CN107722254B - The catalyst and catalysis process for preparing fatty poly-ester carbonate are reacted with cyclohexene oxide for carbon dioxide - Google Patents
The catalyst and catalysis process for preparing fatty poly-ester carbonate are reacted with cyclohexene oxide for carbon dioxide Download PDFInfo
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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Abstract
The invention discloses a kind of react for carbon dioxide with cyclohexene oxide to prepare the catalyst of fatty poly-ester carbonate, the catalyst is 2, 6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline Zn complex, the present invention discloses the method for preparing fatty poly-ester carbonate is reacted with cyclohexene oxide using the catalyst carbon dioxide, the quality of the catalyst is the 0.1 ~ 1% of cyclohexene oxide quality, it is 60 ~ 150 DEG C that carbon dioxide, which reacts reaction temperature when preparing fatty poly-ester carbonate with cyclohexene oxide, carbon dioxide pressure is 1 ~ 6MPa, reaction time is 6 ~ 50h, the carbon dioxide is reacted with cyclohexene oxide to be prepared the entire copolyreaction of fatty poly-ester carbonate and carries out under solvent-free conditions.Catalyst of the invention has the advantages that high catalytic efficiency, good reaction selectivity, catalytic reaction condition are mild, easy to operate when being copolymerized for carbon dioxide and cyclohexene oxide.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to one kind for carbon dioxide with cyclohexene oxide the system of reacting
The catalyst and catalysis process of standby fatty poly-ester carbonate.
Background technique
Increase severely with the development of the global economy with world population, the limited carbon money of reserves on the earth such as coal, oil and natural gas
Source is consumed constantly.Some day, the mankind are faced with the stem reality of existing carbon resource, lack of energy at last.It finds
The work of new carbon source is very urgent.In addition, excessively exploitation and using these non-renewable carbon resources causing to discharge into atmosphere
Carbon dioxide is growing day by day, has caused a series of serious disastrous effects such as " greenhouse effects ".Meanwhile carbon dioxide is also a kind of recyclable
The carbon source utilized, reserves are more than the summation of coal, petroleum, natural gas.Therefore, using carbon dioxide as the starting of organic chemical industry
Raw material not only solves environmental problem, but also develops new carbon source, is the good method killed two birds with one stone.
Under normal conditions, carbon dioxide is Thermodynamically stable and kinetic inertness, chemical utilization it is difficult, still
By many years effort, certain progress is still achieved.It has been found that carbon dioxide can participate in some polymerization reactions and organic small
The synthetic reaction of molecule.It is related to the reduction process of carbon dioxide carbon atom in certain reactions, consumes energy larger, industrialization cost is very
Height only rests on phase of basic research.It is synthesized currently, there are about 1.1 hundred million tons of carbon dioxide every year for organic chemicals, wherein
80% contributes to the industrial production of urea, and the industrial structure is excessively single.So carbon dioxide chemistry is converted with the process of utilization also
Need further to be explored.Wherein, no matter the copolyreaction of carbon dioxide and epoxide examines from economic or environment angle
Consider, is all undoubtedly one of the chemical process of most application value and prospect.For many years, total about carbon dioxide and epoxide
The research of poly- reaction is in the ascendant always.
Carbon dioxide and epoxide are cheap and easy to get, traditional with phosgene/glycol polycondensation, cyclic carbonate ring opening copolymer etc.
Synthetic method is compared, and this method has significant Green Chemistry feature.It does not need to add any organic solvent in reaction process；It is raw
At fatty poly-ester carbonate can be degraded into harmless small organic molecule under field conditions (factors), therefore effectively prevent to environment
Secondary pollution.
Catalyst be influence carbon dioxide reacted with epoxide prepare fatty poly-ester carbonate realization industrialized production
Key factor.Ionue study group, Tokyo Univ Japan reports carbon dioxide and propylene oxide in ZnEt for the first time within 19962:
H2The copolyreaction occurred under the mixture through catalytic that O (molar ratio 1:1) is formed.Later, multiple study groups surround the effect of catalyst
Rate and cost expand the research work to carbon dioxide and epoxide copolyreaction.Current developed catalytic body owner
There are diethyl zinc catalyst system, phenoxy group zinc catalyst, beta-diimine zinc catalyst system, zinc carboxylate catalyst system, Salen gold
Belong to catalyst system, porphyrin metal catalyst system, DMC catalyst system, rare-earth catalysis system etc..Wherein with Salen metal catalytic body
System and beta-diimine zinc catalyst system are that the Schiff base complex catalyst of representative receives significant attention.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provide it is a kind of for carbon dioxide with cyclohexene oxide the system of reacting
The catalyst and catalysis process of standby fatty poly-ester carbonate, the catalyst raw material is cheap, preparation is simple, high catalytic efficiency, reaction
Selectivity is good.
