CN103396457B - The preparation method of a kind of Schiff's base cobalt compound, its preparation method and polycarbonate - Google Patents
The preparation method of a kind of Schiff's base cobalt compound, its preparation method and polycarbonate Download PDFInfo
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Abstract
The invention provides a kind of Schiff's base cobalt compound, there is structure shown in formula (I) or formula (II).Schiff's base cobalt compound provided by the invention has biphenyl bimetallic center structure, this bimetallic center structure makes Schiff's base cobalt compound have higher catalytic activity and selectivity, and there is good catalytic performance in wide temperature range, Schiff's base cobalt compound provided by the invention can play katalysis under low concentration and high temperature, the reaction of efficient catalytic carbonic acid gas and epoxide.In addition, Schiff's base cobalt compound provided by the invention also has higher selectivity, can highly selective obtain chain polycarbonate.Experimental result shows, is adopting the Schiff's base cobalt compound of structure shown in 0.01g formula (I) as catalyzer, and the reaction at 60 DEG C of catalysis 7.4g propylene oxide and carbonic acid gas, after reaction 8h, reaction conversion ratio reaches 35%.
Description
Technical field
The present invention relates to technical field of polymer, particularly relate to the preparation method of a kind of Schiff's base cobalt compound, its preparation method and polycarbonate.
Background technology
Along with the acceleration of world industry process, consume energy increasing, Carbon emission increases severely, and makes the CO in air
2concentration constantly raises, and causes global warming.According to reckoning, CO
2when concentration is increased to 600ppm from 300ppm, surface temperature must raise 2 ~ 3 degrees Celsius.According to statistics, the CO in air is discharged in the current whole world every year
2more than 24,000,000,000 tons, wherein about 15,000,000,000 tons are absorbed by the photosynthesis of plant, therefore have a net increase of CO in annual air
29000000000 tons.No matter from the energy, carbon source and alleviate CO
2to which aspect of pollution of environment, control CO
2discharge and strengthen CO
2exploitation be all a problem with great strategic significance.
Use carbonic acid gas can synthesize basic chemical, fuel and macromolecular material as carbon oxygen resource; for the mankind break away from the energy because excessive use fossil resource causes, resources and environment crisis provides new approaches, this field is also therefore subject to scientific circles and industrial community is paid close attention to jointly.Wherein with carbonic acid gas and epoxide for raw material, the aliphatic polycarbonate that copolymerization generates under the effect of catalyzer is a kind of degradable high polymer material, there is the performance of good ventilation property, excellent blocking oxygen and water, can engineering plastics, Dispoable medical wrapping material and packaging material for food etc. be used as.
1969, aboveground auspicious its assistant gentle found CO
2polycarbonate can be generated with epoxide copolymerization.They successfully use ZnEt first
2catalyst system catalysis CO
2with the alternating copolymerization of rac-PO.In succession there is again a series of catalyst system such as zinc alkyl(s)/reactive hydrogen catalyst system, zinc carboxylate system, bimetallic cyaniding objects system, rare-earth ternary catalyst system, catalysis of metalloporphyrin system, phenol zinc salt catalyst system and diimine zinc class catalyzer afterwards.The research and development of these systems have well promoted the development of aliphatic polycarbonate, and some system is applied to industrial production, but it is low still to there is catalytic activity, the problem of long reaction time.
For the problems referred to above, within 2003, start to have occurred schiff bases complex catalyst system, this system is made up of schiff bases complex and quaternary ammonium salt, has higher catalytic activity and selectivity.But require that catalyst concn is high, range of reaction temperature is little, still limit carbonic acid gas and epoxide reactive utilization.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of Schiff's base cobalt compound, its preparation method and polycarbonate, Schiff's base cobalt compound provided by the invention has good thermal adaptability, can the copolyreaction of efficient catalytic carbonic acid gas and epoxy compounds under compared with low catalyst concentration and comparatively high temps.
The invention provides a kind of Schiff's base cobalt compound, there is structure shown in formula (I) or formula (II):
（I）；
（II）；
Wherein, R
1and R
2independently selected from aliphatic group.
Preferably, described R
1and R
2independently selected from-CH
3,-CH
2cH
3,-CH (CH
3)
2or-C (CH
3)
3.
The invention provides a kind of preparation method of Schiff's base cobalt compound, comprise the following steps:
Reacting having the Schiff's base of structure and the salt compounds of cobalt shown in formula (III) in a solvent, obtaining the Schiff's base cobalt complex with structure shown in formula (IV);
（III）；
In formula (III), R
1and R
2independently selected from aliphatic group;
（IV)；
In formula (IV), R
1and R
2independently selected from aliphatic group;
Under oxygen atmosphere, the described Schiff's base cobalt complex with structure shown in formula (IV) is reacted in organic solvent with 2,4-DNP, be there is the Schiff's base cobalt compound of (I) shown structure;
（I）；
In formula (I), R
1and R
2independently selected from aliphatic group;
Or
Under oxygen atmosphere, the described Schiff's base cobalt complex with structure shown in formula (IV) is reacted in organic solvent with acetic acid, obtain the Schiff's base cobalt compound with the shown structure of formula (II);
（II）；
In formula (II), R
1and R
2independently selected from aliphatic group.
Preferably, the preparation method described in the Schiff's base of structure shown in formula (III) comprises the following steps:
The tetraamine compound with structure shown in formula V is reacted with the substituted salicylic aldehydes with formula (VI) structure, obtains the Schiff's base with structure shown in formula (III);
（V）；
（VI）；
In formula (VI), R
1and R
2independently selected from aliphatic group.
Preferably, the salt compounds of described cobalt is Cobaltous diacetate, cobalt chloride or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
Preferably, in the Schiff's base of structure shown in described formula (III) and the salt compounds of cobalt, the mol ratio of cobalt is 1:(2 ~ 5).
Preferably, the Schiff's base cobalt complex of structure shown in described formula (IV) and the mol ratio of 2,4-DNP are 1:(2 ~ 5);
Shown in described formula (IV), the schiff bases complex of structure and the mol ratio of acetic acid are 1:(2 ~ 5).
The invention provides a kind of preparation method of polycarbonate, comprise the following steps:
Under the effect of catalyzer and promotor, carbonic acid gas and epoxide are carried out copolyreaction, obtains polycarbonate;
The Schiff's base cobalt compound that described catalyzer obtains for preparation method described in the Schiff's base cobalt compound described in technique scheme or technique scheme.
Preferably, described promotor is one or more in two (dihalotriphenylphosphoranes base) ammonium chloride, DMAP, N-Methylimidazole, tricyclohexyl phosphine, 4 bromide and Tetrabutyl amonium bromide.
Preferably, the mol ratio of described Schiff's base cobalt compound and promotor is 1:(1 ~ 1.5);
The total mole number of described Schiff's base cobalt compound and promotor and the mol ratio of propylene oxide are 1:(1000 ~ 40000).
