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 PDFInfo
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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
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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CN111303217A (en) * | 2020-04-03 | 2020-06-19 | 陕西煤业化工技术研究院有限责任公司 | Preparation and application of salen type Schiff base modified DMC catalyst |
CN111269148B (en) * | 2020-04-08 | 2022-02-08 | 台州职业技术学院 | Preparation method of Sacubitril intermediate |
CN111269148A (en) * | 2020-04-08 | 2020-06-12 | 台州职业技术学院 | Preparation method of Sacubitril intermediate |
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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CN115920969B (en) * | 2022-12-05 | 2023-12-29 | 中国人民解放军军事科学院***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 |
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