CN106083907B - A kind of schiff bases aluminum complex and its preparation method and application - Google Patents
A kind of schiff bases aluminum complex and its preparation method and application Download PDFInfo
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- CN106083907B CN106083907B CN201610473151.8A CN201610473151A CN106083907B CN 106083907 B CN106083907 B CN 106083907B CN 201610473151 A CN201610473151 A CN 201610473151A CN 106083907 B CN106083907 B CN 106083907B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
Abstract
The present invention provides a kind of schiff bases aluminum complexes and its preparation method and application, schiff bases aluminum complex provided by the invention has formula (I) structure, it is high that the present invention provides complex-catalyzed activity, and it is capable of the reaction of catalytic preparation of cyclic carbonic ester, polyester, polycarbonate and polycarbonate-polyester, catalyst has a wide range of application, and catalytic activity is high, has good prospects for commercial application.
Description
Technical field
The present invention relates to catalyst technical field more particularly to a kind of schiff bases aluminum complex and preparation method thereof and answer
With.
Background technique
Schiff bases is a kind of organic compound containing C=N group, and schiff bases is easy and the multiplicity in structure because of its preparation
Property, make one of spatial chemistry model mostly important in metal coordination chemistry.It is existing largely to have more than one since century
The report of schiff base metal complex is closed, still, from current report as can be seen that different schiff base metal complexes is to anti-
The catalytic effect answered also differs greatly.
With being constantly progressive for society, industrialized process accelerates, and the demand to high molecular material is also higher and higher, and passes
The material of system, such as polyethylene, polypropylene, polystyrene due to depending on unduly to petroleum resources, and are not easily decomposed and make
At factors such as white pollutions, gradually by social cleaning.Therefore, there is the material of degradable property to become the heat nowadays studied for synthesis
Point direction.Polycarbonate and polyester polymer have the characteristics that it is degradable, can be respectively by epoxides and carbon dioxide or ring
Oxide polymerize to obtain with cyclic acid anhydride.Wherein epoxides and cyclic acid anhydride are cheap chemical products, and titanium dioxide
Carbon can reduce its greenhouse effects as carbon source and epoxides copolymerization；Meanwhile the synthesis of this kind of degradation material has reaction
The advantages that condition is relatively mild, the polymer of easily preparation high molecular weight polymer and different modifying group.Can be used for preparing can
Degradation biological material, and pass through the modified material for preparing different function.
In addition, epoxides can carry out cycloaddition reaction under the effect of the catalyst with carbon dioxide, five-membered ring is generated
Shape carbonic ester, the product have preferable stability, can be widely applied to weaving, printing and dyeing, Polymer Synthesizing and electrochemistry
Equal fields.
Therefore, research using carbon dioxide or epoxide as the reaction synthesizing annular carbonate of reaction raw materials, polyester,
Polycarbonate and polycarbonate-polyester copolymer are the hot spots studied at present.
Summary of the invention
In view of this, technical problem to be solved by the present invention lies in provide a kind of schiff bases aluminum complex and its preparation
Methods and applications, schiff bases aluminum complex provided by the invention can catalytically synthesizing cyclic carbonate ester, polyester, polycarbonate and
Polycarbonate-polyester polymer, and high catalytic efficiency.
The present invention provides a kind of schiff bases aluminum complexes, have structure shown in formula (I):
Wherein, R1And R2Independently selected from aliphatic group.
Preferably, the R1And R2The aliphatic group for being 1~30 independently selected from carbon atom number.
The present invention also provides a kind of preparation methods of schiff bases aluminium compound, comprising the following steps:
To there is the schiff bases of structure shown in formula (II) to react in a solvent with aluminum source compound, obtain with formula (I) institute
Show the schiff bases aluminum complex of structure；
In formula (II), R1And R2Independently selected from aliphatic group.
Preferably, the schiff bases with structure shown in formula (II) preparation method the following steps are included:
To there is the tetraamine compound of structure shown in formula (III) to react with the substituted salicylic aldehydes with formula (IV) structure,
Obtain the schiff bases with structure shown in formula (II)；
In formula (IV), R1And R2Independently selected from aliphatic group.
The present invention also provides a kind of preparation methods of cyclic carbonate, comprising:
By epoxide, carbon dioxide, catalyst and co-catalyst hybrid reaction, cyclic carbonate is obtained；
The catalyst is of the present invention with structure schiff bases aluminum complex shown in formula (I)；
The epoxide is the ring of the aryl substitution of the epoxide of the alkyl substituent of C1~C15, C6~C20
Oxygen compound or glycidol ether.
Preferably, the epoxide is propylene oxide, ethylene oxide, epoxychloropropane, 1,2- epoxypentane, second two
One or more of alcohol diglycidyl ether, butanediol diglycidyl ether and neopentylglycol diglycidyl ether
The present invention also provides a kind of preparation methods of polycarbonate, comprising:
By epoxide, carbon dioxide, catalyst and co-catalyst hybrid reaction, polycarbonate is obtained；
The catalyst is of the present invention with structure schiff bases aluminum complex shown in formula (I)；
The epoxide is the cyclenes hydrocarbon oxide of C5~C8.
The present invention also provides a kind of preparation methods of polyester, comprising:
By epoxide, cyclic acid anhydride, catalyst and co-catalyst hybrid reaction, polyester is obtained；
The catalyst is of the present invention with structure schiff bases aluminum complex shown in formula (I).
The present invention also provides a kind of preparation methods of polycarbonate-polyester copolymer, comprising:
By carbon dioxide, epoxide, cyclic acid anhydride, catalyst and co-catalyst hybrid reaction, polycarbonate-is obtained
Polyester copolymer；
The catalyst is of the present invention with structure schiff bases aluminum complex shown in formula (I).
Preferably, the co-catalyst is bis- (dihalotriphenylphosphoranes base) ammonium chlorides, 4-dimethylaminopyridine, 1,8- diaza
Bicyclic [5.4.0] 11 carbon -7- alkene, tri- azabicyclic of 1,5,7- [4.4.0] decyl- 5- alkene, N- methylimidazole, tricyclohexyl phosphine,
One of tetrabutylammonium chloride and tetrabutylammonium bromide etc. are a variety of.
Compared with prior art, the present invention provides a kind of schiff bases aluminum complex and its preparation method and application, this hairs
The schiff bases aluminum complex of bright offer has formula (I) structure, and it is high that the present invention provides complex-catalyzed activity, and can be catalyzed system
The reaction of standby cyclic carbonate, polyester, polycarbonate and polycarbonate-polyester, catalyst have a wide range of application, and are catalyzed and live
Property it is high, there is good prospects for commercial application, the experimental results showed that, catalyst provided by the invention is in wider temperature range
All have preferable catalytic performance.
Specific embodiment
The present invention provides a kind of schiff bases aluminum complexes, have structure shown in formula (I):
Wherein, R1And R2Independently selected from aliphatic group.