Preferably, the pressure of described carbonic acid gas is 2MPa ~ 5MPa.
Preferably, the temperature of described copolyreaction is 30 DEG C ~ 90 DEG C;
The time of described copolyreaction is 0.5h ~ 24h.
The invention provides a kind of Schiff's base cobalt compound, there is structure shown in formula (I) or formula (II).The present invention reacts to have the Schiff's base of structure and the salt compounds of cobalt shown in formula (III), obtains the Schiff's base cobalt complex with structure shown in formula (IV); Again under oxygen atmosphere, the Schiff's base cobalt complex having a structure shown in formula (IV) by described and 2,4-DNP react, and obtain the schiff base compounds with formula (I) described structure; Or under oxygen atmosphere, by described Schiff's base cobalt complex and the acetic acid reaction with structure shown in formula (IV), obtain the Schiff's base cobalt compound with structure shown in formula (II).The present invention is by the Schiff's base cobalt compound that obtains and promotor acting in conjunction, and the copolyreaction of catalysis carbonic acid gas and epoxide, obtains polycarbonate.Schiff's base cobalt compound provided by the invention has biphenyl bimetallic center structure, this bimetallic center structure makes Schiff's base cobalt compound have higher catalytic activity and selectivity, and there is good catalytic performance in wide temperature range, Schiff's base cobalt compound provided by the invention can play katalysis under low concentration and high temperature, the reaction of efficient catalytic carbonic acid gas and epoxide.In addition, Schiff's base cobalt compound provided by the invention also has higher selectivity, can highly selective obtain chain polycarbonate.Experimental result shows, is adopting the Schiff's base cobalt compound of structure shown in 0.01g formula (I) as catalyzer, and the reaction at 60 DEG C of catalysis 7.4g propylene oxide and carbonic acid gas, after reaction 8h, reaction conversion ratio reaches 35%.
Embodiment
A kind of Schiff's base cobalt compound, has structure shown in formula (I) or formula (II):
（I）；
（II）；
Wherein, R
1and R
2independently selected from aliphatic group, preferably, independently-CH is selected from
3,-CH
2cH
3,-CH (CH
3)
2or-C (CH
3)
3, preferred, R
1and R
2be-CH simultaneously
3,-CH
2cH
3,-CH (CH
3)
2or-C (CH
3)
3.
Four C=N functional groups that the present invention utilizes four amine structures to provide, provide two melts combine centers, thus obtain two centers Schiff's base cobalt compound.Bicentric introducing makes Schiff's base cobalt compound can the reaction of efficient catalytic carbonic acid gas and epoxide under low concentration and comparatively high temps, highly selective obtain chain polycarbonate.
The invention provides a kind of preparation method of Schiff's base cobalt compound, comprise the following steps:
The Schiff's base of structure formula (III) Suo Shi and the salt compounds of cobalt are reacted in a solvent, obtains the Schiff's base cobalt complex with structure shown in formula (IV);
（III）；
In formula (III), R
1and R
2independently selected from aliphatic group;
（IV）；
In formula (IV), R
1and R
2independently selected from aliphatic group;
Under oxygen atmosphere, the described Schiff's base cobalt complex with structure shown in formula (IV) is reacted in organic solvent with 2,4-DNP, be there is the Schiff's base cobalt compound of (I) shown structure;
（I）；
In formula (I), R
1and R
2independently selected from aliphatic group;
Or
Under oxygen atmosphere, the described Schiff's base cobalt complex with structure shown in formula (IV) is reacted in organic solvent with acetic acid, obtain the Schiff's base cobalt compound with the shown structure of formula (II);
（II）；
In formula (II), R
1and R
2independently selected from aliphatic group.
The present invention with the salt compounds of the Schiff's base of structure formula (III) Suo Shi and cobalt for raw material, there is the Schiff's base of structure shown in formula (III) react described in a solvent with the salt compounds of cobalt, obtain the Schiff's base cobalt complex with the shown structure of formula (IV).In the present invention, R in described formula (III)
1and R
2independently selected from aliphatic group, preferably, independently selected from-CH
3,-CH
2cH
3,-CH (CH
3)
2or-C (CH
3)
3.In the present invention, the preparation method described in the Schiff's base of structure shown in formula (III) preferably includes following steps:
The tetraamine compound with structure shown in formula V is reacted with the substituted salicylic aldehydes with formula (VI) structure, obtains the Schiff's base with structure shown in formula (III);
（V）；
（VI）；
In formula (VI), R
1and R
2independently selected from aliphatic group.
The present invention is to have the tetraamine compound of structure shown in formula V and to have the substituted salicylic aldehydes of formula (VI) structure for raw material, the described tetraamine compound with structure shown in formula V is reacted in organic solvent with the substituted salicylic aldehydes with formula (VI) structure, obtains the Schiff's base with structure shown in formula (III).In the present invention, R in described formula (VI)
1and R
2independently selected from aliphatic group, preferably, independently selected from-CH
3,-CH
2cH
3,-CH (CH
3)
2or-C (CH
3)
3.In the present invention, R is worked as
1and R
2be-CH simultaneously
3time, described substituted salicylic aldehydes is 3,5-dimethyl salicylic aldehyde; Work as R
1and R
2be-CH simultaneously
2cH
3time, described substituted salicylic aldehydes is 3,5-diethyl salicylic aldehyde; Work as R
1and R
2be-CH (CH simultaneously
3)
2time, described substituted salicylic aldehydes is 3,5-di-isopropyl salicylic aldehyde; Work as R
1and R
2be-C (CH simultaneously
3)
3time, described substituted salicylic aldehydes is 3,5-di-tert-butyl salicylaldehyde.
The tetraamine compound with formula V structure and the substituted salicylic aldehydes with structure shown in formula (VI) preferably to mix with tosic acid and react in organic solvent by the present invention, obtain the Schiff's base with the shown structure of formula (III).In the present invention, described organic solvent is preferably alcohol compound, methylene dichloride and toluene, is more preferably toluene.In the present invention, described in there is the tetraamine compound of formula V structure and the described mol ratio with the substituted salicylic aldehydes of structure shown in formula (VI) is preferably 1:(4 ~ 15), be more preferably 1:(4 ~ 10), most preferably be 1:(4 ~ 6); The mass ratio of described tetraamine compound and tosic acid is preferably (15 ~ 30): 1, is more preferably (20 ~ 25): 1; The consumption of described organic solvent preferably makes tetraamine compound mass concentration in organic solvent be 0.01g/mL ~ 0.1g/mL, is more preferably 0.015g/mL ~ 0.05g/mL.In the present invention, the temperature that the tetraamine compound described in formula V structure and the substituted salicylic aldehydes with structure shown in formula (VI) react is preferably 100 DEG C ~ 110 DEG C; The time of described reaction is preferably 24h ~ 72h, is more preferably 36h ~ 60h, most preferably is 42h ~ 54h, is the most preferably 48h.
