One kind preparing poly- plutonium carbonate for being catalyzed carbon dioxide and 7-oxa-bicyclo[4.1.0 copolyreaction
The catalyst of hexene ester
Technical field
The invention belongs to technical field of organic synthesis, and in particular to one kind is total for being catalyzed carbon dioxide and 7-oxa-bicyclo[4.1.0
The catalyst of poly- reaction preparation polycyclohexene.
Background technique
Comprehensive utilization carbon dioxide will be helpful to solve the problems, such as the exhausted of future source of energy, this has caused global scientific worker
Attention.For example, carbon dioxide can be reacted with hydrogen reducing generates the low carbon compounds such as methane, formic acid, methanol;Carbon dioxide is also
It can the low-carbon alkenes 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 react with hydrogen prepares dimethyl ether, generates acetaldehyde 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 comes as oxidant using with greater advantages.Dioxy
Change carbon and reacts generation ethylene with methane, ethane under the action of catalyst.Except this, carbon dioxide can also be with methanol oxidation carbonate synthesis
Dimethyl ester, with ethylene oxide synthesis ethylene carbonate and propylene oxide synthesizing acrylic ester etc..
There is good biological degradability by the fatty poly-ester carbonate of Material synthesis of carbon dioxide, this research is also
Solve one of the approach of " white pollution ".Therefore, carry out the research of carbon dioxide and epoxides synthctic fat adoption carbonic ester
Work has great significance.However carbon dioxide thermodynamic stability with higher, it is difficult to participate in chemical reaction, need phase
The effective catalyst answered activates.Since nearly 30 years, various countries researcher is to used in epoxide and carbon dioxide copolymerization
Catalyst have conducted extensive research exploitation, succeeded in developing the different catalyst of various active perhaps, can be divided mainly into following three
Class: 1. organo-metallic compounds 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 at least the additive reaction of two reactive hydrogen atoms is contained;2. coordinated metal complex;3. rare earth
Close object.But the problems such as above-mentioned generally existing catalytic efficiency of catalyst is low, reaction selectivity is poor, high production cost, to limit
Its heavy industrialization application.
Reported in carbon dioxide and the catalyst system of epoxide copolymerization, Schiff base metal complexes to be urged
Change system has good catalytic effect, and using beta-diimine zinc catalyst system and SalenMX catalyst system 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, higher cost.If can be further
It improves its catalytic activity or reduces preparation cost, such catalyst will have good prospects for commercial application.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of total for being catalyzed carbon dioxide and 7-oxa-bicyclo[4.1.0
The catalyst of poly- reaction preparation polycyclohexene, catalyst of the invention are copolymerized for carbon dioxide and 7-oxa-bicyclo[4.1.0
When have the advantages that high catalytic efficiency, good reaction selectivity, catalytic reaction condition are mild, easy to operate.
In order to solve the above technical problems, the invention adopts the following technical scheme:
It is a kind of to prepare the catalyst of polycyclohexene, institute for being catalyzed carbon dioxide and 7-oxa-bicyclo[4.1.0 copolyreaction
The catalyst stated is 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine Zn complex;Structural formula is as follows:
。
2,6- bis- (2- aldehyde radical Phenoxymethyl) the pyridine contracting 2- furylamine Zn complex is prepared by the following method:
(1) 2- furylamine, 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine are dissolved in methanol and form solution respectively, in room
The methanol solution of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine is added drop-wise in the methanol solution of 2- furylamine under temperature, is dripped
Bi Hou is heated to reflux, and stirs 0.5 ~ 1h, and ether washing is dry, obtains 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furans
Methylamine ligand;
(2) it weighs 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine ligand to be put into container, vacuumizes, fill
Nitrogen is added toluene and dissolves 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine ligand, in ice under nitrogen protection
Cooling lower toluene solution of the addition containing diethyl zinc of salt bath, after stirring 0.5 ~ 1h, removes ice salt bath, stirring at normal temperature 1h, decompression
It takes solvent and unreacted diethyl zinc away, obtains the cooperation of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine zinc
Object.
