEG C.25mL acetic acid is measured again, is added dropwise with constant pressure funnel into three-necked flask, is stopped after completion of dropwise addition Only heat, continue to stir 2 hours.Suction filtration after finally mixed solution is cooled down 2 hours with ice-water bath, then with 25mL cold water and methanol Cyclic washing is precipitated to white, by gained be deposited at 40 DEG C be dried in vacuo 6 hours be (R, R) -1,2- cyclohexanediamine list - (+) tartrate.
(2) SalenH2 synthesis：1000mL three-necked flasks are fixed in oil bath pan, pacified respectively at its three openings Mechanical agitator, constant pressure funnel and spherical reflux condensing tube are loaded onto, connects and leads to condensed water after pipeline, is added in flask (R, R) -1,2- cyclohexanediamine list-(+) tartrate prepared by 14.58g above-mentioned steps, 15.8g potassium carbonate and 75mL distilled water, Open mechanical agitator to be allowed to dissolve, add 300mL ethanol, mixed solution is heated to 80 DEG C.125mL is first used in beaker Ethanol dissolves 26.85g 3, and 5- di-tert-butyl salicylaldehydes are slowly added dropwise in above-mentioned mixed solution by constant pressure funnel, acute Flowed back 2 hours under strong stirring, close and add 75mL distilled water after heater into flask, make to be cooled to room temperature, continue to stir 2 Hour.Suction filtration after finally mixed solution is cooled down 1 hour with ice-water bath.Filter cake is removed and is put into beaker, 250mL dichloros are added Methane is dissolved, then with distilled water and saturated common salt water washing for several times, through anhydrous Na2SO4Rotavapor under vacuum is used after water removal Dichloromethane solvent is extracted, with ethyl alcohol recrystallization after being dried 6 hours in 40 DEG C of vacuum drying chambers, obtaining yellow powder is SalenH2。
(3) synthesis of Chiral cobalt complex：100mL three-necked flasks are fixed on magnetic stirring apparatus, two side joint bend pipes lead to Enter nitrogen protection, middle interface installs constant pressure funnel, and SalenH2 prepared by 3.65g above-mentioned steps is added in flask Dichloromethane is refined with 25mL, magnetic stirring apparatus is opened and is allowed to dissolve.L.42g it acetic anhydride cobalt will be dissolved in 30mL methanol, lead to Cross constant pressure funnel to be added dropwise in flask, can now generate a large amount of red solids, notice that can observation agitator just Often work, nitrogen protects lower press filtration after mixed solution is cooled down 0.5 hour with ice-water bath after completion of dropwise addition, and three are washed with methanol Secondary, it 6 hours is SalenCo that gained, which precipitates 40 DEG C of vacuum drying,(II)。
(4)SalenCo(III)CN synthesis：0.4g p-methyl benzenesulfonic acids are dissolved in 30mL acetone, by 1.2g SalenCo(II)It is dissolved in 40mL dichloromethane, then both is mixed, be passed through dry oxygen, is stirred at room temperature 1 hour.Decompression is extracted Solvent, washed once with a small amount of n-hexane, and precipitation is collected by filtration, and vacuum drying obtains blackish green pulverulent solids Salen-Co(III)OTs.Salen-Co prepared by 1.0g above-mentioned steps(III)OTs is dissolved in 50mL dichloromethane, pours into pear shape separatory funnel In, with 100mL saturations K3[Co(CN)6] aqueous solution concussion washing 3 times.Organic layer anhydrous Na2SO4It is concentrated under reduced pressure after drying, then Washed with a small amount of n-hexane, precipitation is collected by filtration, further vacuum drying obtains pulverulent solids, as SalenCo(III)CN is urged Agent.
Catalyst characteristics functional group analysis is analyzed using BRUKER VERTEX70 infrared spectrometers, spectral region 400cm-1-4000cm-1, scanning resolution 4.0cm-1, sweep speed is 10.0KHz, and sample and background single channel sweep time are all For 32s.Catalyst SalenCo(III)CN and SalenH2, SalenCo(III)CN IR Characterization figure as shown in Figure 3,4, in figure It can be seen that SalenCo(III)CN is in 2129cm-1There is the last one peak at place, is v (CN) characteristic peak herein.Due to adding in course of reaction The reagent K entered3[Co(CN)6]2In, v (CN) peak position is in 2189cm-1, show that the coordination environment of CN in raw material has occurred and that and change Become, be complexed with the metallic cobalt center in Salen parts.In addition, [C36H52N2O2Co]+Electrospray ionization mass spectrum (ESI-MS) analysis result For：Theoretical value, 603.3；Actual value, 603.3.
