One kind is used to be catalyzed carbon dioxide and 7-oxa-bicyclo[4.1.0 copolyreaction prepares poly- plutonium carbonate
The catalyst of hexene ester
Technical field
The invention belongs to technical field of organic synthesis, and in particular to one kind is total to for being catalyzed carbon dioxide with 7-oxa-bicyclo[4.1.0
Poly- reaction prepares the catalyst of polycyclohexene.
Background technology
Comprehensive utilization carbon dioxide will be helpful to the exhausted problem for solving future source of energy, and this has caused global scientific worker
Attention.For example, carbon dioxide can react the low carbon compounds such as generation methane, formic acid, methanol with hydrogen reducing;Carbon dioxide is also
Can the low-carbon alkene such as direct hydrogenation synthesizing ethylene, propylene.In addition to the studies above direction, carbon dioxide can be in the effect of copper catalyst
Lower and hydrogen reaction prepares dimethyl ether, and acetaldehyde is generated with hydrogen under silver-colored rhodium catalyst.If hydrogenation of carbon dioxide reduction is not
A large amount of hydrogen sources are only needed also to expend mass energy, then carbon dioxide is used with greater advantages as oxidant.Dioxy
Change carbon and generate ethene with methane, ethane reaction under catalyst action.Except this, carbon dioxide can also be with methanol oxidation carbonate synthesis
Dimethyl ester, with ethylene oxide synthesis ethylene carbonate, and expoxy propane synthesizing acrylic ester etc..
Fatty poly-ester carbonate using carbon dioxide as Material synthesis has good biological degradability, and this research is also
Solves one of the approach of " white pollution ".Therefore, the research of carbon dioxide and epoxides synthctic fat adoption carbonic ester is carried out
Work has great significance.But carbon dioxide has higher thermodynamic stability, it is difficult to participates in chemical reaction, it is necessary to phase
The effective catalyst answered activates.Since nearly 30 years, various countries researcher is to used in epoxide and carbon dioxide copolymerization
Catalyst carried out numerous studies exploitation, succeeded in developing the different catalyst of various active perhaps, can be divided mainly into following three
Class:1. organo-metallic compound, by metal alkyl and at least contain the additive reaction of two active hydrogens and obtain, wherein most active
It is to be obtained by dialkyl group zinc with least containing the additive reaction of two reactive hydrogen atoms;2. coordinated metal complex;3. rare earth
Compound.But the problems such as above-mentioned catalyst generally existing catalytic efficiency is low, reaction selectivity is poor, production cost is high, so as to limit
Its heavy industrialization application.
It is used for what is reported in catalyst system and catalyzing of the carbon dioxide with epoxide copolymerization, Schiff base metal complexes are urged
Change system has good catalytic effect, and using beta-diimine zinc catalyst system and catalyzing and SalenMX catalyst system and catalyzings as representative, what is obtained is total to
Ester chain content is higher in polymers, narrow molecular weight distribution.But catalyst preparation process is complicated, cost is higher.If can be further
Improve its catalytic activity or reduce and prepare cost, such catalyst will have good prospects for commercial application.
The content of the invention
For problems of the prior art, the present invention provides one kind and is total to for being catalyzed carbon dioxide with 7-oxa-bicyclo[4.1.0
Poly- reaction prepares the catalyst of polycyclohexene, and catalyst of the invention is copolymerized for carbon dioxide and 7-oxa-bicyclo[4.1.0
When there is the advantages of high catalytic efficiency, good reaction selectivity, catalytic reaction condition are gentle, easy to operate.
In order to solve the above technical problems, the present invention uses following technical scheme:
It is a kind of to be used to be catalyzed the catalyst that carbon dioxide prepares polycyclohexene with 7-oxa-bicyclo[4.1.0 copolyreaction, it is described
Catalyst is 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine Zn complexes;Structural formula is as follows:
。
2, the 6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine Zn complexes are made using following methods:
(1)Respectively by 2- furylamines, 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine, which is dissolved in methanol, forms solution, at room temperature
By 2,6- bis-(2- aldehyde radical Phenoxymethyls)The methanol solution of pyridine is added drop-wise in the methanol solution of 2- furylamines, is added dropwise
Afterwards, it is heated to reflux, stirs 0.5 ~ 1h, ether washing, dry, obtain 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furans first
Amine ligand;
(2)Weigh 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine parts are put into container, are vacuumized, nitrogen charging
Gas, under nitrogen protection, add toluene dissolving 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine parts, in cryosel
Bath cooling is lower to add the toluene solution containing diethyl zinc, after stirring 0.5 ~ 1h, removes ice salt bath, stirring at normal temperature 1h, decompression is taken out
Solvent and unreacted diethyl zinc are walked, obtains 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine Zn complexes.