In order to solve the above technical problems, the invention adopts the following technical scheme:
It is a kind of to react the catalyst for preparing fatty poly-ester carbonate, the catalyst with cyclohexene oxide for carbon dioxide
For 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline Zn complex, structural formula is as follows:
。
The method for preparing fatty poly-ester carbonate is reacted with cyclohexene oxide using the catalyst carbon dioxide,
The quality of the catalyst is the 0.1 ~ 1% of cyclohexene oxide quality.
It is 60 ~ 150 that the carbon dioxide, which reacts reaction temperature when preparing fatty poly-ester carbonate with cyclohexene oxide,
DEG C, carbon dioxide pressure is 1 ~ 6MPa, and the reaction time is 6 ~ 50h.
Preferably, the carbon dioxide reacts the entire copolyreaction for preparing fatty poly-ester carbonate with cyclohexene oxide
It carries out under solvent-free conditions.
The present invention utilizes 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline Zn complex catalysis two
The step of carbonoxide and cyclohexene oxide copolyreaction prepare the method for fatty poly-ester carbonate is as follows:
(1) will cooperate as the 2,6- bis- of catalyst (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline zinc
Object is put into vacuum drying autoclave, and 1 ~ 2h is dried in vacuo under the conditions of temperature is 100 DEG C, is cooled to room temperature, is filled with
Carbon dioxide is to normal pressure；Cyclohexene oxide is added into reaction kettle, is warming up to 60 ~ 150 DEG C, is filled with carbon dioxide, keeps pressure
In 1 ~ 6MPa, magnetic agitation is cooled to room temperature after reacting 6 ~ 50h, stops reaction；The quality of the catalyst is oxidation ring
The 0.1 ~ 1% of hexene mass；
(2) reaction solution is taken out, unreacted cyclohexene oxide is distilled off, residue methylene chloride dissolved, mistake
Filter instills in the methanol of high-speed stirred 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 copolyreaction product polycyclohexene；Wherein the methanol quality be filtrate quality 200 ~
500%。
The present invention is under above-mentioned reaction condition, the fatty poly-ester carbonate of available different molecular weight, catalytic efficiency
Up to 1832g polymer/g zinc, polycarbonate molar content is more than 95% in copolymer.
Catalyst 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline zinc cooperation of the present invention
Object the preparation method is as follows:
(1) preparation of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline ligand: 2,6- bis- is taken
(2- aldehyde radical Phenoxymethyl) pyridine and 2- amino -6- picoline are dissolved in methanol respectively, at room temperature 2- while stirring
The methanol solution of amino -6- picoline is added drop-wise in the methanol solution of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine, is dripped
Bi Hou is heated to reflux, and continues 0.5 ~ 2h of stirring, filters out sediment, and sediment is washed with ether, dry, obtains white powder；
Wherein the molar ratio of (the 2- aldehyde radical Phenoxymethyl) pyridine of 2,6- bis- and 2- amino -6- picoline is 0.45 ~ 0.55:1；
(2) preparation of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline Zn complex: weighing 2,
6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline ligand is put into container, to container vacuum-pumping, is then filled
Enter nitrogen and toluene is added and dissolves 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- first under nitrogen protection to normal pressure
Yl pyridines ligand, the toluene solution that diethyl zinc is added in the case where ice salt bath is cooling remove ice salt bath, room temperature after stirring 0.5 ~ 1h
0.5 ~ 1h is stirred, decompression takes toluene and unreacted diethyl zinc away, obtains white powder, (the 2- aldehyde radical benzene of as 2,6- bis-
Oxygen methyl) pyridine contracting 2- amino -6- picoline Zn complex；2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6-
The molar ratio of picoline ligand and diethyl zinc is 1:1 ~ 1.3.