After the tetraamine compound described in completing with formula V structure and the reaction of substituted salicylic aldehydes with structure shown in formula (VI), organic solvent in the reaction product obtained preferably removes by the present invention, the reaction product methylene dichloride of removing organic solvent is dissolved, then the mixing solutions obtained is joined in ethanol and carry out sedimentation, will after the solid drying obtained, obtain the Schiff's base with structure shown in formula (III).The method of the present invention to described removing organic solvent does not have special restriction, adopt the technical scheme of place to go well known to those skilled in the art organic solvent, as when adopting toluene to be organic solvent, the reaction product obtained is spin-dried for by the present invention, removing organic solvent wherein.The consumption of the present invention to described methylene dichloride does not have special restriction, the reaction product obtained can be dissolved; The present invention does not have special restriction to the consumption of described ethanol yet, can by complete for reaction product sedimentation.Described mixing solutions is preferably added drop-wise in ethanol by the present invention, stirs and carries out sedimentation, and then filtration, drying obtain the Schiff's base with structure shown in formula (III).The method of the present invention to described stirring does not have special restriction, adopt the technical scheme of stirring well known to those skilled in the art, in the present invention, the time of described stirring is preferably 20min ~ 50min, be more preferably 25min ~ 40min, most preferably be 30min ~ 35min.The present invention does not have special restriction to described filtration and dry method, and adopt filtration well known to those skilled in the art and dry technical scheme, in the present invention, described drying is preferably vacuum-drying.
After obtaining having the Schiff's base of structure shown in formula (III), the present invention has the Schiff's base of structure and the salt compounds of cobalt shown in formula (III) react described in a solvent, obtains the Schiff's base cobalt complex with the shown structure of formula (IV).The present invention preferably in a nitrogen atmosphere, has the Schiff's base of structure and the capable reaction of salt compounds of cobalt shown in formula (III) by described.In the present invention, the salt compounds of described cobalt is preferably Cobaltous diacetate, cobalt chloride or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, is more preferably Cobaltous diacetate, and can be the Cobaltous diacetate of band crystal water, can be Glacial acetic acid cobalt, the present invention have special restriction to this yet.In the present invention, described in there is cobalt in the Schiff's base of structure shown in formula (III) and the salt compounds of cobalt mol ratio be preferably 1:(2 ~ 5), be more preferably 1:(2 ~ 2.5); Described organic solvent is preferably one or more in alcohol compound and methylene dichloride, is more preferably one or more in methyl alcohol, ethanol and methylene dichloride; The consumption of described organic solvent preferably makes described Schiff's base mass concentration in organic solvent be 0.01g/mL ~ 0.02g/mL, is more preferably 0.012g/mL ~ 0.018g/mL.In the present invention, described in there is the temperature that the Schiff's base of structure shown in formula (III) and the salt compounds of cobalt react be preferably room temperature, heat without the need to carrying out or lower the temperature; Preferably react under the condition stirred, the method for the present invention to described stirring does not have special restriction, adopts the technical scheme of stirring well known to those skilled in the art; The time of described reaction is preferably 2 hours ~ 5 hours, is more preferably 3 hours ~ 4 hours.
After there is described in completing the reaction of the Schiff's base of structure and the salt compounds of cobalt shown in formula (III), the present invention preferably under nitrogen atmosphere, the reaction product obtained is carried out suction filtration, by the solid drying obtained, obtains the Schiff's base cobalt complex with structure shown in formula (IV).The method of the present invention to described suction filtration does not have special restriction, adopts the technical scheme of suction filtration well known to those skilled in the art; The method of the present invention to described drying does not have special restriction, adopts the technical scheme of drying well known to those skilled in the art, and in the present invention, described drying is preferably vacuum-drying.
After obtaining having the Schiff's base cobalt complex of structure shown in formula (IV), the present invention is under oxygen atmosphere, by the described Schiff's base cobalt complex with structure shown in formula (IV) and 2,4-, nitrophenols reacts in organic solvent, obtains the Schiff's base cobalt compound with the shown structure of formula (I).The present invention is preferably by the described Schiff's base cobalt complex and 2 with structure shown in formula (IV), 2, 4-dinitrophenol and lithium chloride mix in organic solvent, under oxygen atmosphere, stir the mixing solutions obtained react, obtain the Schiff's base cobalt compound with structure shown in formula (I).In the present invention, shown in described formula (IV), the Schiff's base cobalt complex of structure and the mol ratio of 2,4-DNP are preferably 1:(2 ~ 5), be more preferably 1:(2 ~ 3); The mass ratio of described 2,4-DNP and lithium chloride is preferably (1 ~ 5): 1, is more preferably (1.5 ~ 3); Described organic solvent be preferably in tetrahydrofuran (THF) and methylene dichloride one or both; The Schiff's base cobalt complex mass concentration in organic solvent described in the consumption of described organic solvent preferably makes with structure shown in formula (IV) is 0.01g/mL ~ 0.02g/mL, is more preferably 0.012g/mL ~ 0.018g/mL.In the present invention, described in there is the temperature that the schiff bases complex of structure shown in formula (IV) and 2,4-DNP react be preferably 25 DEG C ~ 40 DEG C, be more preferably 30 DEG C ~ 35 DEG C; The time of described reaction is preferably 5h ~ 24h, is more preferably 8h ~ 20h, most preferably is 12h ~ 18h.
There is described in completing the Schiff's base cobalt complex and 2 of structure shown in formula (IV), after the reaction of 2, 4-dinitrophenol, the reaction soln obtained preferably is adopted saturated sodium bicarbonate aqueous solution cleaning by the present invention, clean with saturated aqueous common salt again, by dry for the organic phase obtained, then product drying obtained adopts pillar layer separation to purify, and obtains the Schiff's base cobalt compound with structure shown in formula (I).In the present invention, the number of times of described saturated sodium bicarbonate aqueous solution cleaning is preferably 2 times ~ 5 times, is more preferably 3 times; The number of times of described saturated aqueous common salt cleaning is preferably 2 times ~ 5 times, is more preferably 3 times, preferably cleans each time after the organic phase obtained merges and adopts anhydrous magnesium sulfate drying.The present invention does not have special restriction to the method that described pillar layer separation is purified, and adopts the technical scheme that pillar layer separation well known to those skilled in the art is purified.
After obtaining having the Schiff's base cobalt complex of structure shown in formula (IV), the present invention is under oxygen atmosphere, the described Schiff's base cobalt complex with structure shown in formula (IV) is reacted in organic solvent with acetic acid, obtains the Schiff's base cobalt compound with the shown structure of formula (II).The present invention adopt described in technique scheme by the technical scheme of Schiff's base cobalt compound of structure shown in the Schiff's base cobalt complex preparation formula (I) of structure described formula (IV) Suo Shi, preparation has the Schiff's base cobalt compound of structure shown in formula (II), different formulas, in the technical program, adopt the 2,4-DNP of acetic acid replacement described in technique scheme.