The step(1)2- furylamines and 2,6- bis-(2- aldehyde radical Phenoxymethyls)The mol ratio of pyridine is 1:0.4~0.6.
The step(2)In 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamines part and diethyl zinc rub
You are than being 1:1~1.25.
It is used to be catalyzed carbon dioxide and the catalysis of 7-oxa-bicyclo[4.1.0 copolyreaction preparation polycyclohexene using described
Agent is catalyzed the method that carbon dioxide prepares polycyclohexene with 7-oxa-bicyclo[4.1.0 copolyreaction, it is characterised in that step is such as
Under:
A, by 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine Zn complexes are put into vacuum drying reactor,
Carbon dioxide is filled with to normal pressure, 7-oxa-bicyclo[4.1.0 is added into reactor, is warming up to 60 ~ 150 DEG C, carbon dioxide is filled with and keeps pressure
By force after 1 ~ 6MPa, 6 ~ 50h of stirring reaction, room temperature is cooled to, stops reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue is post-treated to obtain polycyclohexene.
2,6- bis- in the step a(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamines Zn complex and 7-oxa-bicyclo[4.1.0
Mass ratio be 0.001 ~ 0.01:1.
The process of the post processing is:Residue is dissolved with dichloromethane, filter, filtrate successively with diluted acid, diluted alkaline and
After distilling water washing, instill in the methanol of stirring, separate out white solid thing;Filtering, vacuum drying, produces poly- carbonic acid cyclohexene
Ester.
The present invention prepares the reaction of polycyclohexene in the catalyst carbon dioxide and 7-oxa-bicyclo[4.1.0 copolymerization
Under the conditions of, the polycyclohexene of different molecular weight can be obtained, catalytic efficiency is up to 236g polymer/g catalysis
Agent, makrolon content is more than 95% in polycyclohexene.
Beneficial effects of the present invention:The catalyst of the present invention has when being copolymerized for carbon dioxide with 7-oxa-bicyclo[4.1.0 urges
The advantages of changing efficiency high, good reaction selectivity, gentle, easy to operate catalytic reaction condition.
Embodiment
With reference to specific embodiment, the present invention will be further described.It should be understood that following examples are merely to illustrate this
Invention can make one not for limitation the scope of the present invention, the person skilled in the art in the field according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
2, the 6- bis- of the present embodiment(2- aldehyde radical Phenoxymethyls)The preparation method of pyridine contracting 2- furylamine Zn complexes is as follows;
(1)Respectively by 0.97g(0.01mol)2- furylamines, 1.74g(0.005mol)2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyrrole
Pyridine, which is dissolved in 20mL methanol, forms solution, at room temperature by 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridinemethanol solution is added drop-wise to 2-
In furylamine methanol solution, after being added dropwise, it is heated to reflux, stirs 0.5h, ether washing, dry, obtain 2,6- bis-(2- aldehyde
Base Phenoxymethyl)Pyridine contracting 2- furylamine parts;2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine parts
Structural formula is
Nmr analysis result is:
1H NMR (400 MHz, CDCl3): δ 4.91(s, 4H, CH2), 5.32(s, 4H, CH2), 6.07~8.1(m,
17H, aromatic H), 8.4(s, 2H, CH);
(2)Weigh 0.1mol2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine parts are put into container, are vacuumized,
Inflated with nitrogen, under nitrogen protection, add 200mL toluene dissolving 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamines are matched somebody with somebody
Body, the toluene solution containing 0.125mol diethyl zincs is added under ice salt bath cooling(10%vol), after stirring 0.5h, remove ice
Salt bath, stirring at normal temperature 1h, decompression take solvent and unreacted diethyl zinc away, produce 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyrrole
Pyridine contracting 2- furylamine Zn complexes.
Embodiment 2
2, the 6- bis- of the present embodiment(2- aldehyde radical Phenoxymethyls)The preparation method of pyridine contracting 2- furylamine Zn complexes is as follows;
(1)Respectively by 0.97g(0.01mol)2- furylamines, 1.39g(0.004mol)2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyrrole
Pyridine, which is dissolved in 20mL methanol, forms solution, at room temperature by 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridinemethanol solution is added drop-wise to 2-
In furylamine methanol solution, after being added dropwise, it is heated to reflux, stirs 1h, ether washing, dry, obtain 2,6- bis-(2- aldehyde radicals
Phenoxymethyl)Pyridine contracting 2- furylamine parts;
(2)Weigh 0.1mol2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine parts are put into container, are vacuumized,
Inflated with nitrogen, under nitrogen protection, add 200mL toluene dissolving 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamines are matched somebody with somebody
Body, the toluene solution containing 0.1mol diethyl zincs is added under ice salt bath cooling(10%vol), after stirring 0.8h, remove cryosel
Bath, stirring at normal temperature 1h, decompression take solvent and unreacted diethyl zinc away, produce 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine
Contracting 2- furylamine Zn complexes.