Wherein, the R1Be preferably selected from carbon atom number be 1~30 aliphatic group, more preferably carbon atom number be 2~
The aliphatic group that 20 aliphatic group, most preferably carbon atom number are 3~15, most preferably carbon atom number are 5~10
Aliphatic group, more specifically, the R1Selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, just
Amyl, isopentyl, n-hexyl or n-heptyl；The R2It is preferably selected from the aliphatic group that carbon atom number is 1~30, more preferably
The aliphatic group that the aliphatic group that carbon atom number is 2~20, most preferably carbon atom number are 3~15, most preferably carbon are former
The aliphatic group that subnumber is 5~10, more specifically, the R2Selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, different
Butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl or n-heptyl.
The present invention also provides a kind of preparation methods of schiff bases aluminium compound, comprising the following steps:
To have the schiff bases and aluminum source compound hybrid reaction in a solvent of structure shown in formula (II), obtain with formula
(I) the schiff bases aluminum complex of structure shown in；
In formula (II), R1And R2Independently selected from aliphatic group.
According to the present invention, the present invention will have the schiff bases of structure shown in formula (II) and aluminum source compound anti-in a solvent
It answers, obtains the schiff bases aluminum complex with structure shown in formula (I)；Wherein, the schiff bases with structure shown in formula (II)
In R1And R2Range of choice and aforementioned formula (I) compound in R1And R2Range of choice it is identical, source of aluminium compound is excellent
It is selected as diethyl aluminum chloride or diethyl aluminum chloride solution, the more preferably toluene solution of diethyl aluminum chloride；The reaction
Solvent is preferably one or more of ether, chloroform, pentane, n-hexane and toluene, more preferably ether or n-hexane；Institute
The molar ratio for stating aluminium in schiff bases and source of aluminium compound with structure shown in formula (II) is 1:(1.5~3), more preferably
1:2；The dosage of the organic solvent of the reaction preferably makes the mass concentration 0.01g/mL of the schiff bases in organic solvent
~0.05g/mL, more preferably 0.030g/mL~0.036g/mL.The temperature of the reaction is room temperature, without being added
Heat or cooling；Reactive mode is preferably reacted under agitation, and it is special that the present invention does not have the method for the stirring
Limitation, using the technical solution of stirring well known to those skilled in the art；The time of the reaction is preferably 10 hours~
18 hours, more preferably 15 hours~18 hours；After completion of the reaction, the present invention preferably under nitrogen atmosphere, the reaction that will be obtained
Product is filtered, and obtained solid is dry, obtains the schiff bases aluminum complex with structure shown in formula (I).The present invention couple
The method of the suction filtration does not have special limitation, using the technical solution of suction filtration well known to those skilled in the art；This hair
The bright method to the drying is to carry out under nitrogen atmosphere；In the present invention, the drying is preferably dried in vacuo.
In the present invention, the schiff bases with structure shown in formula (II) is preferably prepared in accordance with the following methods:
To there is the tetraamine compound of structure shown in formula (III) to react with the substituted salicylic aldehydes with formula (IV) structure,
Obtain the schiff bases with structure shown in formula (II)；
In formula (IV), R1And R2Independently selected from aliphatic group.
According to the present invention, the present invention will have the tetraamine compound of structure shown in formula (III) and have formula (IV) structure
Substituted salicylic aldehydes reaction, obtain the schiff bases with structure shown in formula (II)；Wherein, the substitution bigcatkin willow of formula (IV) structure
In aldehyde, the R1And R2Range of choice and aforementioned formula (I) compound in R1And R2Range of choice it is identical, more specifically, institute
Stating the substituted salicylic aldehydes with formula (IV) structure is 3,5- dimethyl salicylide, 3,5- diethyl salicylide, 3,5- diisopropyl
Salicylide or 3,5- di-tert-butyl salicylaldehyde；The solvent of the reaction is preferably in alcohol compound, methylene chloride and toluene
One or more of one or more, more preferably methanol, ethyl alcohol, methylene chloride and toluene；It is described that there is formula (III) structure
Tetraamine compound and the molar ratios of the substituted salicylic aldehydes with structure shown in formula (IV) be preferably 1:(4~15), more
Preferably 1:(4~10), most preferably 1:(4~6)；The dosage of the solvent of reaction preferably makes tetraamine compound in organic solvent
In mass concentration be 0.01g/mL~0.1g/mL, more preferably 0.015g/mL~0.05g/mL；The temperature of the reaction is excellent
It is selected as room temperature~110 DEG C, more preferably 110 DEG C；The time of the reaction preferably for 24 hours~72h, more preferably 36h~60h,
Most preferably 42h~54h, the most preferably 48h.
In the present invention, in order to go on smoothly reaction, the present invention is additionally added catalyst, and the catalyst is preferably to toluene
Sulfonic acid；The mass ratio of the tetraamine compound and p-methyl benzenesulfonic acid is preferably (15~30): 1, more preferably (20~25): 1.
After completion of the reaction, the present invention preferably removes the organic solvent in obtained reaction product, and the reaction for removing organic solvent is produced
Object is dissolved with methylene chloride, and then obtained mixed solution is added in ethyl alcohol and is settled, after the drying of obtained solid
Obtain the schiff bases with structure shown in formula (II).The present invention does not have special limitation to the method for removing organic solvent,
Using the technical solution of place to go organic solvent well known to those skilled in the art, such as when using toluene for reaction dissolvent,
Obtained reaction product is spin-dried for by the present invention, removes organic solvent therein.The present invention does not have the dosage of the methylene chloride
Special limitation can dissolve obtained reaction product；The present invention is to the dosage of the ethyl alcohol also not special limit
System, can settle completely reaction product.The mixed solution is preferably added drop-wise in ethyl alcohol by the present invention, and stirring is sunk
Drop, then filters, is dried to obtain the schiff bases with structure shown in formula (II).The present invention is not special to the method for the stirring
Limitation, using the technical solution of stirring well known to those skilled in the art, in the present invention, the time of the stirring is excellent
It is selected as 20min~50min, more preferably 25min~40min, most preferably 30min~35min.The present invention to it is described filtering and
Dry method does not have special limitation, using filtering well known to those skilled in the art and dry technical solution,
In the present invention, the drying is preferably dried in vacuo.
The present invention also provides a kind of preparation methods of cyclic carbonate, comprising:
By epoxide, carbon dioxide, catalyst and co-catalyst hybrid reaction, cyclic carbonate is obtained；
The catalyst is with structure schiff bases aluminum complex shown in formula (I).