Schiff's base cobalt compound provided by the invention has bimetallic center, there is higher catalytic activity and selectivity and thermal adaptability, can under low concentration and comparatively high temps, the reaction of efficient catalytic carbonic acid gas and epoxide, and there is higher selectivity.
The invention provides a kind of preparation method of polycarbonate, comprise the following steps:
Under the katalysis of catalyzer and promotor, carbonic acid gas and epoxide carry out copolyreaction, obtain polycarbonate;
The Schiff's base cobalt compound that described catalyzer obtains for preparation method described in the Schiff's base cobalt compound described in technique scheme or technique scheme.
The present invention by carbonic acid gas and epoxide under the effect of catalyzer and promotor, carry out copolyreaction, obtain polycarbonate, the Schiff's base cobalt compound that described catalyzer obtains for preparation method described in the Schiff's base cobalt compound described in technique scheme or technique scheme.In the present invention, described copolyreaction is preferably carried out under the condition of anhydrous and oxygen-free, preferably epoxide, catalyzer and promotor is mixed to join and dewaters in the autoclave of deoxygenation through high temperature, then pass into carbonic acid gas wherein, carry out copolyreaction;
The kind of the present invention to described epoxide is not particularly limited, well known to those skilled in the art and carbon dioxide reaction is adopted to prepare the epoxide of polycarbonate, in the present invention, described epoxide is preferably one or more in oxyethane, propylene oxide, epoxy cyclohexane, Styrene oxide 98min., epoxy chloropropane, ethylene glycol diglycidylether, butanediol diglycidyl ether and neopentylglycol diglycidyl ether.In the present invention, described promotor is one or more in two (dihalotriphenylphosphoranes base) ammonium chloride (PPNCl), DMAP (DMAP), N-Methylimidazole, tricyclohexyl phosphine, 4 bromide and Tetrabutyl amonium bromide, be more preferably in PPNCl and DMAP one or both, most preferably be PPNCl.In the present invention, the mol ratio of described catalyzer and described promotor is preferably 1:(0.5 ~ 5), be more preferably 1:(0.5 ~ 3), most preferably be 1:(0.5 ~ 1.5); The total mole number of described catalyzer and promotor and the mol ratio of described epoxide are preferably 1:(1000 ~ 40000), be more preferably (2000 ~ 38000), most preferably be 1:(5000 ~ 35000), be the most preferably 1:(10000 ~ 25000);
In the present invention, the pressure of described carbonic acid gas is preferably 0.2MPa ~ 5MPa, is more preferably 3MPa ~ 4MPa; The temperature of described copolyreaction is preferably 30 DEG C ~ 90 DEG C, is more preferably 40 DEG C ~ 80 DEG C, most preferably is 50 DEG C ~ 70 DEG C, is the most preferably 55 DEG C ~ 5 DEG C; The time of described copolyreaction is preferably 0.5h ~ 24h, is more preferably 1h ~ 21h, most preferably is 3h ~ 18h, is the most preferably 6h ~ 15h.
After described copolyreaction completes, reaction system preferably cools by the present invention, discharges residual gas, taking out minute quantity mixture for measuring H-NMR, calculating transformation efficiency.The reaction product methylene dichloride obtained is dissolved, then the solution obtained is added in ethanol, leave standstill after stirring, precipitation sedimentation obtained is dissolved in methylene dichloride again, by the solution sedimentation in ethanol obtained, then precipitation sedimentation obtained is dry, obtains polycarbonate.Reactor is preferably placed in frozen water and lowers the temperature rapidly by the present invention, then slowly releases and participates in gas to Pressure Drop to normal atmosphere, then opens reactor taking-up reaction product.The consumption of the present invention to described methylene dichloride and ethanol does not have special restriction, can realize the dissolving to reaction product and sedimentation.In the present invention, the time of described stirring is preferably 10 minutes ~ 25 minutes, is more preferably 15 minutes ~ 20 minutes; The described standing time is preferably 20 minutes ~ 40 minutes, is more preferably 25 minutes ~ 35 minutes, most preferably is 30 minutes; The described number of times by the resolution of precipitate obtained, sedimentation is preferably 2 times ~ 5 times, is more preferably 3 times ~ 4 times.
The invention provides a kind of Schiff's base cobalt compound, containing bimetallic active center in this compound, there is higher catalytic activity and selectivity, and can use in wide temperature range.The present invention is using this Schiff's base cobalt compound as catalyzer, the copolyreaction of catalysis carbonic acid gas and epoxide, under the catalyst levels and higher catalytic temperature of low concentration, this catalyzer still can the synthesis of efficient catalytic polycarbonate, has higher reaction conversion ratio.And Schiff's base cobalt compound provided by the invention has higher selectivity, can control the ratio of polycarbonate and cyclic carbonate in reaction product, and time the highest, the selectivity of polycarbonate can reach >99%.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method to Schiff's base cobalt compound provided by the invention, its preparation method and polycarbonate is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
15g3,5-di-tert-butyl salicylaldehyde, 2.14g biphenyl tetramine and 0.1g tosic acid are added in 150mL toluene, heating dewaters, and after reaction 48h, obtains Tan solid or dope after being spin-dried for by toluene;
The Tan solid obtained or dope 50mL methylene dichloride are dissolved, is added drop-wise in 1000mL ethanol, filter after stirring 30min and obtain yellow solid, vacuum-drying, obtain Schiff's base.
The productive rate that the present invention calculates Schiff's base is 80%.
The present invention utilizes nucleus magnetic resonance to analyze the Schiff's base obtained in the present embodiment, and obtain its hydrogen spectrum, result shows:
1hNMR (300MHz, CDCl
3): δ=13.60 (s, OH4H), 8.79 (d, NCH4H), 7.64 (d, ArH, 2H), 7.51 (d, ArH, 6H), 7.42 (d, ArH, 2H), 7.30 (d, ArH, 4H), 1.50 (d, CCH
3, 36H), 1.37 (d, CCH
3, 36H);
The present invention utilizes mass spectrograph to analyze the Schiff's base that the present embodiment obtains, and result shows: MALDI-TOF (CDCl
3), m/z=1079.8;
The present invention utilizes ultimate analysis to analyze the Schiff's base that the present embodiment obtains, and obtains its each atom content: Elem.Anal.(%): Calcd.C80.11; H8.78; N5.19.Found:C78.63; H9.17; N6.68;
As can be seen from above proton nmr spectra, mass spectroscopy and results of elemental analyses, Schiff's base prepared by the present embodiment has structure, wherein R shown in formula (III)
1and R
2be the tertiary butyl.