Embodiment 2
When catalyst prepares makrolon for carbon dioxide and epoxides copolyreaction, concretely comprise the following steps：Will reaction Kettle is vacuumized after cleaning, and is preheated to 110 DEG C, with carbon dioxide replacement three times, keeps vacuum state, reactor is cooled into 25 DEG C, catalyst and expoxy propane are weighed, polymerization temperature is warming up to, carbon dioxide is passed through to pressure is set, starts mechanical agitation, Start timing.After reaction terminates, mechanical agitation is first closed, 25 DEG C are cooled to, relief valve is opened and releases unreacted carbon dioxide, Open and quickly removed after reactor for carrying out1H NMR and the reaction product of gpc analysis test, sample preparation test.By residue polymerization Product, which takes out, to be fitted into small beaker, adds a small amount of CH2Cl2, stirring is allowed to dissolve, then is poured slowly into equipped with 4 times of volumes methanols In beaker, there will be white polymeric product precipitation, then product is dissolved, repeatedly obtain pure target product after washing, as gather Carbonic ester.
In the present embodiment, 0.4mol Salen-Co are added in reactor(III)CN and 14mL expoxy propane, setting reaction temperature Spend for 75 DEG C, be passed through 5.0MPa carbon dioxide, start mechanical agitation, react 4 hours, polymerization result:TOF=54.89h-1, choosing Selecting property=97%, Mn=12.2kg/mol, PDI=1.04.
Embodiment 3
Reactor adds 0.1mol Salen-Co in the present embodiment(III)CN and 0.1mol co-catalysts PPNCl, 14mL ring Ethylene Oxide, sets reaction temperature as 50 DEG C, is passed through 2.0MPa carbon dioxide, starts mechanical agitation, reacts 2 hours.Polymerization knot Really:TOF=378.59h-1, selectivity=94%, Mn=27.7kg/mol, PDI=1.01.
Embodiment 4
Using method same as Example 1, metal cyanides uses six cyano group potassium ferrates, and metal M salt uses acetic acid Zinc, metal M salt and SalenH2 mol ratio are 1:0.5, prepare Salen-Zn(II)CN catalyst, and for being catalyzed carbon dioxide Makrolon is prepared with epoxides copolyreaction, after reactor is cleaned and dried, 0.1mol Salen-Zn are added(II)CN and 0.1mol co-catalysts PPNCl, 14mL expoxy propane, sets reaction temperature as 50 DEG C, is passed through 2.0MPa carbon dioxide, starts Mechanical agitation, reacts 2 hours.Polymerization result：TOF=132.71h-1, selectivity=95%, Mn=13.22kg/mol, PDI= 1.06。
Embodiment 5
Using method same as Example 1, metal cyanides uses six cyano group potassium ferrates, and metal M salt uses chlorination Aluminium, metal M salt and SalenH2 mol ratio are 1:1.2, prepare Salen-Al(III)CN catalyst, after reactor is cleaned and dried, Add 0.1mol Salen-Al(III)CN and 0.1mol co-catalysts PPNCl, 14mL expoxy propane, sets reaction temperature as 50 DEG C, 2.0MPa carbon dioxide is passed through, mechanical agitation is started, reacted 2 hours, polymerization result：TOF=164.52h-1, selectivity =93%, Mn=16.3kg/mol, PDI=1.05.
Comparative example 1
Step is largely same as Example 1, by 1.0g Salen-Co(III)OTs solid powder is dissolved in 50mL dichloromethanes Alkane, is poured into pear shape separatory funnel, with 100mL saturation NaCl aqueous solution concussion washing 3 times.Organic layer anhydrous Na2SO4Dry After be concentrated under reduced pressure, then washed with a small amount of n-hexane, precipitation be collected by filtration, further vacuum drying obtains pulverulent solids, is Salen-Co(III)Cl catalyst.By Salen-Co(III)Cl catalyst is used for carbon dioxide and prepared by epoxides copolyreaction Makrolon, after reactor is cleaned and dried, adds 0.4mol Salen-Co(III)Cl and 14mL expoxy propane, sets reaction temperature For 25 DEG C, 5.0MPa carbon dioxide is passed through, mechanical agitation is started, reacted 4 hours.Polymerization result：TOF=23.52h-1, selection Property=94%, Mn=10.4kg/mol, PDI=1.41.
Comparative example 2
Step is largely same as Example 1, by 1.0g Salen-Co(III)OTs solid powder is dissolved in 50mL dichloromethanes Alkane, is poured into pear shape separatory funnel, with 100mL saturation NaBr aqueous solution concussion washing 3 times.Organic layer anhydrous Na2SO4Dry After be concentrated under reduced pressure, then washed with a small amount of n-hexane, precipitation be collected by filtration, further vacuum drying obtains pulverulent solids, is Salen-Co(III)Br catalyst, makrolon is prepared for carbon dioxide and epoxides copolyreaction, and reactor is cleaned and dried Afterwards, 0.1mol Salen-Co are added(III)Br and 0.1mol co-catalysts PPNCl, 14mL expoxy propane, set reaction temperature as 50 DEG C, 2.0MPa carbon dioxide is passed through, mechanical agitation is started, reacted 2 hours.Polymerization result：TOF=348.92h-1, selection Property=42%, Mn=12.7kg/mol, PDI=1.37.