According to the present invention, the present invention obtains epoxide, carbon dioxide, catalyst and co-catalyst hybrid reaction
Cyclic carbonate；The epoxide is preferably the aryl of the epoxide of the alkyl substituent of C2~C10, C7~C15
Substituted epoxide or glycidol ether, the more preferably epoxide of the alkyl substituent of C3~C7, C10~C12
Aryl replace epoxide or glycidol ether, most preferably propylene oxide, ethylene oxide, epoxychloropropane, oxidation
One of styrene, ethylene glycol diglycidylether, butanediol diglycidyl ether and neopentylglycol diglycidyl ether or
It is several；The co-catalyst is preferably bis- (dihalotriphenylphosphoranes base) ammonium chlorides (PPNCl), 4-dimethylaminopyridine (DMAP), N-
Methylimidazole, tricyclohexyl phosphine, 11 carbon -7- alkene of 1,8- diazabicyclo [5.4.0], tri- azabicyclic of 1,5,7- [4.4.0]
One or more of decyl- 5- alkene, tetrabutylammonium chloride and tetrabutylammonium bromide, more preferably one of PPNCl and DMAP
Or two kinds, most preferably PPNCl.In the present invention, the molar ratio of the catalyst and the co-catalyst be preferably 1:(1~
2), more preferably 1:(1~1.5)；The total mole number of the catalyst and co-catalyst and the molar ratio of the epoxides are excellent
It is selected as 1:(300~2000): (1000~40000), more preferably 1:(300~1000): (1000~6000)；The titanium dioxide
The pressure of carbon is preferably 2MPa~5MPa, more preferably 2MPa~3MPa；The temperature of the catalysis reaction is preferably 50 DEG C~90
DEG C, more preferably 60 DEG C~90 DEG C, most preferably 70 DEG C~80 DEG C, the most preferably 80 DEG C；The time of the copolyreaction is excellent
It is selected as 0.5h~for 24 hours, more preferably 1h~21h, most preferably 3h~18h, the most preferably 6h~15h.
In the present invention, after the reaction was completed, the present invention is preferably cooling by reaction system, residual gas is released, by what is obtained
Reaction product is dissolved with methylene chloride, and then obtained solution is added in ethyl alcohol, stands after stirring, the precipitating that sedimentation is obtained
It is again dissolved in methylene chloride, obtained solution is settled in ethanol, then the precipitating drying that sedimentation is obtained, polymerize
Object.Reaction kettle is preferably placed in ice water by the present invention to cool down rapidly, then slowly releases participation gas to pressure and is down to atmosphere
Pressure, then open reaction kettle and take out reaction product.The present invention does not have special limitation, energy to the dosage of the methylene chloride and ethyl alcohol
Enough dissolutions and sedimentation realized to reaction product.In the present invention, the time of the stirring is preferably 10 minutes~25 points
Clock, more preferably 15 minutes~20 minutes；The time of the standing is preferably 20 minutes~40 minutes, more preferably 25 minutes~
35 minutes, most preferably 30 minutes；The precipitating dissolution that will be obtained, sedimentation number be preferably 2 times~5 times, more preferably 3
It is secondary~4 times.
The present invention also provides a kind of preparation methods of polycarbonate, comprising:
By epoxide, carbon dioxide, catalyst and co-catalyst hybrid reaction, polycarbonate is obtained；
The catalyst is of the present invention with structure schiff bases aluminum complex shown in formula (I).
The epoxide is the epoxide or glycidol ether of the alkyl substituent containing C5~C8.
According to the present invention, the present invention obtains epoxide, carbon dioxide, catalyst and co-catalyst hybrid reaction
Polycarbonate；The epoxide is preferably the cyclenes hydrocarbon oxide of C5~C8, the more preferably cycloolefin of C6~C7
Oxide, most preferably one or both of cyclohexene oxide and cyclopentene oxide；The co-catalyst is preferably double
(dihalotriphenylphosphoranes base) ammonium chloride (PPNCl), 4-dimethylaminopyridine (DMAP), N- methylimidazole, tricyclohexyl phosphine, 1,8- bis-
11 carbon -7- alkene of azabicyclo [5.4.0], tri- azabicyclic of 1,5,7- [4.4.0] decyl- 5- alkene, tetrabutylammonium chloride and four fourths
One or more of base ammonium bromide, more preferably one or both of PPNCl and DMAP, most preferably PPNCl.In this hair
In bright, the molar ratio of the catalyst and the co-catalyst is preferably 1:(1~2), more preferably 1:(1~1.5)；It is described to urge
The molar ratio of the total mole number of agent and co-catalyst and the epoxides is preferably 1:(300~2000): (1000~
40000), more preferably 1:(300~1000): (1000~6000)；The pressure of the carbon dioxide is preferably 2MPa~5MPa,
More preferably 2MPa~3MPa；The temperature of the catalysis reaction is preferably 50 DEG C~90 DEG C, more preferably 60 DEG C~90 DEG C, optimal
70 DEG C~80 DEG C are selected as, the most preferably 80 DEG C；The time of the copolyreaction is preferably 0.5h~for 24 hours, and more preferably 1h~
21h, most preferably 3h~18h, the most preferably 6h~15h.
In the present invention, after the reaction was completed, the present invention is preferably cooling by reaction system, residual gas is released, by what is obtained
Reaction product is dissolved with methylene chloride, and then obtained solution is added in ethyl alcohol, stands after stirring, the precipitating that sedimentation is obtained
It is again dissolved in methylene chloride, obtained solution is settled in ethanol, then the precipitating drying that sedimentation is obtained, polymerize
Object.Reaction kettle is preferably placed in ice water by the present invention to cool down rapidly, then slowly releases participation gas to pressure and is down to atmosphere
Pressure, then open reaction kettle and take out reaction product.The present invention does not have special limitation, energy to the dosage of the methylene chloride and ethyl alcohol
Enough dissolutions and sedimentation realized to reaction product.In the present invention, the time of the stirring is preferably 10 minutes~25 points
Clock, more preferably 15 minutes~20 minutes；The time of the standing is preferably 20 minutes~40 minutes, more preferably 25 minutes~
35 minutes, most preferably 30 minutes；The precipitating dissolution that will be obtained, sedimentation number be preferably 2 times~5 times, more preferably 3
It is secondary~4 times.
The present invention provides a kind of preparation methods of polyester, comprising:
By epoxide, cyclic acid anhydride, catalyst and co-catalyst hybrid reaction, polyester is obtained；
The catalyst is of the present invention with structure schiff bases aluminum complex shown in formula (I).