Embodiment 2
The present invention adopts the technical scheme of embodiment 1 to prepare Schiff's base, unlike, the present embodiment adopts 3,5-di-tert-butyl salicylaldehydes in 3,5-dimethyl salicylic aldehyde replacement embodiment 1.
The reaction product obtained is carried out hydrogen nuclear magnetic resonance spectrum analysis, mass spectroscopy and ultimate analysis by the present invention, and result shows, Schiff's base prepared by the present embodiment has structure, wherein R shown in formula (III)
1and R
2be methyl.
Embodiment 3
The present invention adopts the technical scheme of embodiment 1 to prepare Schiff's base, unlike, the present embodiment adopts 3,5-di-tert-butyl salicylaldehydes in 3,5-diethyl salicylic aldehyde replacement embodiment 1.
The reaction product obtained is carried out hydrogen nuclear magnetic resonance spectrum analysis, mass spectroscopy and ultimate analysis by the present invention, and result shows, Schiff's base prepared by the present embodiment has structure, wherein R shown in formula (III)
1and R
2be ethyl.
Embodiment 4
The present invention adopts the technical scheme of embodiment 1 to prepare Schiff's base, unlike, the present embodiment adopts 3,5-di-tert-butyl salicylaldehydes in 3,5-di-isopropyl salicylic aldehyde replacement embodiment 1.
The reaction product obtained is carried out hydrogen nuclear magnetic resonance spectrum analysis, mass spectroscopy and ultimate analysis by the present invention, and result shows, Schiff's base prepared by the present embodiment has structure, wherein R shown in formula (III)
1and R
2be sec.-propyl.
Embodiment 5
The Schiff's base prepare 1g embodiment 1 and 0.3284g Cobaltous diacetate join in 150mL methyl alcohol, under nitrogen atmosphere after stirring reaction 5h, by the reaction product suction filtration under nitrogen atmosphere obtained, by dry under vacuo for the product obtained, obtain red solid, this red solid is schiff bases complex.
The present invention calculates the productive rate 90% of schiff bases complex.
The present invention utilizes mass spectrograph to analyze the schiff bases complex that the present embodiment obtains, and result shows: MALDI-TOF (CDCl
3), m/z=1192.5;
The present invention utilizes ultimate analysis to analyze the schiff bases complex that the present embodiment obtains, and obtains its each atom content: Elem.Anal.(%): Calcd.C72.46; H7.60; N4.69.Found:C77.63; H8.26; N3.89;
Shown by above analytical results, the schiff bases complex that the present embodiment prepares has structure, wherein R shown in formula (IV)
1and R
2be the tertiary butyl.
Embodiment 6
The technical scheme of embodiment 5 is adopted to prepare schiff bases complex, unlike, the Schiff's base that the embodiment 1 that the Schiff's base that the present embodiment adopts embodiment 2 to obtain replaces embodiment 5 to adopt prepares.
The reaction product obtained is carried out mass spectroscopy and ultimate analysis by the present invention, and result shows, the schiff bases complex that the present embodiment obtains has structure, wherein R shown in formula (IV)
1and R
2be methyl.
Embodiment 7
The technical scheme of embodiment 5 is adopted to prepare schiff bases complex, unlike, the Schiff's base that the embodiment 1 that the Schiff's base that the present embodiment adopts embodiment 3 to obtain replaces embodiment 5 to adopt prepares.
The reaction product obtained is carried out mass spectroscopy and ultimate analysis by the present invention, and result shows, the schiff bases complex that the present embodiment obtains has structure, wherein R shown in formula (IV)
1and R
2be ethyl.
Embodiment 8
The technical scheme of embodiment 5 is adopted to prepare schiff bases complex, unlike, the Schiff's base that the embodiment 1 that the Schiff's base that the present embodiment adopts embodiment 4 to obtain replaces embodiment 5 to adopt prepares.
The reaction product obtained is carried out mass spectroscopy and ultimate analysis by the present invention, and result shows, the schiff bases complex that the present embodiment obtains has structure, wherein R shown in formula (IV)
1and R
2be sec.-propyl.
Embodiment 9
Schiff bases complex 1g embodiment 5 prepared, 0.32g2,4-dinitrophenol and 0.21g lithium chloride are added in 150mL methylene dichloride, under oxygen atmosphere, stir 8h;
The reaction product 150mL saturated sodium bicarbonate aqueous solution obtained is washed 3 times, then washes 3 times with 100mL saturated common salt, after merging organic phase, use anhydrous magnesium sulfate drying 2h;
Adopt column chromatography to purify to dried product separation, obtain red brown solid.
The productive rate 70% of the red brown solid that the present invention calculates.
The present invention utilizes mass spectrograph to analyze the red brown solid that the present embodiment obtains, and result shows: MALDI-TOF (CDCl
3), m/z=1192.5;
The present invention utilizes ultimate analysis to analyze the red brown solid that the present embodiment obtains, and obtains its each atom content: Elem.Anal.(%): Calcd.C64.69; H6.20; N7.18.Found:C67.33; H7.51; N6.92;
Shown by above analytical results, the red brown solid that the present embodiment obtains is for having the Schiff's base cobalt compound of result shown in formula (I), wherein R
1and R
2be the tertiary butyl.
Embodiment 10
The technical scheme of embodiment 9 is adopted to prepare Schiff's base cobalt compound, the schiff bases complex that the embodiment 5 that the schiff bases complex adopting embodiment 6 to obtain unlike the present embodiment replaces embodiment 9 to adopt prepares.
The reaction product obtained is carried out mass spectroscopy and ultimate analysis by the present invention, and result shows, the reaction product that the present embodiment prepares is for having structure Schiff's base cobalt compound shown in formula (I), wherein R
1and R
2be methyl.
Embodiment 11
The technical scheme of embodiment 9 is adopted to prepare Schiff's base cobalt compound, the schiff bases complex that the embodiment 5 that the schiff bases complex adopting embodiment 7 to obtain unlike the present embodiment replaces embodiment 9 to adopt prepares.
The reaction product obtained is carried out mass spectroscopy and ultimate analysis by the present invention, and result shows, the reaction product that the present embodiment prepares is for having structure Schiff's base cobalt compound shown in formula (I), wherein R
1and R
2be ethyl.
Embodiment 12
The technical scheme of embodiment 9 is adopted to prepare Schiff's base cobalt compound, the schiff bases complex that the embodiment 5 that the schiff bases complex adopting embodiment 7 to obtain unlike the present embodiment replaces embodiment 9 to adopt prepares.
The reaction product obtained is carried out mass spectroscopy and ultimate analysis by the present invention, and result shows, the reaction product that the present embodiment prepares is for having structure Schiff's base cobalt compound shown in formula (I), wherein R
1and R
2be sec.-propyl.
Embodiment 13
The present invention adopts the technical scheme of embodiment 9 to prepare Schiff's base cobalt compound, unlike, the present invention adopts by 2,4-dinitrophenols in acetic acid replacement embodiment 9.