Step (1) the 2- furylamine and 2, the molar ratio of 6- bis- (2- aldehyde radical Phenoxymethyl) pyridine are 1:0.4 ~ 0.6.
(2- aldehyde radical Phenoxymethyl) the pyridine contracting 2- furylamine ligand of 2,6- bis- and diethyl zinc rubs in the step (2)
You are than being 1:1 ~ 1.25.
Using described for being catalyzed the catalysis of carbon dioxide and 7-oxa-bicyclo[4.1.0 copolyreaction preparation polycyclohexene
The method that agent is catalyzed carbon dioxide and 7-oxa-bicyclo[4.1.0 copolyreaction preparation polycyclohexene, it is characterised in that step is such as
Under:
A, 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine Zn complex is put into vacuum drying reaction
In kettle, carbon dioxide is filled with to normal pressure, 7-oxa-bicyclo[4.1.0 is added into reaction kettle, is warming up to 60 ~ 150 DEG C, is filled with carbon dioxide
It keeps pressure in 1 ~ 6MPa, after being stirred to react 6 ~ 50h, is cooled to room temperature, stop reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue is post-treated to obtain poly- carbonic acid hexamethylene
Enester.
(2- aldehyde radical Phenoxymethyl) the pyridine contracting 2- furylamine Zn complex of 2,6- bis- and 7-oxa-bicyclo[4.1.0 in the step a
Mass ratio be 0.001 ~ 0.01:1.
The process of the post-processing are as follows: residue is dissolved with methylene chloride, filter, filtrate successively use diluted acid, diluted alkaline and
It after distilling water washing, instills in the methanol of stirring, white solid object is precipitated;Filtering is dried in vacuo to get poly- carbonic acid cyclohexene
Ester.
Reaction of the present invention in the catalyst carbon dioxide and 7-oxa-bicyclo[4.1.0 copolymerization preparation polycyclohexene
Under the conditions of, the polycyclohexene of available different molecular weight, catalytic efficiency is up to 236g polymer/g catalysis
Agent, polycarbonate content is more than 95% in polycyclohexene.
Beneficial effects of the present invention: catalyst of the invention has when being copolymerized for carbon dioxide with 7-oxa-bicyclo[4.1.0 urges
Change the advantage that high-efficient, good reaction selectivity, catalytic reaction condition are mild, easy to operate.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
The preparation method of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine Zn complex of the present embodiment is such as
Under;
(1) respectively by 0.97g(0.01mol) 2- furylamine, 1.74g(0.005mol) (the 2- aldehyde radical benzene oxygen first of 2,6- bis-
Base) pyridine is dissolved in 20mL methanol and forms solution, (2- aldehyde radical Phenoxymethyl) the pyridinemethanol solution of 2,6- bis- dripped at room temperature
It is added in 2- furylamine methanol solution, after being added dropwise, is heated to reflux, stir 0.5h, ether washing is dry, obtains 2,6-
Two (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine ligands;2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamines
The structural formula of ligand is
Nmr analysis result are as follows:
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) 0.1mol2 is weighed, 6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine ligand is put into container, is taken out
Vacuum, inflated with nitrogen are added 200mL toluene and dissolve 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furans under nitrogen protection
The toluene solution (10%vol) containing 0.125mol diethyl zinc is added in the case where ice salt bath is cooling in methylamine ligand, after stirring 0.5h,
Ice salt bath, stirring at normal temperature 1h are removed, decompression takes solvent and unreacted diethyl zinc away to get (the 2- aldehyde radical benzene oxygen of 2,6- bis-
Methyl) pyridine contracting 2- furylamine Zn complex.