Catalyst of the invention has high catalytic efficiency, selecting response when being copolymerized for carbon dioxide and cyclohexene oxide
The advantage that property is good, catalytic reaction condition is 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 catalyst 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline Zn complex
It is as follows:
(1) respectively by 2- amino -6- picoline 1.08g(0.01mol), 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine
It 1.74g(0.005mol) is dissolved in 15mL methanol, at room temperature, the methanol solution of 2- amino -6- picoline is added drop-wise to 2,6-
It in the methanol solution of two (2- aldehyde radical Phenoxymethyl) pyridines, is heated to reflux after dripping, continues to stir 2h, filter out sediment,
Sediment is washed with ether, it is dry, it obtains 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline and matches
Body；The structural formula of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline ligand is
Structural characterization is carried out to ligand:1H NMR (400 MHz, CDCl3): δ 2.67(s, 6H, -CH3), 5.82
(s, 4H, -CH2), 6.8~8.6(m, 17H, aromatic H), 8.83(s, 2H, -CH)；
(2) it weighs 0.1mol2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline ligand and is put into appearance
It in device, vacuumizes, inflated with nitrogen, under nitrogen protection, 200mL toluene is added and dissolves double 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridines
Toluene solution (10 vol containing 0.1mol diethyl zinc are added in the case where ice salt bath is cooling in contracting 2- amino -6- picoline 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 2,6-
Two (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline zinc catalysts.
Embodiment 2
The preparation method of catalyst 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline Zn complex
It is as follows:
(1) respectively by 2- amino -6- picoline 1.08g(0.01mol), 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine
It 1.91g(0.0055mol) is dissolved in 15mL methanol, at room temperature, the methanol solution of 2- amino -6- picoline is added drop-wise to 2,6-
It in the methanol solution of two (2- aldehyde radical Phenoxymethyl) pyridines, is heated to reflux after dripping, continues to stir 1h, filter out sediment,
Sediment is washed with ether, it is dry, it obtains 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline and matches
Body；
(2) it weighs 0.1mol2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline ligand and is put into appearance
It in device, vacuumizes, inflated with nitrogen, under nitrogen protection, 200mL toluene is added and dissolves double 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridines
The toluene solution (10 containing 0.13mol diethyl zinc is added in the case where ice salt bath is cooling in contracting 2- amino -6- picoline ligand
Vol %), after stirring 1h, remove ice salt bath, stirring at normal temperature 0.5h, decompression take away solvent and unreacted diethyl zinc to get
2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline zinc catalyst.
Embodiment 3
Carbon dioxide is catalyzed using catalyst 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline zinc
The method for preparing fatty poly-ester carbonate is reacted with cyclohexene oxide, steps are as follows:
(1) by 0.10g2,6- bis- made from embodiment 1 (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline
Zinc catalyst is put into vacuum drying autoclave and (has been pre-placed stirrer in autoclave), is 100 in temperature
It is dried in vacuo 1h under the conditions of DEG C, is cooled to room temperature, is filled with carbon dioxide to normal pressure；10.42mL(10g is added into reaction kettle) oxygen
Change cyclohexene, be warming up to 150 DEG C, be filled with carbon dioxide, keep pressure 4MPa, magnetic agitation is cooled to room temperature, stops after reacting 30h
Only react；
(2) reaction solution is taken out, unreacted cyclohexene oxide is distilled off, residue dissolved with methylene chloride, mistake
Filter slowly instills in the methanol of high-speed stirred after filtrate successively uses diluted acid, diluted alkaline and distillation water washing, i.e. precipitation white solid
Object；White solid precipitate is filtered out, is dried in vacuo to get copolyreaction product polycyclohexene；The wherein first
Alcohol quality is the 300% of filtrate quality.
Tg = 116oC,M n = 2.82×104G/mol, warp1H NMR analysis, polycarbonate mole contains in polymer
Amount is 96.3%, and catalytic efficiency is 1417 g polymer/g zinc.(wherein: TgIndicate glass transition temperature,M nIndicate that number is divided equally
Son amount).