According to the present invention, the present invention obtains epoxide, cyclic acid anhydride, catalyst and co-catalyst hybrid reaction
Polyester；Wherein, the epoxides is preferably the aryl substitution of the epoxide of the alkyl substituent of C1~C15, C6~C20
Epoxide, glycidol ether or C3~C10 cyclenes hydrocarbon oxide, the more preferably alkyl substituent of C2~C10
Epoxide, C7~C15 the cycloolefin oxidation of epoxide, glycidol ether or C5~C8 that replaces of aryl
The epoxide of the aryl substitution of object, the most preferably epoxide of the alkyl substituent of C3~C7, C10~C12 shrinks
The cyclenes hydrocarbon oxide of glycerin ether or C6~C7, more specifically, the epoxide are propylene oxide, ethylene oxide, ring
Oxygen chloropropane, styrene oxide, ethylene glycol diglycidylether, butanediol diglycidyl ether, neopentyl glycol 2-glycidyl
One or more of ether, cyclohexene oxide and cyclopentene oxide.The acid anhydrides is energy well known to those skilled in the art
Enough and epoxide reaction prepares the common cyclic acid anhydride of polyester, such as five-membered cyclic acid anhydrides or six-membered cyclic acid anhydrides, specifically
, the acid anhydrides is preferably phthalic anhydride, maleic anhydride, dimethyl succinic acid acid anhydride, suitable succinic anhydride, carbic acid
One of acid anhydride, cyclobutane -1,2- dicarboxylic acid anhydride, cis- hexamethylene -1,2- dicarboxylic anhydride and 4- methyl hexahydrophthalic anhydride etc. are several
Kind, more preferably one or more of phthalic anhydride, maleic anhydride and carbic anhydride, most preferably adjacent benzene two
Formic anhydride and maleic anhydride.The co-catalyst is preferably bis- (dihalotriphenylphosphoranes base) ammonium chlorides (PPNCl), 4- dimethylamino pyrrole
Pyridine (DMAP), N- methylimidazole, tricyclohexyl phosphine, 11 carbon -7- alkene of 1,8- diazabicyclo [5.4.0], tri- azepine of 1,5,7-
One of two rings [4.4.0] decyl- 5- alkene, tetrabutylammonium chloride and tetrabutylammonium bromide are a variety of, more preferably PPNCl and
One or both of DMAP, most preferably PPNCl.In the present invention, the molar ratio of the catalyst and the co-catalyst
Preferably 1:(1~2), more preferably 1:(1~1.5)；The total mole number of the catalyst and co-catalyst and the cyclic annular acid
Acid anhydride, epoxides molar ratio be preferably 1:(300~2000): (1000~40000), more preferably 1:(300~1000):
(1000~6000).
In the present invention, the temperature of the reaction is preferably 50 DEG C~90 DEG C, more preferably 60 DEG C~90 DEG C, most preferably 70
DEG C~80 DEG C, the most preferably 80 DEG C；The time of the reaction is preferably 0.5h~for 24 hours, more preferably 1h~21h, most preferably
For 3h~18h, the most preferably 6h~15h.
After completion of the reaction, the present invention is preferably cooling by reaction system, releases residual gas, and obtained reaction product is used
Obtained solution, is then added in ethyl alcohol, stands after stirring by methylene chloride dissolution, and the precipitating that sedimentation obtains is again dissolved in two
In chloromethanes, obtained solution is settled, then the precipitating drying that sedimentation is obtained in ethanol, obtains polymer.The present invention is excellent
Reaction kettle is placed in ice water by choosing to cool down rapidly, then slowly releases participation gas to pressure and is down to atmospheric pressure, then opens anti-
Kettle is answered to take out reaction product.The present invention does not have special limitation to the dosage of the methylene chloride and ethyl alcohol, can be realized to anti-
Answer the dissolution and sedimentation of product.In the present invention, the time of the stirring is preferably 10 minutes~25 minutes, more preferably
15 minutes~20 minutes；The time of the standing is preferably 20 minutes~40 minutes, more preferably 25 minutes~35 minutes, optimal
It is selected as 30 minutes；The precipitating dissolution that will be obtained, the number settled are preferably 2 times~5 times, more preferably 3 times~4 times.
The present invention also provides a kind of preparation methods of polycarbonate-polyester copolymer, comprising:
By carbon dioxide, epoxide, acid anhydrides, catalyst and co-catalyst hybrid reaction, polycarbonate-polyester is obtained
Copolymer；
The catalyst is of the present invention with structure schiff bases aluminum complex shown in formula (I).
According to the present invention, the present invention by carbon dioxide, epoxide, acid anhydrides, catalyst and co-catalyst hybrid reaction,
Obtain polycarbonate-polyester copolymer；Wherein, the epoxides is preferably the epoxy compound of the alkyl substituent of C1~C15
Object, C6~C20 aryl replace epoxide, glycidol ether or C3~C10 cyclenes hydrocarbon oxide, more preferably
Epoxide, glycidol ether or the C5 that the epoxide of the alkyl substituent of C2~C10, the aryl of C7~C15 replace
The cyclenes hydrocarbon oxide of~C8, the most preferably epoxide of the alkyl substituent of C3~C7, the aryl of C10~C12 take
The cyclenes hydrocarbon oxide of the epoxide in generation, glycidol ether or C6~C7, more specifically, the epoxide are ring
Ethylene Oxide, ethylene oxide, epoxychloropropane, styrene oxide, ethylene glycol diglycidylether, butanediol diglycidyl ether,
One or more of neopentylglycol diglycidyl ether, cyclohexene oxide and cyclopentene oxide.The acid anhydrides is ability
The common cyclic acid anhydride that polyester can be prepared known to field technique personnel with epoxide reaction, such as five-membered cyclic acid anhydrides or
Six-membered cyclic acid anhydrides, specifically, the acid anhydrides is preferably phthalic anhydride, maleic anhydride, dimethyl succinic acid acid anhydride, suitable fourth two
Acid anhydrides, carbic anhydride, cyclobutane -1,2- dicarboxylic acid anhydride, cis- hexamethylene -1,2- dicarboxylic anhydride and 4- methyl hexahydrobenzene
One of one or more of acid anhydride etc., more preferably phthalic anhydride, maleic anhydride and carbic anhydride are several
Kind, most preferably phthalic anhydride and maleic anhydride.The co-catalyst is preferably bis- (dihalotriphenylphosphoranes base) ammonium chlorides
(PPNCl), 4-dimethylaminopyridine (DMAP), N- methylimidazole, tricyclohexyl phosphine, 1,8- diazabicyclo [5.4.0] 11
One of carbon -7- alkene, tri- azabicyclic of 1,5,7- [4.4.0] decyl- 5- alkene, tetrabutylammonium chloride and tetrabutylammonium bromide are more
Kind, more preferably one or both of PPNCl and DMAP, most preferably PPNCl.The pressure of the carbon dioxide is preferably
2MPa~5MPa, more preferably 2MPa~3MPa.In the present invention, the molar ratio of the catalyst and the co-catalyst is preferred
For 1:(1~2), more preferably 1:(1~1.5)；The total mole number of the catalyst and co-catalyst and the cyclic acid anhydride, ring
The molar ratio of oxide is preferably 1:(300~2000): (1000~40000), more preferably 1:(300~1000): (1000~
6000)。
In the present invention, the temperature of the reaction is preferably 50 DEG C~90 DEG C, more preferably 60 DEG C~90 DEG C, most preferably 70
DEG C~80 DEG C, the most preferably 80 DEG C；The time of the reaction is preferably 0.5h~for 24 hours, more preferably 1h~21h, most preferably
For 3h~18h, the most preferably 6h~15h.
After completion of the reaction, the present invention is preferably cooling by reaction system, releases residual gas, and obtained reaction product is used
Obtained solution, is then added in ethyl alcohol, stands after stirring by methylene chloride dissolution, and the precipitating that sedimentation obtains is again dissolved in two
In chloromethanes, obtained solution is settled, then the precipitating drying that sedimentation is obtained in ethanol, obtains polymer.The present invention is excellent
Reaction kettle is placed in ice water by choosing to cool down rapidly, then slowly releases participation gas to pressure and is down to atmospheric pressure, then opens anti-
Kettle is answered to take out reaction product.The present invention does not have special limitation to the dosage of the methylene chloride and ethyl alcohol, can be realized to anti-
Answer the dissolution and sedimentation of product.In the present invention, the time of the stirring is preferably 10 minutes~25 minutes, more preferably
15 minutes~20 minutes；The time of the standing is preferably 20 minutes~40 minutes, more preferably 25 minutes~35 minutes, optimal
It is selected as 30 minutes；The precipitating dissolution that will be obtained, the number settled are preferably 2 times~5 times, more preferably 3 times~4 times.