Embodiment 2
The preparation method of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine Zn complex of the present embodiment is such as
Under;
(1) respectively by 0.97g(0.01mol) 2- furylamine, 1.39g(0.004mol) (the 2- aldehyde radical benzene oxygen first of 2,6- bis-
Base) pyridine is dissolved in 20mL methanol and forms solution, (2- aldehyde radical Phenoxymethyl) the pyridinemethanol solution of 2,6- bis- dripped at room temperature
It is added in 2- furylamine methanol solution, after being added dropwise, is heated to reflux, stir 1h, ether washing is dry, obtains 2,6- bis-
(2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine ligand;
(2) 0.1mol2 is weighed, 6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine ligand is put into container, is taken out
Vacuum, inflated with nitrogen are added 200mL toluene and dissolve 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furans under nitrogen protection
Methylamine ligand is added the toluene solution (10%vol) containing 0.1mol diethyl zinc in the case where ice salt bath is cooling, after stirring 0.8h, removes
Deicing salt bath, stirring at normal temperature 1h, decompression take solvent and unreacted diethyl zinc away to get (the 2- aldehyde radical benzene oxygen first of 2,6- bis-
Base) pyridine contracting 2- furylamine Zn complex.
Embodiment 3
The preparation method of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine Zn complex of the present embodiment is such as
Under;
(1) respectively by 0.97g(0.01mol) 2- furylamine, 2.08g(0.006mol) (the 2- aldehyde radical benzene oxygen first of 2,6- bis-
Base) pyridine is dissolved in 25mL methanol and forms solution, (2- aldehyde radical Phenoxymethyl) the pyridinemethanol solution of 2,6- bis- dripped at room temperature
It is added in 2- furylamine methanol solution, after being added dropwise, is heated to reflux, stir 1h, ether washing is dry, obtains 2,6- bis-
(2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine ligand;
(2) 0.1mol2 is weighed, 6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine ligand is put into container, is taken out
Vacuum, inflated with nitrogen are added 200mL toluene and dissolve 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furans under nitrogen protection
The toluene solution (10%vol) containing 0.12mol diethyl zinc is added in the case where ice salt bath is cooling in methylamine ligand, after stirring 0.5h,
Ice salt bath, stirring at normal temperature 1h are removed, decompression takes solvent and unreacted diethyl zinc away to get (the 2- aldehyde radical benzene oxygen of 2,6- bis-
Methyl) pyridine contracting 2- furylamine zinc catalyst.
Embodiment 4
The present embodiment is catalyzed titanium dioxide using 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine Zn complex
Carbon and the method for 7-oxa-bicyclo[4.1.0 copolyreaction preparation polycyclohexene are as follows:
A, by 0.10g 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine zinc catalyst is put into vacuum drying
Autoclave in (stirrer has been pre-placed in autoclave), temperature be 100 DEG C under the conditions of be dried in vacuo 1h, it is cold
But to room temperature, carbon dioxide is filled with to normal pressure;20.84mL(20g is added into reaction kettle) 7-oxa-bicyclo[4.1.0,60 DEG C are warming up to,
It is filled with carbon dioxide, keeps pressure in 3.5MPa, magnetic agitation is cooled to room temperature after reacting 20h, stops reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue dissolved with methylene chloride, mistake
Filter slowly instills in the methanol of stirring after filtrate successively uses diluted acid, diluted alkaline and distillation water washing, i.e. precipitation white solid object;It crosses
Filter is dried in vacuo to get polycyclohexene 15.5g;Wherein the methanol is the 300% of filtrate quality.
The ownership of polymer each characteristic peak in infrared spectroscopy 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 analyzes carbon dioxide and the alternating copolymerization rate of 7-oxa-bicyclo[4.1.0,
Catalytic efficiency is 155 g polymer/g catalyst.(whereinM nIndicate number-average molecular weight).
Embodiment 5
The present embodiment is catalyzed titanium dioxide using 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine Zn complex
Carbon and the method for 7-oxa-bicyclo[4.1.0 copolyreaction preparation polycyclohexene are as follows:
A, by 0.10g 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine zinc catalyst is put into vacuum drying
Autoclave in (stirrer has been pre-placed in autoclave), temperature be 100 DEG C under the conditions of be dried in vacuo 1h, it is cold
But to room temperature, carbon dioxide is filled with to normal pressure;20.84mL(20g is added into reaction kettle) 7-oxa-bicyclo[4.1.0,100 DEG C are warming up to,
It is filled with carbon dioxide, keeps pressure in 6MPa, magnetic agitation is cooled to room temperature after reacting 50h, stops reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue dissolved with methylene chloride, mistake
Filter slowly instills in the methanol of stirring after filtrate successively uses diluted acid, diluted alkaline and distillation water washing, i.e. precipitation white solid object;It crosses
Filter is dried in vacuo to get polycyclohexene 18.7g;Wherein the methanol is the 500% of filtrate quality.