Embodiment 5
Carbon dioxide is catalyzed using catalyst 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline zinc
The method for preparing fatty poly-ester carbonate is reacted with cyclohexene oxide, steps are as follows:
(1) by 0.10g2,6- bis- made from embodiment 2 (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline
Zinc catalyst is put into vacuum drying autoclave and (has been pre-placed stirrer in autoclave), is 100 in temperature
It is dried in vacuo 2h under the conditions of DEG C, is cooled to room temperature, is filled with carbon dioxide to normal pressure；20.84mL(20g is added into reaction kettle) oxygen
Change cyclohexene, be warming up to 110 DEG C, be filled with carbon dioxide, keep pressure 4MPa, magnetic agitation is cooled to room temperature, stops after reaction for 24 hours
Only react；
(2) reaction solution is taken out, unreacted cyclohexene oxide is distilled off, residue dissolved with methylene chloride, mistake
Filter slowly instills in the methanol of high-speed stirred after filtrate successively uses diluted acid, diluted alkaline and distillation water washing, i.e. precipitation white solid
Object；White solid precipitate is filtered out, is dried in vacuo to get copolyreaction product polycyclohexene；The wherein first
Alcohol quality is the 500% of filtrate quality.
Tg = 118oC,M n =3.79×104G/mol, warp1H NMR analysis, polycarbonate mole contains in polymer
Amount is 97.2%, and catalytic efficiency is 1832g polymer/g zinc.(wherein: TgIndicate glass transition temperature,M nIndicate the equal molecule of number
Amount).
Embodiment 6
Carbon dioxide is catalyzed using catalyst 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline zinc
The method for preparing fatty poly-ester carbonate is reacted with cyclohexene oxide, steps are as follows:
(1) by 0.10g2,6- bis- made from embodiment 3 (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline
Zinc catalyst is put into vacuum drying autoclave and (has been pre-placed stirrer in autoclave), is 100 in temperature
It is dried in vacuo 1.5h under the conditions of DEG C, is cooled to room temperature, is filled with carbon dioxide to normal pressure；104.2mL is added into reaction kettle
(100g) cyclohexene oxide, is warming up to 120 DEG C, is filled with carbon dioxide, keeps pressure 6MPa, and magnetic agitation is cold after reacting 50h
To room temperature, stop reaction；
(2) reaction solution is taken out, unreacted cyclohexene oxide is distilled off, residue dissolved with methylene chloride, mistake
Filter slowly instills in the methanol of high-speed stirred after filtrate successively uses diluted acid, diluted alkaline and distillation water washing, i.e. precipitation white solid
Object；White solid precipitate is filtered out, is dried in vacuo to get copolyreaction product polycyclohexene；The wherein first
Alcohol quality is the 300% of filtrate quality.
Tg = 117oC,M n =4.81×104G/mol, warp1H NMR analysis, polycarbonate mole contains in polymer
Amount is 97.4%, and catalytic efficiency is 1652 g polymer/g zinc.(wherein: TgIndicate glass transition temperature,M nIndicate that number is divided equally
Son amount).
Embodiment 7
Carbon dioxide is catalyzed using catalyst 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline zinc
The method for preparing fatty poly-ester carbonate is reacted with cyclohexene oxide, steps are as follows:
(1) by 0.10g 2,6- bis- made from embodiment 1 (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline
Zinc catalyst is put into vacuum drying autoclave and (has been pre-placed stirrer in autoclave), is 100 in temperature
It is dried in vacuo 2h under the conditions of DEG C, is cooled to room temperature, is filled with carbon dioxide to normal pressure；10.42mL(10g is added into reaction kettle) oxygen
Change cyclohexene, be warming up to 60 DEG C, be filled with carbon dioxide, keep pressure 1MPa, magnetic agitation is cooled to room temperature after reacting 6h, stops
Reaction；
(2) reaction solution is taken out, unreacted cyclohexene oxide is distilled off, residue dissolved with methylene chloride, mistake
Filter slowly instills in the methanol of high-speed stirred after filtrate successively uses diluted acid, diluted alkaline and distillation water washing, i.e. precipitation white solid
Object；White solid precipitate is filtered out, is dried in vacuo to get copolyreaction product polycyclohexene；The wherein first
Alcohol quality is the 200% of filtrate quality.
Tg = 114oC,M n =2.33×104G/mol, warp1H NMR analysis, polycarbonate mole contains in polymer
Amount is 95.2%, and catalytic efficiency is 1311 g polymer/g zinc.(wherein: TgIndicate glass transition temperature,M nIndicate that number is divided equally
Son amount).