The present invention provides a kind of schiff bases aluminum complex and its preparation method and application, schiff bases aluminium provided by the invention
Complex has formula (I) structure, and it is high that the present invention provides complex-catalyzed activity, and being capable of catalytic preparation of cyclic carbonic ester, poly-
The reaction of ester, polycarbonate and polycarbonate-polyester, catalyst have a wide range of application, and catalytic activity is high, the use of catalyst
Amount can be down to the 0.3 ‰ of monomer dosage, and raw material high conversion rate in reacting, and the time of reaction is short, the performance of obtained polymer
It is good, there is good prospects for commercial application, the experimental results showed that, catalyst provided by the invention is equal in wider temperature range
With preferable catalytic performance.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
15g 3,5- di-tert-butyl salicylaldehyde, 2.14g biphenyl tetramine and 0.1g p-methyl benzenesulfonic acid are added to 150mL toluene
In, azeotropic water removing reacts, and after 48h, Tan solid or dope are obtained after toluene vacuum is drained；
Obtained Tan solid or dope 50mL methylene chloride are dissolved, are added drop-wise in 1000mL ethyl alcohol, is stirred
Yellow solid is obtained by filtration after 30min, is dried in vacuo, obtains the schiff bases with formula (II) structure.
The yield that the schiff bases with formula (II) structure is calculated in the present invention is 80%.
The present invention analyzes the schiff bases obtained in the present embodiment with formula (II) structure using nuclear magnetic resonance, obtains
It is composed to its hydrogen, the results showed that1H NMR (300MHz, CDCl3): δ=13.60 (s, OH 4H), 8.79 (d, NCH 4H), 7.64
(d, ArH, 2H), 7.51 (d, ArH, 6H), 7.42 (d, ArH, 2H), 7.30 (d, ArH, 4H), 1.50 (d, CCH3, 36H), 1.37
(d, CCH3, 36H)；
The present invention analyzes the schiff bases with formula (II) structure that the present embodiment obtains using mass spectrograph, as a result table
It is bright: MALDI-TOF (CHCl3), m/z=1079.8；
The schiff bases (II) that the present invention obtains the present embodiment using elemental analysis is analyzed, and is obtained its each atom and is contained
Amount: Elem.Anal. (%): Calcd.C 80.11；H 8.78；N 5.19.Found:C78.63；H 9.17；N 6.68；
The Schiff manufactured in the present embodiment it can be seen from the above nuclear magnetic resonance spectroscopy, mass spectral analysis and elemental analysis result
Alkali has structure shown in formula (II), wherein R1And R2It is tert-butyl.
Embodiment 2
The present invention prepares schiff bases using the technical solution of embodiment 1, unlike, the present embodiment uses 3,5- dimethyl
Salicylide replaces the 3,5- di-tert-butyl salicylaldehyde in embodiment 1.
Obtained reaction product is carried out hydrogen nuclear magnetic resonance spectrum analysis, mass spectral analysis and elemental analysis by the present invention, as a result table
Bright, schiff bases manufactured in the present embodiment has structure shown in formula (II), wherein R1And R2It is methyl.
Embodiment 3
The present invention prepares schiff bases using the technical solution of embodiment 1, unlike, the present embodiment uses 3,5- diethyl
Salicylide replaces the 3,5- di-tert-butyl salicylaldehyde in embodiment 1.
Obtained reaction product is carried out hydrogen nuclear magnetic resonance spectrum analysis, mass spectral analysis and elemental analysis by the present invention, as a result table
Bright, schiff bases manufactured in the present embodiment has structure shown in formula (II), wherein R1And R2It is ethyl.
Embodiment 4
The present invention prepares schiff bases using the technical solution of embodiment 1, unlike, the present embodiment uses 3,5- diisopropyl
Base salicylide replaces the 3,5- di-tert-butyl salicylaldehyde in embodiment 1.
Obtained reaction product is carried out hydrogen nuclear magnetic resonance spectrum analysis, mass spectral analysis and elemental analysis by the present invention, as a result table
Bright, schiff bases manufactured in the present embodiment has structure shown in formula (II), wherein R1And R2It is isopropyl.
Embodiment 5
Under nitrogen atmosphere, schiff bases prepared by 0.5g embodiment 1 is dissolved into 15ml n-hexane, is slowly added dropwise
The toluene solution (0.9mol/L) of 1.03ml diethyl aluminum chloride, after being stirred to react 18h under nitrogen atmosphere, obtained product exists
It is filtered under nitrogen atmosphere, obtained product is dried under vacuum, yellow solid is obtained, which is schiff bases aluminum complex.
The yield 83% of schiff bases complex is calculated in the present invention.
The present invention analyzes schiff bases obtained in the present embodiment using nuclear magnetic resonance, obtains its hydrogen spectrum, as a result table
It is bright:1H NMR (300MHz, CDCl3): δ=9.12 (d, NCH 4H), 7.93,7.90,7.87,7.70,7.67,7.54,7.35
(m, ArH, 14H), 1.62 (s, CCH3, 36H), 1.34 (d, CCH3, 36H).
The present invention closes object to the schiff bases aluminium that the present embodiment obtains using mass spectrograph and analyzes, the results showed that ESI-MS
(CHCl3), m/z=1146.7 (- 2Cl+H2O)。
The result shows that, the schiff bases complex that the present embodiment is prepared has structure shown in formula (I) by analyzing above,
Middle R1And R2It is tert-butyl.
Embodiment 6
Schiff bases complex is prepared using the technical solution of embodiment 5, unlike, the present embodiment is obtained using embodiment 2
To the schiff bases schiff bases that is prepared of embodiment 1 that replaces embodiment 5 to use.
Obtained reaction product is carried out nuclear magnetic resonance spectroscopy, mass spectral analysis by the present invention, the results showed that, the present embodiment obtains
Schiff bases complex there is structure shown in formula (I), wherein R1And R2It is methyl.
Embodiment 7
Schiff bases complex is prepared using the technical solution of embodiment 5, unlike, the present embodiment is obtained using embodiment 3
To the schiff bases schiff bases that is prepared of embodiment 1 that replaces embodiment 5 to use.
Obtained reaction product is carried out nuclear magnetic resonance spectroscopy, mass spectral analysis by the present invention, the results showed that, the present embodiment obtains
Schiff bases complex there is structure shown in formula (I), wherein R1And R2It is ethyl.
Embodiment 8
Schiff bases complex is prepared using the technical solution of embodiment 5, unlike, the present embodiment is obtained using embodiment 4
To the schiff bases schiff bases that is prepared of embodiment 1 that replaces embodiment 5 to use.