Embodiment 3
2, the 6- bis- of the present embodiment(2- aldehyde radical Phenoxymethyls)The preparation method of pyridine contracting 2- furylamine Zn complexes is as follows;
(1)Respectively by 0.97g(0.01mol)2- furylamines, 2.08g(0.006mol)2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyrrole
Pyridine, which is dissolved in 25mL methanol, forms solution, at room temperature by 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridinemethanol solution is added drop-wise to 2-
In furylamine methanol solution, after being added dropwise, it is heated to reflux, stirs 1h, ether washing, dry, obtain 2,6- bis-(2- aldehyde radicals
Phenoxymethyl)Pyridine contracting 2- furylamine parts;
(2)Weigh 0.1mol2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine parts are put into container, are vacuumized,
Inflated with nitrogen, under nitrogen protection, add 200mL toluene dissolving 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamines are matched somebody with somebody
Body, the toluene solution containing 0.12mol diethyl zincs is added under ice salt bath cooling(10%vol), after stirring 0.5h, remove ice
Salt bath, stirring at normal temperature 1h, decompression take solvent and unreacted diethyl zinc away, produce 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyrrole
Pyridine contracting 2- furylamine zinc catalysts.
Embodiment 4
The present embodiment utilizes 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamines Zn complex be catalyzed carbon dioxide with
The method that 7-oxa-bicyclo[4.1.0 copolyreaction prepares polycyclohexene is as follows:
A, by 0.10g 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine zinc catalysts are put into vacuum drying height
Press in reactor(Stirrer has been pre-placed in autoclave), 1h is dried in vacuo under the conditions of being 100 DEG C in temperature, is cooled to
Room temperature, carbon dioxide is filled with to normal pressure;20.84mL is added into reactor(20g)7-oxa-bicyclo[4.1.0,60 DEG C are warming up to, is filled with
Carbon dioxide, pressure is kept in 3.5MPa, magnetic agitation, after reacting 20h, be cooled to room temperature, stop reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue is dissolved with dichloromethane, filtered, filter
Liquid with after diluted acid, diluted alkaline and distillation water washing, slowly instills in the methanol of stirring successively, that is, separates out white solid thing;Filtering, very
Sky is dried, and produces polycyclohexene 15.5g;Wherein described methanol is the 300% of filtrate quality.
The ownership of polymer each characteristic peak in infrared spectrum is as follows:1467,1366,2993 cm-1(CH3);787,
1460,2875 cm-1(CH2);2890 cm-1, 1332 cm-1(CH);1755 cm-1(C=O);1241 cm-1(C-O).Nuclear-magnetism hydrogen
Compose (400MHz, CDCl3):[m, the CH (CO of δ 4.83)], 4.0 [m, CH2(CO3)], 3.7 [CH2(O) and CH (O)], 1.42 (d,
CH3)。
M n=18.2 kg/mol, warp1It is 95.8% that H NMR, which analyze carbon dioxide and the alternating copolymerization rate of 7-oxa-bicyclo[4.1.0,
Catalytic efficiency is 155 g polymer/g catalyst.(WhereinM nRepresent number-average molecular weight).
Embodiment 5
The present embodiment utilizes 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamines Zn complex be catalyzed carbon dioxide with
The method that 7-oxa-bicyclo[4.1.0 copolyreaction prepares polycyclohexene is as follows:
A, by 0.10g 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine zinc catalysts are put into vacuum drying height
Press in reactor(Stirrer has been pre-placed in autoclave), 1h is dried in vacuo under the conditions of being 100 DEG C in temperature, is cooled to
Room temperature, carbon dioxide is filled with to normal pressure;20.84mL is added into reactor(20g)7-oxa-bicyclo[4.1.0,100 DEG C are warming up to, is filled with
Carbon dioxide, pressure is kept in 6MPa, magnetic agitation, after reacting 50h, be cooled to room temperature, stop reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue is dissolved with dichloromethane, filtered, filter
Liquid with after diluted acid, diluted alkaline and distillation water washing, slowly instills in the methanol of stirring successively, that is, separates out white solid thing;Filtering, very
Sky is dried, and produces polycyclohexene 18.7g;Wherein described methanol is the 500% of filtrate quality.