The present invention utilizes mass spectrograph to analyze the reaction product that the present embodiment obtains, and result shows: MALDI-TOF(CDCl
3), m/z=1192.5;
The present invention utilizes ultimate analysis to analyze the reaction product that the present embodiment obtains, and obtains its each atom content: Elem.Anal.(%): Calcd.C69.60; H7.38; N4.27.Found:C67.58; H9.15; N5.84;
Shown by above interpretation of result, the reaction product that the present embodiment obtains is for having the Schiff's base cobalt compound of structure shown in formula (II), wherein R
1and R
2be the tertiary butyl.
Embodiment 14
The present invention adopts the technical scheme of embodiment 13 to prepare Schiff's base cobalt compound, unlike, the Schiff's base cobalt compound that the embodiment 9 that the Schiff's base cobalt compound that the present embodiment adopts embodiment 10 to prepare replaces embodiment 13 to adopt prepares.
The reaction product obtained is carried out mass spectroscopy and ultimate analysis by the present invention, and result shows, the reaction product that the present embodiment obtains is for having the Schiff's base cobalt compound of structure shown in formula (II), wherein R
1and R
2be methyl.
Embodiment 15
The present invention adopts the technical scheme of embodiment 13 to prepare Schiff's base cobalt compound, unlike, the Schiff's base cobalt compound that the embodiment 9 that the Schiff's base cobalt compound that the present embodiment adopts embodiment 11 to prepare replaces embodiment 13 to adopt prepares.
The reaction product obtained is carried out mass spectroscopy and ultimate analysis by the present invention, and result shows, the reaction product that the present embodiment obtains is for having the Schiff's base cobalt compound of structure shown in formula (II), wherein R
1and R
2be ethyl.
Embodiment 16
The present invention adopts the technical scheme of embodiment 13 to prepare Schiff's base cobalt compound, unlike, the Schiff's base cobalt compound that the embodiment 9 that the Schiff's base cobalt compound that the present embodiment adopts embodiment 12 to prepare replaces embodiment 13 to adopt prepares.
The reaction product obtained is carried out mass spectroscopy and ultimate analysis by the present invention, and result shows, the reaction product that the present embodiment obtains is for having the Schiff's base cobalt compound of structure shown in formula (II), wherein R
1and R
2be sec.-propyl.
Embodiment 17
The Schiff's base cobalt compound obtain 2.18g propylene oxide, 0.0177g embodiment 9 and 0.0052gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature stirs at 60 DEG C, reaction 3h;
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure, the reaction product 15mL methylene dichloride obtained is dissolved, the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, precipitation sedimentation obtained carries out vacuum-drying, obtains reaction product.
The polymkeric substance obtained carries out by the present invention
1h-NMR analyzes, and result shows, in the product that the present embodiment obtains, the overwhelming majority is polycarbonate, and cyclic carbonate ester content is less than 3%;
Take polystyrene as standard substance, the present invention utilizes gel permeation chromatography to analyze the polycarbonate obtained in the present embodiment, and the number-average molecular weight obtaining polycarbonate is 7.5 ten thousand, and molecular weight distribution is 1.04.
Embodiment 18
The Schiff's base cobalt compound obtain 2g propylene oxide, 0.0269g embodiment 13 and 0.0119gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature stirs at 90 DEG C, reaction 1h;
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure, the reaction product 15mL methylene dichloride obtained is dissolved, then the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min.Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, the solid vacuum-drying after washing, obtains reaction product.
The polymkeric substance obtained carries out by the present invention
1h-NMR analyzes, and result shows, cyclic carbonate ester content about 60% in the product that the present embodiment obtains;
Take polystyrene as standard substance, the present invention utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 4.5 ten thousand, and molecular weight distribution is 1.14.
Embodiment 19
The Schiff's base cobalt compound obtain 2g propylene oxide, 0.0269g embodiment 13 and 0.0119gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature stirs at 40 DEG C, reaction 1h;
Be placed in frozen water by reactor after reaction terminates and lower the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure, is dissolved by reaction product 15mL methylene dichloride, is slowly dropped to by the solution obtained in 200mL ethanol, static 30min after stirring 15min.Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, reaction product sedimentation obtained carries out vacuum-drying, obtains reaction product.
The polymkeric substance obtained carries out by the present invention
1h-NMR analyzes, and result shows, in the product that the present embodiment obtains, cyclic carbonate ester content is less than 2%;
Take polystyrene as standard substance, the present invention utilizes gel permeation chromatography to analyze the polycarbonate obtained in the present embodiment, and the number-average molecular weight obtaining polycarbonate is 50,000, and molecular weight distribution is 1.12.
Embodiment 20
The Schiff's base cobalt compound obtain 2g propylene oxide, 0.0269g embodiment 13 and 0.0119gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature stirs at 50 DEG C, reaction 1h;
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure, the reaction product 15mL methylene dichloride obtained is dissolved, the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, reaction product vacuum-drying sedimentation obtained, obtains reaction product.
The reaction product obtained is carried out by the present invention
1h-NMR analyzes, and result shows, in the product that the present embodiment obtains, and cyclic carbonate ester content about 60%;
Take polystyrene as standard substance, the present invention utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 5.2 ten thousand, and molecular weight distribution is 1.09.
Embodiment 21
The Schiff's base cobalt compound prepare 2g propylene oxide, 0.0269g embodiment 13 and 0.0119gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature, 70 DEG C of stirrings, reacts 1h;
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure, the reaction product 15mL methylene dichloride obtained is dissolved, the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, solid vacuum-drying sedimentation obtained, obtains reaction product.
The polymkeric substance obtained carries out by the present invention
1h-NMR analyzes, and result shows, in the reaction product that the present embodiment obtains, and cyclic carbonate ester content about 60%;
Take polystyrene as standard substance, the present invention utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 5.2 ten thousand, and molecular weight distribution is 1.11.
Embodiment 22
The Schiff's base cobalt compound prepare 2.48g propylene oxide, 0.0028g embodiment 9 and 0.0025gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 5MPa, control temperature, 40 DEG C of stirrings, reacts 24h;
Be placed in frozen water by reactor after reaction terminates and lower the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure, is dissolved by product 15mL methylene dichloride, is slowly dropped to by the solution obtained in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeats 3 times, by the solid vacuum-drying after sedimentation, obtains reaction product.
The polymkeric substance obtained carries out by the present invention
1h-NMR analyzes, and result shows, in the present embodiment, the transformation efficiency of polyreaction is about 20%; Cyclic carbonate about 10% in the product obtained;
Take polystyrene as standard substance, the present invention utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 10.5 ten thousand, and molecular weight distribution is 1.08.