Obtained reaction product is carried out nuclear magnetic resonance spectroscopy, mass spectral analysis by the present invention, the results showed that, the present embodiment obtains
Schiff bases complex there is structure shown in formula (I), wherein R1And R2It is isopropyl.
Embodiment 9
Schiff bases aluminium compound and 0.0052gPPNCl that 1.50g propylene oxide, 0.0150g embodiment 5 obtain are helped and urged
Agent is mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto, is pressurizeed
To 2MPa, controls temperature and be stirred at 60 DEG C, react 2h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, it is complete in the product that the present embodiment obtains
Portion is cyclic carbonate, conversion ratio 55%.
Embodiment 10
The schiff bases aluminium compound and 0.0119gPPNCl co-catalyst that 2g propylene oxide, 0.0110g embodiment 5 are obtained
It is mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto, is forced into
2MPa, control temperature stir at 80 DEG C, react 2h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 92%.
Embodiment 11
The schiff bases aluminium compound and 0.0206gPPNCl co-catalyst that 2g propylene oxide, 0.0220g embodiment 5 are obtained
It is mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto, is forced into
2MPa, control temperature stir at 50 DEG C, react 6h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 40%.
Embodiment 12
The schiff bases aluminium compound and 0.0103gPPNCl co-catalysis that 1.8g propylene oxide, 0.0186g embodiment 6 are obtained
Agent is mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto, is forced into
4MPa, control temperature stir at 60 DEG C, react 2h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 23%.
Embodiment 13
The schiff bases aluminium compound and 0.0110g tetrabutyl phosphonium bromide that 2.0g propylene oxide, 0.0198g embodiment 6 are obtained
Ammonium co-catalyst is mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto
Body is forced into 2MPa, and control temperature stirs at 60 DEG C, reacts 2.5h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 34%.
Embodiment 14
The schiff bases aluminium compound that 1.7g propylene oxide, 0.0164g embodiment 5 are obtained and 0.0122g tetrabutyl chlorination
Ammonium co-catalyst is mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto
Body is forced into 3MPa, and control temperature stirs at 60 DEG C, reacts 6h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 91%.
Embodiment 15
The schiff bases aluminium compound that 1.7g propylene oxide, 0.0186g embodiment 5 are obtained and 0.0148g tetrabutyl chlorination
Ammonium co-catalyst is mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto
Body is forced into 3MPa, and control temperature stirs at 80 DEG C, reacts 4h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 86%.
Embodiment 16
Tri- nitrogen of schiff bases aluminium compound and 0.0061g1,5,7- that 1.6g propylene oxide, 0.0150g embodiment 7 are obtained
Miscellaneous two ring [4.4.0] decyl- 5- alkene co-catalyst is mixed to join in the autoclave by high temperature water removal deoxygenation, is led to thereto
Enter high-purity carbon dioxide gas, be forced into 4MPa, control temperature stirs at 80 DEG C, reacts 5h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 45%.
Embodiment 17
The schiff bases aluminium compound and 0.0054g4- dimethyl pyrazole that 1.3g propylene oxide, 0.0117g embodiment 8 are obtained
Pyridine co-catalyst is mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto
Body is forced into 4MPa, and control temperature stirs at 75 DEG C, reacts 6h；
Reaction kettle is placed in ice water after reaction and is cooled down rapidly, then slow release residual gas to pressure drops to greatly
Air pressure.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 42%.
Embodiment 18
The schiff bases aluminium compound and 0.0108g tetrabutyl bromine that 1.8g styrene oxide, 0.0150g embodiment 5 are obtained
Change ammonium co-catalyst to be mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto
Body is forced into 4MPa, and control temperature stirs at 70 DEG C, reacts 3h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 68%.
Embodiment 19
Schiff bases aluminium compound and 0.0119gPPNCl that 2.3g 7-oxa-bicyclo[4.1.0,0.0269g embodiment 5 obtain are helped and urged
Agent is mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto, is pressurizeed
To 2MPa, controls temperature and stirred at 80 DEG C, react 6h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Obtained reaction product 15mL methylene chloride is dissolved, obtained solution is slowly added dropwise into 200mL ethyl alcohol by atmospheric pressure,
Static 30min after stirring 15min；Polymer after precipitating is dissolved with methylene chloride again, is settled in ethanol, is repeated 3 times,
The reaction product vacuum drying that sedimentation is obtained, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, in the product that the present embodiment obtains
All polycarbonate, conversion ratio 51%；
The present invention analyzes the polycarbonate that the present embodiment obtains using gel permeation chromatography, obtains polycarbonate
Number-average molecular weight is 1.5 ten thousand.
Embodiment 20
The schiff bases aluminium compound and 0.0238g PPNCl that 2g 7-oxa-bicyclo[4.1.0,0.0269g embodiment 5 are prepared
Co-catalyst is mixed to join in the autoclave by high temperature water removal deoxygenation, is passed through high-purity carbon dioxide gas thereto,
It is forced into 2MPa, control temperature is stirred at 80 DEG C, reacts 6h；
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Obtained reaction product 15mL methylene chloride is dissolved, obtained solution is slowly added dropwise into 200mL ethyl alcohol by atmospheric pressure,
Static 30min after stirring 15min；Polymer after precipitating is dissolved with methylene chloride again, is settled in ethanol, is repeated 3 times,
The solid vacuum drying that sedimentation is obtained, obtains reaction product.
The present invention carries out obtained polymer1H-NMR analysis, the results showed that, in the reaction product that the present embodiment obtains
All polycarbonate, conversion ratio about 68%；
The present invention analyzes the polycarbonate that the present embodiment obtains using gel permeation chromatography, obtains polycarbonate
Number-average molecular weight is 1.2 ten thousand.
Embodiment 21
Schiff bases aluminium compound prepared by 1.8g 7-oxa-bicyclo[4.1.0,0.84g phthalic anhydride, 0.0214g example 5 and
0.0114g PPNCl co-catalyst is mixed to join in the reaction kettle through high temperature water removal deoxygenation, is controlled temperature at 80 DEG C, is reacted
2h。
After reaction, reaction kettle is placed in ice water and is cooled down rapidly.Product 15ml methylene chloride dissolves, by what is obtained
Solution is slowly added dropwise into 200ml ethyl alcohol, stirs static 30min after 15min；Polymer after precipitating is used into methylene chloride again
Dissolution, settles in ethanol, is repeated 3 times.The solid vacuum drying that sedimentation is obtained, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, it is produced in the reaction that the present embodiment obtains
The all polyester of object, the reaction conversion ratio of phthalic anhydride reaches 97% in the present embodiment.
The polyester that the present embodiment obtains is analyzed using gel permeation chromatography, the number-average molecular weight for obtaining polyester is
2.1 ten thousand.
Embodiment 22
Schiff bases aluminium compound prepared by 2.5g propylene oxide, 0.84g phthalic anhydride, 0.0214g example 5 and
0.0114g PPNCl co-catalyst is mixed to join in the autoclave through high temperature water removal deoxygenation, controls temperature at 80 DEG C, instead
Answer 1.5h.