The infrared spectrum of makrolon and1H NMR nuclear magnetic spectrograms reference picture 1,2, it can be seen that 1235cm-1With 1747cm-1Absworption peak most strong at two, is the characteristic peak of the C-O and C=O keys of carbonate unit in polymerizate；1090cm-1 There is a very weak absworption peak at place, is ether chain link C-O keys in polymerizate, illustrates that its content is few, it was demonstrated that SalenCo(III)CN is urged The product that change carbon dioxide and Polymerization of Propylene Oxide are obtained is perfect alternate polymerizate, selectivity height.Comparative example is with implementing Example is compared, and shows to use catalyst of the present invention, in higher reaction temperatures, still possesses higher activity and selectivity.

Claims (10)

1. a kind of Salen catalyst using CN as axial ligand, it is characterised in that molecular structural formula is：
Wherein,
M=Cr, Co, Zn, Ni, Mn, Fe or Al；
R1/R2=H or (1R, 2R)-trans- (CH2)4；
R3/R4=H, Cl, Br or t-Bu.
2. a kind of preparation method of Salen catalyst as claimed in claim 1, it is characterised in that specifically include following steps：
(1) SalenH2 is synthesized；
(2) SalenH2 is synthesized into Salen-M with the ethanol solution hybrid reaction of metal M salt；
(3) Salen-M is synthesized into the Salen catalyst using CN as axial ligand with the aqueous solution hybrid reaction of metal cyanides.
3. the preparation method of Salen catalyst according to claim 2, it is characterised in that described SalenH2 passes through ring Hexamethylene diamine or ethylenediamine are obtained with the reaction of 3,5- di-tert-butyl salicylaldehydes.
4. the preparation method of Salen catalyst according to claim 2, it is characterised in that the metal M described in step (2) Salt is selected from zinc acetate, nickel acetate, manganese acetate, manganese nitrate, ferrous sulfate, ferric sulfate, frerrous chloride, cobalt chloride, thiocyanation cobalt, second Sour cobalt, chromium chloride, chromium acetate or aluminium chloride.
5. the preparation method of Salen catalyst according to claim 4, it is characterised in that step (2) is protected in nitrogen Under, by SalenH2 and dichloromethane mixed dissolution, it is added dropwise the ethanol solution of metal M salt at room temperature, metal M salt and SalenH2's Mol ratio is 1:0.5-2.
6. the preparation method of Salen catalyst according to claim 2, it is characterised in that the metal cyanogen described in step (3) Compound is selected from the sour potassium of the high cobalt of six cyano group, six cyano group potassium ferrates, the sour calcium of the high cobalt of six cyano group, the sour potassium of four cyano nickel, the high cobalt of six cyano group Sour lithium, six cyano group high chromic acid content potassium, six cyano group high chromic acid content calcium or six cyano group high chromic acid content lithiums.
7. the preparation method of Salen catalyst according to claim 6, it is characterised in that step (3) is concretely comprised the following steps： P-methyl benzenesulfonic acid is dissolved in acetone, Salen-M is dissolved in dichloromethane, then both are mixed, oxygen is passed through, stirs at room temperature 50-70min, extracts and obtains solid product after organic solvent, n-hexane washing, drying and be dissolved in dichloromethane, be added to metal Cyanide saturated aqueous solution simultaneously shakes, and removes water, extracts dichloromethane, n-hexane washing, collects precipitation, 40 DEG C of vacuum drying.
8. the preparation method of Salen catalyst according to claim 7, it is characterised in that described toluene sulfonic acide with The proportioning of acetone is 1g:The proportioning of 70-80mL, Salen-M and dichloromethane is 1g:30-35mL, described solid product and two The proportioning of chloromethanes is 1g:40-60mL.
9. a kind of application of Salen catalyst as claimed in claim 1, it is characterised in that described Salen catalyst is used for Catalysis carbon dioxide and epoxides copolyreaction prepare makrolon.
10. the application of Salen catalyst according to claim 9, it is characterised in that described epoxides and Salen The mol ratio of catalyst is 200-10000:1, described Salen catalyst and the mol ratio of co-catalyst are 1:0-2, during reaction Pressure is 1-10MPa, and reaction temperature is 15-100 DEG C.
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CN111359669A (en) * 2020-04-29 2020-07-03 河北工程大学 Non-covalent supported GOx-Py-Co (Salen) catalyst and synthesis method thereof
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CN115920969A (en) * 2022-12-05 2023-04-07 中国人民解放军军事科学院系统工程研究院 Salen metal ligand immobilized catalyst, and preparation method and application thereof
CN115920969B (en) * 2022-12-05 2023-12-29 中国人民解放军军事科学院系统工程研究院 Salen metal ligand immobilized catalyst, preparation method and application thereof
CN116333294A (en) * 2023-05-04 2023-06-27 辽宁奥克药业股份有限公司 Catalyst for preparing block polyether and preparation method of block polyether
CN116333294B (en) * 2023-05-04 2023-12-29 辽宁奥克药业股份有限公司 Catalyst for preparing block polyether and preparation method of block polyether

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