M n=19.7 kg/mol, warp1H NMR analyzes 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 nIndicate number-average molecular weight).
Embodiment 6
The present embodiment is catalyzed titanium dioxide using 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine Zn complex
Carbon and the method for 7-oxa-bicyclo[4.1.0 copolyreaction preparation polycyclohexene are as follows:
A, by 0.10g 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine zinc catalyst is put into vacuum drying
Autoclave in (stirrer has been pre-placed in autoclave), temperature be 100 DEG C under the conditions of be dried in vacuo 1h, it is cold
But to room temperature, carbon dioxide is filled with to normal pressure;104.2mL(100g is added into reaction kettle) 7-oxa-bicyclo[4.1.0, it is warming up to 150
DEG C, it is filled with carbon dioxide, keeps pressure in 5MPa, magnetic agitation is cooled to room temperature after reacting 12h, stops reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue dissolved with methylene chloride, mistake
Filter slowly instills in the methanol of stirring after filtrate successively uses diluted acid, diluted alkaline and distillation water washing, i.e. precipitation white solid object;It crosses
Filter is dried in vacuo to get polycyclohexene 20.9g;Wherein the methanol is the 400% of filtrate quality.
M n=23.7 kg/mol, warp1H NMR analyzes 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 nIndicate number-average molecular weight).
Embodiment 7
The present embodiment is catalyzed titanium dioxide using 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine Zn complex
Carbon and the method for 7-oxa-bicyclo[4.1.0 copolyreaction preparation polycyclohexene are as follows:
A, by 0.10g 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine zinc catalyst is put into vacuum drying
Autoclave in (stirrer has been pre-placed in autoclave), temperature be 100 DEG C under the conditions of be dried in vacuo 1h, it is cold
But to room temperature, carbon dioxide is filled with to normal pressure;41.68mL(40g is added into reaction kettle) 7-oxa-bicyclo[4.1.0,110 DEG C are warming up to,
It is filled with carbon dioxide, keeps pressure in 4MPa, magnetic agitation is cooled to room temperature after reaction for 24 hours, stops reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue dissolved with methylene chloride, mistake
Filter slowly instills in the methanol of stirring after filtrate successively uses diluted acid, diluted alkaline and distillation water washing, i.e. precipitation white solid object;It crosses
Filter is dried in vacuo to get polycyclohexene 23.6g;Wherein the methanol is the 200% of filtrate quality.
M n=33.5 kg/mol, warp1H NMR analyzes 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 nIndicate number-average molecular weight).
Embodiment 8
The present embodiment is catalyzed titanium dioxide using 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine Zn complex
Carbon and the method for 7-oxa-bicyclo[4.1.0 copolyreaction preparation polycyclohexene are as follows:
A, by 0.10g 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- furylamine zinc catalyst is put into vacuum drying
Autoclave in (stirrer has been pre-placed in autoclave), temperature be 100 DEG C under the conditions of be dried in vacuo 1h, it is cold
But to room temperature, carbon dioxide is filled with to normal pressure;15mL(14.4g is added into reaction kettle) 7-oxa-bicyclo[4.1.0,60 DEG C are warming up to, is filled
Enter carbon dioxide, keep pressure in 1MPa, magnetic agitation is cooled to room temperature after reacting 6h, stops reaction;
B, reaction solution is taken out, unreacted 7-oxa-bicyclo[4.1.0 is distilled off, residue dissolved with methylene chloride, mistake
Filter slowly instills in the methanol of stirring after filtrate successively uses diluted acid, diluted alkaline and distillation water washing, i.e. precipitation white solid object;It crosses
Filter is dried in vacuo to get polycyclohexene 11.27g;Wherein the methanol is the 400% of filtrate quality.
M n=16.3 kg/mol, warp1H NMR analyzes 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 nIndicate number-average molecular weight).
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, 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.