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.
Claims (4)
1. a kind of react the catalyst for preparing fatty poly-ester carbonate for carbon dioxide with cyclohexene oxide, it is characterised in that:
The catalyst is 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline Zn complex, and structural formula is such as
Under:
；
The preparation method is as follows:
(1) preparation of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline ligand: (the 2- aldehyde of 2,6- bis- is taken
Base Phenoxymethyl) pyridine and 2- amino -6- picoline be dissolved in methanol respectively, at room temperature 2- amino-while stirring
The methanol solution of 6- picoline is added drop-wise in the methanol solution of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine, after being added dropwise,
It being heated to reflux, continues 0.5 ~ 2h of stirring, filter out sediment, sediment is washed with ether, and it is dry, obtain white powder；Wherein
The molar ratio of (the 2- aldehyde radical Phenoxymethyl) pyridine of 2,6- bis- and 2- amino -6- picoline is 0.45 ~ 0.55:1；
(2) preparation of 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline Zn complex: 2,6- bis- is weighed
(2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- picoline ligand is put into container, to container vacuum-pumping, is then charged with nitrogen
Gas is added toluene and dissolves 2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- methyl pyrrole under nitrogen protection to normal pressure
Pyridine ligand, the toluene solution that diethyl zinc is added in the case where ice salt bath is cooling remove ice salt bath, stirring at normal temperature after stirring 0.5 ~ 1h
0.5 ~ 1h, decompression take toluene and unreacted diethyl zinc away, obtain white powder, (the 2- aldehyde radical benzene oxygen first of as 2,6- bis-
Base) pyridine contracting 2- amino -6- picoline Zn complex；2,6- bis- (2- aldehyde radical Phenoxymethyl) pyridine contracting 2- amino -6- methyl
The molar ratio of pyridine ligand and diethyl zinc is 1:1 ~ 1.3.
2. catalyst carbon dioxide according to claim 1 is reacted with cyclohexene oxide prepares fatty poly-ester carbonate
Method, it is characterised in that: the quality of the catalyst be cyclohexene oxide quality 0.1 ~ 1%.
3. carbon dioxide according to claim 2 reacts the method for preparing fatty poly-ester carbonate with cyclohexene oxide,
Be characterized in that: reaction temperature is 60 ~ 150 DEG C, and carbon dioxide pressure is 1 ~ 6MPa, and the reaction time is 6 ~ 50h.
4. carbon dioxide according to claim 2 reacts the method for preparing fatty poly-ester carbonate with cyclohexene oxide,
Be characterized in that: the carbon dioxide reacts the entire copolyreaction for preparing fatty poly-ester carbonate with cyclohexene oxide solvent-free
Under the conditions of carry out.
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| CN113501950B (en) * | 2021-07-16 | 2023-01-17 | 郑州大学第一附属医院 | Metal complex catalyst for effectively preparing biocompatible polycarbonate and application thereof |
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|---|---|---|---|---|
| CN103242520A (en) * | 2013-05-13 | 2013-08-14 | 河南理工大学 | Method for preparing aliphatic polycarbonate by catalytic copolymerization of carbon dioxide and cyclohexene oxide by utilizing 2-furan formic acid zinc complex |
| CN103447091A (en) * | 2013-09-05 | 2013-12-18 | 中国科学院长春应用化学研究所 | Quadridentate pyridyl schiff base metal complex and preparation method thereof as well as preparation method of cyclic carbonate |
| CN103755943A (en) * | 2013-07-25 | 2014-04-30 | 河南理工大学 | Catalyst and method of preparing polycarbonate cyclohexene ester by using catalyst |
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| CN103242520A (en) * | 2013-05-13 | 2013-08-14 | 河南理工大学 | Method for preparing aliphatic polycarbonate by catalytic copolymerization of carbon dioxide and cyclohexene oxide by utilizing 2-furan formic acid zinc complex |
| CN103755943A (en) * | 2013-07-25 | 2014-04-30 | 河南理工大学 | Catalyst and method of preparing polycarbonate cyclohexene ester by using catalyst |
| CN103447091A (en) * | 2013-09-05 | 2013-12-18 | 中国科学院长春应用化学研究所 | Quadridentate pyridyl schiff base metal complex and preparation method thereof as well as preparation method of cyclic carbonate |
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