Embodiment 23
The Schiff's base cobalt compound obtain 2.48g propylene oxide, 0.0028g embodiment 9 and 0.0025gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 1MPa, control temperature, 40 DEG C of stirrings, reacts 24h;
Be placed in frozen water by reactor after reaction terminates and lower the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure, is dissolved by product 15mL methylene dichloride, is slowly dropped to by the solution obtained in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeats 3 times, by the solid vacuum-drying after sedimentation, obtains reaction product.
The polymkeric substance obtained is carried out
1h-NMR analyzes, and result shows, in the present embodiment, the transformation efficiency of polymer reaction is about 15%, cyclic carbonate about 22% in the reaction product that the present embodiment obtains;
The present invention is standard substance with polystyrene, utilizes gel permeation chromatography to analyze the polycarbonate obtained, and the number-average molecular weight obtaining polycarbonate is 90,000, and molecular weight distribution is 1.04.
Embodiment 24
The Schiff's base cobalt compound obtain 2.232g propylene oxide, 0.03g embodiment 9 and 0.01105gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature, 40 DEG C of stirrings, reacts 1h;
Be placed in frozen water by reactor after reaction terminates and lower the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure, is dissolved by product 15mL methylene dichloride, is slowly dropped to by the solution obtained in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeats 3 times, by the solid vacuum-drying after sedimentation, obtains reaction product.
The reaction product obtained is carried out by the present invention
1h-NMR analyzes, and result shows, the reaction conversion ratio in the present embodiment reaches 40%, and in the reaction product obtained, cyclic carbonate ester content is less than 3%.
The present invention is standard substance with polystyrene, utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 4.5 ten thousand, and molecular weight distribution is 1.07.
Embodiment 25
The Schiff's base cobalt compound obtain 2.232g propylene oxide, 0.03g embodiment 9 and 0.0133gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature, 40 DEG C of stirrings, reacts 1h;
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure, after driving still, product 15mL methylene dichloride is dissolved, the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, solid vacuum-drying sedimentation obtained, obtains reaction product.
The reaction product obtained is carried out by the present invention
1h-NMR analyzes, and result shows, the reaction conversion ratio in the present embodiment reaches 47%, and in the reaction product that the present embodiment obtains, cyclic carbonate ester content is less than 3%.
The present invention is standard substance with polystyrene, utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 5.1 ten thousand, and molecular weight distribution is 1.07.
Embodiment 26
The Schiff's base cobalt compound obtain 2.232g propylene oxide, 0.03g embodiment 9 and 0.0166gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature, 40 DEG C of stirrings, reacts 1h;
Be placed in frozen water by reactor after reaction terminates and lower the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure.After driving still, product 15mL methylene dichloride is dissolved, the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, solid vacuum-drying sedimentation obtained, obtains reaction product.
The reaction product obtained is carried out
1h-NMR analyzes, and result shows, the reaction conversion ratio in the present embodiment reaches 51%, and in the reaction product that the present embodiment obtains, cyclic carbonate ester content is 8%.
The present invention is standard substance with polystyrene, utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 5.1 ten thousand, and molecular weight distribution is 1.12.
Embodiment 27
The Schiff's base cobalt compound obtain 2.232g propylene oxide, 0.03g embodiment 9 and 0.0221gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature, 40 DEG C of stirrings, reacts 1h;
Be placed in frozen water by reactor after reaction terminates and lower the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure.After driving still, product 15mL methylene dichloride is dissolved, the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, solid vacuum-drying sedimentation obtained, obtains reaction product.
The reaction product obtained is carried out by the present invention
1h-NMR analyzes, and result shows, in the present embodiment, reaction conversion ratio reaches 53%, cyclic carbonate ester content about 13% in the reaction product that the present embodiment obtains.
The present invention is standard substance with polystyrene, utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 4.9 ten thousand, and molecular weight distribution is 1.13.
Embodiment 28
The Schiff's base cobalt compound obtain 1.9067g propylene oxide, 0.0205g embodiment 9 and 0.0091gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature, 60 DEG C of stirrings, reacts 0.25h;
Be placed in frozen water by reactor after reaction terminates and lower the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure.After driving still, product 15mL methylene dichloride is dissolved, the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, solid vacuum-drying sedimentation obtained, obtains reaction product.
The reaction product obtained is carried out by the present invention
1h-NMR analyzes, and result shows, the reaction conversion ratio in the present embodiment reaches 25%, and in the reaction product that the present embodiment obtains, cyclic carbonate ester content is less than 3%.
The present invention is standard substance with polystyrene, utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 4.8 ten thousand, and molecular weight distribution is 1.05.
Embodiment 29
The Schiff's base cobalt compound obtain 1.9067g propylene oxide, 0.0205g embodiment 9 and 0.0091gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature, 60 DEG C of stirrings, reacts 1.5h;
Be placed in frozen water by reactor after reaction terminates and lower the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure.After driving still, product 15mL methylene dichloride is dissolved, the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, solid vacuum-drying sedimentation obtained, obtains reaction product.
The reaction product obtained is carried out by the present invention
1h-NMR analyzes, and result shows, the reaction conversion ratio in the present embodiment reaches 80%, and in the reaction product that the present embodiment obtains, cyclic carbonate ester content is less than 3%.
The present invention is standard substance with polystyrene, utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 5.8 ten thousand, and molecular weight distribution is 1.09.
Embodiment 30
The Schiff's base cobalt compound prepare 2.68g propylene oxide, 0.0090g embodiment 9 and 0.0040gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 2MPa, control temperature, 60 DEG C of stirrings, reacts 5.5h;
Be placed in frozen water by reactor after reaction terminates and lower the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure.After driving still, product 15mL methylene dichloride is dissolved, the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, solid vacuum-drying sedimentation obtained, obtains reaction product.
The reaction product obtained is carried out by the present invention
1h-NMR analyzes, and result shows, the reaction conversion ratio in the present embodiment reaches 67%, cyclic carbonate ester content about 5% in the reaction product that the present embodiment obtains.
The present invention is standard substance with polystyrene, utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 8.8 ten thousand, and molecular weight distribution is 1.13.
Embodiment 31
The Schiff's base cobalt compound prepare 7.4g propylene oxide, 0.01g embodiment 9 and 0.00732gPPNCl promotor are mixed to join and dewater in the autoclave of deoxygenation through high temperature, pass into high-purity carbon dioxide gas wherein, be forced into 3MPa, control temperature, 60 DEG C of stirrings, reacts 24h;
Be placed in frozen water by reactor after reaction terminates and lower the temperature rapidly, then slow releasing residual gas drops to normal atmosphere to pressure.After driving still, product 15mL methylene dichloride is dissolved, the solution obtained slowly is dropped in 200mL ethanol, static 30min after stirring 15min; Again dissolved with methylene dichloride by polymkeric substance after precipitation, sedimentation in ethanol, repeat 3 times, solid vacuum-drying sedimentation obtained, obtains reaction product.