M n=19.7 kg/mol, warp1H NMR analyze carbon dioxide and the alternating copolymerization rate of 7-oxa-bicyclo[4.1.0 is
96.2%, catalytic efficiency is 187 g polymer/g catalyst.(WhereinM nRepresent number-average molecular weight).
Embodiment 6
The present embodiment utilizes 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamines Zn complex be catalyzed carbon dioxide with
The method that 7-oxa-bicyclo[4.1.0 copolyreaction prepares polycyclohexene is as follows:
A, by 0.10g 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine zinc catalysts are put into vacuum drying height
Press in reactor(Stirrer has been pre-placed in autoclave), 1h is dried in vacuo under the conditions of being 100 DEG C in temperature, is cooled to
Room temperature, carbon dioxide is filled with to normal pressure;104.2mL is added into reactor(100g)7-oxa-bicyclo[4.1.0,150 DEG C are warming up to, is filled
Enter carbon dioxide, keep pressure magnetic agitation, after reacting 12h, to be cooled to room temperature, stop reaction in 5MPa;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue is dissolved with dichloromethane, filtered, filter
Liquid with after diluted acid, diluted alkaline and distillation water washing, slowly instills in the methanol of stirring successively, that is, separates out white solid thing;Filtering, very
Sky is dried, and produces polycyclohexene 20.9g;Wherein described methanol is the 400% of filtrate quality.
M n=23.7 kg/mol, warp1H NMR analyze carbon dioxide and the alternating copolymerization rate of 7-oxa-bicyclo[4.1.0 is
97.8%, catalytic efficiency is 209g polymer/g catalyst.(WhereinM nRepresent number-average molecular weight).
Embodiment 7
The present embodiment utilizes 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamines Zn complex be catalyzed carbon dioxide with
The method that 7-oxa-bicyclo[4.1.0 copolyreaction prepares polycyclohexene is as follows:
A, by 0.10g 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine zinc catalysts are put into vacuum drying height
Press in reactor(Stirrer has been pre-placed in autoclave), 1h is dried in vacuo under the conditions of being 100 DEG C in temperature, is cooled to
Room temperature, carbon dioxide is filled with to normal pressure;41.68mL is added into reactor(40g)7-oxa-bicyclo[4.1.0,110 DEG C are warming up to, is filled with
Carbon dioxide, pressure is kept in 4MPa, magnetic agitation, after reacting 24h, be cooled to room temperature, stop reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue is dissolved with dichloromethane, filtered, filter
Liquid with after diluted acid, diluted alkaline and distillation water washing, slowly instills in the methanol of stirring successively, that is, separates out white solid thing;Filtering, very
Sky is dried, and produces polycyclohexene 23.6g;Wherein described methanol is the 200% of filtrate quality.
M n=33.5 kg/mol, warp1H NMR analyze carbon dioxide and the alternating copolymerization rate of 7-oxa-bicyclo[4.1.0 is
96.8%, catalytic efficiency is 236g polymer/g catalyst.(WhereinM nRepresent number-average molecular weight).
Embodiment 8
The present embodiment utilizes 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamines Zn complex be catalyzed carbon dioxide with
The method that 7-oxa-bicyclo[4.1.0 copolyreaction prepares polycyclohexene is as follows:
A, by 0.10g 2,6- bis-(2- aldehyde radical Phenoxymethyls)Pyridine contracting 2- furylamine zinc catalysts are put into vacuum drying height
Press in reactor(Stirrer has been pre-placed in autoclave), 1h is dried in vacuo under the conditions of being 100 DEG C in temperature, is cooled to
Room temperature, carbon dioxide is filled with to normal pressure;15mL is added into reactor(14.4g)7-oxa-bicyclo[4.1.0,60 DEG C are warming up to, is filled with two
Carbonoxide, pressure is kept in 1MPa, magnetic agitation, after reacting 6h, be cooled to room temperature, stop reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue is dissolved with dichloromethane, filtered, filter
Liquid with after diluted acid, diluted alkaline and distillation water washing, slowly instills in the methanol of stirring successively, that is, separates out white solid thing;Filtering, very
Sky is dried, and produces polycyclohexene 11.27g;Wherein described methanol is the 400% of filtrate quality.
M n=16.3 kg/mol, warp1H NMR analyze carbon dioxide and the alternating copolymerization rate of 7-oxa-bicyclo[4.1.0 is
95.2%, catalytic efficiency is 112.7g polymer/g catalyst.(WhereinM nRepresent number-average molecular weight).
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
For art personnel it should be appreciated that the present invention is not limited to the above embodiments, described in above-described embodiment and specification is explanation
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.