After reaction, reaction kettle is placed in ice water and is cooled down rapidly.Product 15ml methylene chloride dissolves, by what is obtained
Solution is slowly added dropwise into 200ml ethyl alcohol, stirs static 30min after 15min；Polymer after precipitating is used into methylene chloride again
Dissolution, settles in ethanol, is repeated 3 times.The solid vacuum drying that sedimentation is obtained, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, it is produced in the reaction that the present embodiment obtains
The all polyester of object, the reaction conversion ratio of phthalic anhydride reaches 100% in the present embodiment.
The present invention divides the polyester that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polyester is 1.5 ten thousand.
Embodiment 23
Schiff bases aluminium compound prepared by 1.9g 7-oxa-bicyclo[4.1.0,0.62g phthalic anhydride, 0.0197g example 5 and
0.0108g PPNCl co-catalyst is mixed to join in the autoclave through high temperature water removal deoxygenation, controls temperature at 60 DEG C, instead
Answer 4h.
After reaction, reaction kettle is placed in ice water and is cooled down rapidly.Product 5ml methylene chloride dissolves, by what is obtained
Solution is slowly added dropwise into 200ml ethyl alcohol, stirs static 30min after 15min；Polymer after precipitating is used into methylene chloride again
Dissolution, settles in ethanol, is repeated 3 times.The solid vacuum drying that sedimentation is obtained, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, it is produced in the reaction that the present embodiment obtains
The all polyester of object, the reaction conversion ratio of phthalic anhydride reaches 64% in the present embodiment.
The present invention divides the polyester that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polyester is 0.9 ten thousand.
Embodiment 24
Schiff bases aluminium compound prepared by 2.0g 7-oxa-bicyclo[4.1.0,0.56g phthalic anhydride, 0.0198g example 5 and
0.0074g PPNCl co-catalyst is mixed to join in the autoclave through high temperature water removal deoxygenation, is passed through carbon dioxide 2MPa,
Temperature is controlled at 80 DEG C, reacts 5h.
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure, a small amount of sample are used for1H-NMR analysis.Product with 15ml methylene chloride dissolve, by obtained solution be slowly added dropwise to
In 200ml ethyl alcohol, static 30min after 15min is stirred；Polymer after precipitating is dissolved with methylene chloride again, in ethanol
Sedimentation, is repeated 3 times.The solid vacuum drying that sedimentation is obtained, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the present embodiment obtains the poly- carbonic acid of polyester-
The terpolymer of ester, wherein the reaction conversion ratio of phthalic anhydride reaches 100%, and the conversion ratio of 7-oxa-bicyclo[4.1.0 is
74%.
The polyester-polycarbonate that the present embodiment obtains is analyzed using gel permeation chromatography, obtains the number of polymer
Average molecular weight is 2.4 ten thousand.
Embodiment 25
Schiff bases aluminium compound prepared by 1.7g propylene oxide, 0.74g phthalic anhydride, 0.0184g example 5 and
0.0162g PPNCl co-catalyst is mixed to join in the autoclave through high temperature water removal deoxygenation, is passed through carbon dioxide 3MPa,
Temperature is controlled at 70 DEG C, reacts 5h.
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.Product 15ml methylene chloride dissolves, and obtained solution is slowly added dropwise into 200ml ethyl alcohol, quiet after stirring 15min
Only 30min；Polymer after precipitating is dissolved with methylene chloride again, is settled in ethanol, is repeated 3 times.Sedimentation is obtained
Solid vacuum drying, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the present embodiment obtains propylene oxide-neighbour
Phthalate anhydride polyester and propene carbonate, wherein the reaction conversion ratio of phthalic anhydride reaches 100%, and propylene oxide turns
Changing rate is 84%.
The polyester that the present embodiment obtains is analyzed using gel permeation chromatography, the number-average molecular weight for obtaining polymer is
1.2 ten thousand.
Embodiment 26
Schiff bases aluminium compound prepared by 1.5g propylene oxide, 0.45g maleic anhydride, 0.0124g example 5 and
0.0098g PPNCl co-catalyst is mixed to join in the autoclave through high temperature water removal deoxygenation, controls temperature at 60 DEG C, instead
Answer 5h.
After reaction, reaction kettle is placed in ice water and is cooled down rapidly.Product 15ml methylene chloride dissolves, by what is obtained
Solution is slowly added dropwise into 200ml ethyl alcohol, stirs static 30min after 15min；Polymer after precipitating is used into methylene chloride again
Dissolution, settles in ethanol, is repeated 3 times.The solid vacuum drying that sedimentation is obtained, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the present embodiment obtains propylene oxide-horse
Carry out acid anhydrides polyester, wherein the reaction conversion ratio of maleic anhydride reaches 100%.
The polyester that the present embodiment obtains is analyzed using gel permeation chromatography, the number-average molecular weight for obtaining polymer is
1.1 ten thousand.
Embodiment 27
Schiff bases aluminium compound prepared by 1.8g styrene oxide, 0.48g maleic anhydride, 0.0154g example 6 and
0.0112g PPNCl co-catalyst is mixed to join in the autoclave through high temperature water removal deoxygenation, controls temperature at 50 DEG C, instead
Answer 7h.
After reaction, reaction kettle is placed in ice water and is cooled down rapidly.Product 15ml methylene chloride dissolves, by what is obtained
Solution is slowly added dropwise into 200ml ethyl alcohol, stirs static 30min after 15min；Polymer after precipitating is used into methylene chloride again
Dissolution, settles in ethanol, is repeated 3 times.The solid vacuum drying that sedimentation is obtained, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the present embodiment obtains styrene oxide-
Maleic anhydride polyester, wherein the reaction conversion ratio of maleic anhydride reaches 87%.
The polyester that the present embodiment obtains is analyzed using gel permeation chromatography, the number-average molecular weight for obtaining polymer is
0.8 ten thousand.
Embodiment 28
Schiff bases aluminium compound prepared by 1.8g 7-oxa-bicyclo[4.1.0,0.84g carbic anhydride, 0.0244g example 8
With 0.0164g PPNCl co-catalyst be mixed to join through high temperature water removal deoxygenation autoclave in, control temperature at 80 DEG C,
React 2h.
After reaction, reaction kettle is placed in ice water and is cooled down rapidly.Product 15ml methylene chloride dissolves, by what is obtained
Solution is slowly added dropwise into 200ml ethyl alcohol, stirs static 30min after 15min；Polymer after precipitating is used into methylene chloride again
Dissolution, settles in ethanol, is repeated 3 times.The solid vacuum drying that sedimentation is obtained, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the present embodiment obtains 7-oxa-bicyclo[4.1.0-
Carbic anhydride polyester, wherein the reaction conversion ratio of carbic anhydride reaches 94%.
The polyester that the present embodiment obtains is analyzed using gel permeation chromatography, the number-average molecular weight for obtaining polymer is
1.4 ten thousand.
Embodiment 29
Schiff bases aluminium compound prepared by 2.1g 7-oxa-bicyclo[4.1.0,0.41g maleic anhydride, 0.0195g example 5 and
0.0156g PPNCl co-catalyst is mixed to join in the autoclave through high temperature water removal deoxygenation, is passed through high-purity two thereto
Carbon oxide gas is forced into 2MPa, controls temperature at 75 DEG C, reacts 5h.