The reaction product obtained is carried out by the present invention
1h-NMR analyzes, and result shows, the reaction conversion ratio in the present embodiment reaches 35%, in the reaction product that the present embodiment obtains, and cyclic carbonate ester content about 30%.
The present invention is standard substance with polystyrene, utilizes gel permeation chromatography to analyze the polycarbonate that the present embodiment obtains, and the number-average molecular weight obtaining polycarbonate is 11.2 ten thousand, and molecular weight distribution is 1.15.
As seen from the above embodiment, the invention provides a kind of Schiff's base cobalt compound, there is structure shown in formula (I) or formula (II).The present invention reacts to have the Schiff's base of structure and the salt compounds of cobalt shown in formula (III), obtains the Schiff's base cobalt complex with structure shown in formula (IV); Again under oxygen atmosphere, the Schiff's base cobalt complex having a structure shown in formula (IV) by described and 2,4-DNP react, and obtain the schiff base compounds with formula (I) described structure; Or under oxygen atmosphere, by described Schiff's base cobalt complex and the acetic acid reaction with structure shown in formula (IV), obtain the Schiff's base cobalt compound with structure shown in formula (II).The present invention is by the Schiff's base cobalt compound that obtains and promotor acting in conjunction, and the copolyreaction of catalysis carbonic acid gas and epoxide, obtains polycarbonate.Schiff's base cobalt compound provided by the invention has biphenyl bimetallic center structure, this bimetallic center structure makes Schiff's base cobalt compound have higher catalytic activity and selectivity, and there is good catalytic performance in wide temperature range, Schiff's base cobalt compound provided by the invention can play katalysis under low concentration and high temperature, the reaction of efficient catalytic carbonic acid gas and epoxide.In addition, Schiff's base cobalt compound provided by the invention also has higher selectivity, can highly selective obtain chain polycarbonate.Experimental result shows, is adopting the Schiff's base cobalt compound of structure shown in 0.01g formula (I) as catalyzer, catalysis 7.4g propylene oxide and carbonic acid gas at 60 DEG C, react 8h after, reaction conversion ratio reaches 35%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (12)
1. a Schiff's base cobalt compound, has structure shown in formula (I) or formula (II):
Wherein, R
1and R
2independently selected from aliphatic group.
2. Schiff's base cobalt compound according to claim 1, is characterized in that, described R
1and R
2independently selected from-CH
3,-CH
2cH
3,-CH (CH
3)
2or-C (CH
3)
3.
3. a preparation method for Schiff's base cobalt compound, comprises the following steps:
Reacting having the Schiff's base of structure and the salt compounds of cobalt shown in formula (III) in a solvent, obtaining the Schiff's base cobalt complex with structure shown in formula (IV);
In formula (III), R
1and R
2independently selected from aliphatic group;
In formula (IV), R
1and R
2independently selected from aliphatic group;
Under oxygen atmosphere, the described Schiff's base cobalt complex with structure shown in formula (IV) is reacted in organic solvent with 2,4-DNP, be there is the Schiff's base cobalt compound of (I) shown structure;
In formula (I), R
1and R
2independently selected from aliphatic group;
Or
Under oxygen atmosphere, the described Schiff's base cobalt complex with structure shown in formula (IV) is reacted in organic solvent with acetic acid, obtain the Schiff's base cobalt compound with the shown structure of formula (II);
In formula (II), R
1and R
2independently selected from aliphatic group.
4. preparation method according to claim 3, is characterized in that, described in there is the Schiff's base of structure shown in formula (III) preparation method comprise the following steps:
The tetraamine compound with structure shown in formula (V) is reacted with the substituted salicylic aldehydes with formula (VI) structure, obtains the Schiff's base with structure shown in formula (III);
In formula (VI), R
1and R
2independently selected from aliphatic group.
5. preparation method according to claim 3, is characterized in that, the salt compounds of described cobalt is Cobaltous diacetate, cobalt chloride or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
6. preparation method according to claim 3, is characterized in that, in the Schiff's base of structure shown in described formula (III) and the salt compounds of cobalt, the mol ratio of cobalt is 1:(2 ~ 5).
7. preparation method according to claim 3, is characterized in that, shown in described formula (IV), the Schiff's base cobalt complex of structure and the mol ratio of 2,4-DNP are 1:(2 ~ 5);
Shown in described formula (IV), the schiff bases complex of structure and the mol ratio of acetic acid are 1:(2 ~ 5).
8. a preparation method for polycarbonate, comprises the following steps:
Under the katalysis of catalyzer and promotor, carbonic acid gas and epoxide carry out copolyreaction, obtain polycarbonate;
The Schiff's base cobalt compound that described catalyzer obtains for preparation method described in the Schiff's base cobalt compound described in claim 1 ~ 2 any one or claim 3 ~ 7 any one.
9. preparation method according to claim 8, it is characterized in that, described promotor is one or more in two (dihalotriphenylphosphoranes base) ammonium chloride, DMAP, N-Methylimidazole, tricyclohexyl phosphine, 4 bromide and Tetrabutyl amonium bromide.
10. preparation method according to claim 8, is characterized in that, the mol ratio of described catalyzer and promotor is 1:(1 ~ 5);
The total mole number of described catalyzer and promotor and the mol ratio of epoxide are 1:(1000 ~ 40000).
11. preparation methods according to claim 8, is characterized in that, the pressure of described carbonic acid gas is 2MPa ~ 5MPa.
12. preparation methods according to claim 8, is characterized in that, the temperature of described copolyreaction is 30 DEG C ~ 90 DEG C;
The time of described copolyreaction is 0.5h ~ 24h.
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| CN109054011B (en) * | 2018-07-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | Schiff base cobalt compound, preparation method thereof and preparation method of polycarbonate |
| CN109675635B (en) * | 2019-02-22 | 2020-08-04 | 中南大学 | Non-covalent polymer catalyst suitable for 2,3, 6-trimethylphenol oxidation and preparation method thereof |
| CN110041227B (en) * | 2019-05-24 | 2021-03-30 | 福州大学 | Preparation of bimetallic Schiff base Mo complex and application of bimetallic Schiff base Mo complex in catalyzing olefin epoxidation |
| CN111234257B (en) * | 2020-03-13 | 2021-12-07 | 南昌航空大学 | Schiff base zinc complex functionalized polyion liquid and preparation method and application thereof |
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| CN113416147A (en) * | 2021-06-28 | 2021-09-21 | 上海应用技术大学 | Schiff base-metal organic complex and preparation method and application thereof |
| CN114315915B (en) * | 2022-01-17 | 2023-06-20 | 中国科学院长春应用化学研究所 | Binuclear Schiff base cobalt complex and preparation method and application thereof |
| CN114957344A (en) * | 2022-06-30 | 2022-08-30 | 中国科学院长春应用化学研究所 | Trinuclear cobalt compound, electron-withdrawing group multi-polyester material and preparation method thereof |
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