After reaction, reaction kettle is placed in ice water and is cooled down rapidly, then slow release residual gas to pressure drops to
Atmospheric pressure.Product 15ml methylene chloride dissolves, and obtained solution is slowly added dropwise into 200ml ethyl alcohol, quiet after stirring 15min
Only 30min；Polymer after precipitating is dissolved with methylene chloride again, is settled in ethanol, is repeated 3 times.Sedimentation is obtained
Solid vacuum drying, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, the present embodiment obtains the poly- carbonic acid of polyester-
The terpolymer of ester, wherein the reaction conversion ratio of maleic anhydride reaches 100%, and the reaction conversion ratio of 7-oxa-bicyclo[4.1.0 is
62%.
The polyester-polycarbonate that the present embodiment obtains is analyzed using gel permeation chromatography, obtains the number of polymer
Average molecular weight is 1.8 ten thousand.
Embodiment 30
Schiff bases aluminium compound prepared by 2.6g 7-oxa-bicyclo[4.1.0,1.2g phthalic anhydride, 0.01g embodiment 5 and
0.0048g PPNCl co-catalyst is mixed to join in the autoclave through high temperature water removal deoxygenation, controls temperature at 80 DEG C, instead
Answer 5h.
After reaction, reaction kettle is placed in ice water and is cooled down rapidly.Product 15ml methylene chloride dissolves, by what is obtained
Solution is slowly added dropwise into 200ml ethyl alcohol, stirs static 30min after 15min；Polymer after precipitating is used into methylene chloride again
Dissolution, settles in ethanol, is repeated 3 times.The solid vacuum drying that sedimentation is obtained, obtains reaction product.
The present invention carries out obtained reaction product1H-NMR analysis, the results showed that, what the present embodiment obtained is entirely poly-
Ester.The polyester that the present embodiment obtains is analyzed using gel permeation chromatography, the number-average molecular weight for obtaining polymer is 2.4
Ten thousand.It is 142.9 DEG C using the glass transition temperature that differential scanning calorimeter measures polymer.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (9)
1. a kind of schiff bases aluminum complex has structure shown in formula (I):
Wherein, the R1Selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl,
N-hexyl or n-heptyl；
The R2Selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, just oneself
Base or n-heptyl.
2. a kind of preparation method of schiff bases aluminium compound, comprising the following steps:
To there is the schiff bases of structure shown in formula (II) to react in a solvent with aluminum source compound, obtain with knot shown in formula (I)
The schiff bases aluminum complex of structure；
In formula (II), the R1Selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, different
Amyl, n-hexyl or n-heptyl；
The R2Selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, just oneself
Base or n-heptyl.
3. preparation method according to claim 2, which is characterized in that the schiff bases with structure shown in formula (II)
Preparation method the following steps are included:
To there is the tetraamine compound of structure shown in formula (III) to react with the substituted salicylic aldehydes with formula (IV) structure, obtain
Schiff bases with structure shown in formula (II)；
In formula (IV), the R1Selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, different
Amyl, n-hexyl or n-heptyl；
The R2Selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, just oneself
Base or n-heptyl.
4. a kind of preparation method of cyclic carbonate, comprising:
By epoxide, carbon dioxide, catalyst and co-catalyst hybrid reaction, cyclic carbonate is obtained；
The catalyst is described in claim 1 with structure schiff bases aluminum complex or claim 2~3 shown in formula (I)
The preparation of preparation method described in any one has structure schiff bases aluminum complex shown in formula (I)；
The epoxide is the epoxidation of the aryl substitution of the epoxide of the alkyl substituent of C1~C15, C6~C20
Close object or glycidol ether.
5. the preparation method according to claim 4, which is characterized in that the epoxide is propylene oxide, epoxy second
Alkane, epoxychloropropane, 1,2- epoxypentane, styrene oxide, ethylene glycol diglycidylether, butanediol diglycidyl ether and
One or more of neopentylglycol diglycidyl ether.
6. a kind of preparation method of polycarbonate, comprising:
By epoxide, carbon dioxide, catalyst and co-catalyst hybrid reaction, polycarbonate is obtained；
The catalyst is described in claim 1 with structure schiff bases aluminum complex or claim 2~3 shown in formula (I)
The preparation of preparation method described in any one has structure schiff bases aluminum complex shown in formula (I)；
The epoxide is the cyclenes hydrocarbon oxide of C5~C8.
7. a kind of preparation method of polyester, comprising:
By epoxide, cyclic acid anhydride, catalyst and co-catalyst hybrid reaction, polyester is obtained；
The catalyst is described in claim 1 with structure schiff bases aluminum complex or claim 2~3 shown in formula (I)
The preparation of preparation method described in any one has structure schiff bases aluminum complex shown in formula (I).
8. a kind of preparation method of polycarbonate-polyester copolymer, comprising:
By carbon dioxide, epoxide, cyclic acid anhydride, catalyst and co-catalyst hybrid reaction, polycarbonate-polyester is obtained
Copolymer；
The catalyst is described in claim 1 with structure schiff bases aluminum complex or claim 2~3 shown in formula (I)
The preparation of preparation method described in any one has structure schiff bases aluminum complex shown in formula (I).
9. preparation method according to claim 8, which is characterized in that the co-catalyst is bis- (dihalotriphenylphosphoranes base) chlorine
Change ammonium, 4-dimethylaminopyridine, 11 carbon -7- alkene of 1,8- diazabicyclo [5.4.0], tri- azabicyclic of 1,5,7- [4.4.0]
One of decyl- 5- alkene, N- methylimidazole, tricyclohexyl phosphine, tetrabutylammonium chloride and tetrabutylammonium bromide are a variety of.
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| CN106700055A (en) * | 2016-11-11 | 2017-05-24 | 佛山科学技术学院 | Functional group containing polycarbonate-polyester material and preparation method thereof |
| CN107955030B (en) * | 2017-12-12 | 2020-09-08 | 新泰中学 | Chiral aluminum complex containing acetylacetone derivative, and preparation method and application thereof |
| 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 |
| 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 |
| CN110483755A (en) * | 2019-08-16 | 2019-11-22 | 大连理工大学 | A method of preparing polyethylene glycol succinate |
| CN114524929B (en) * | 2021-09-24 | 2023-07-25 | 山东联欣环保科技有限公司 | Preparation method of carbon dioxide-based tetrapolymer |
| CN114763430A (en) * | 2021-12-08 | 2022-07-19 | 山东联欣环保科技有限公司 | Composite degradable polymer with strong ductility and preparation method thereof |
| CN114853819A (en) * | 2022-04-12 | 2022-08-05 | 福州大学 | Trimetal Schiff base complex, preparation method thereof and application thereof in catalyzing ring-opening copolymerization of epoxy compound |
| CN115286781A (en) * | 2022-08-01 | 2022-11-04 | 中国科学院长春应用化学研究所 | Electron-withdrawing group polycarbonate ether polyol and efficient preparation method thereof |
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