CN106083907A - A kind of Schiff's base aluminum complex and its preparation method and application - Google Patents
A kind of Schiff's base aluminum complex and its preparation method and application Download PDFInfo
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- CN106083907A CN106083907A CN201610473151.8A CN201610473151A CN106083907A CN 106083907 A CN106083907 A CN 106083907A CN 201610473151 A CN201610473151 A CN 201610473151A CN 106083907 A CN106083907 A CN 106083907A
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- C—CHEMISTRY; METALLURGY
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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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- C—CHEMISTRY; METALLURGY
- 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
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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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
Abstract
The invention provides a kind of Schiff's base aluminum complex and its preparation method and application, the Schiff's base aluminum complex that the present invention provides has formula (I) structure, the present invention provides complex-catalyzed activity high, and can catalytic preparation of cyclic carbonic ester, polyester, Merlon and the reaction of polycarbonate polyester, catalyst applied range, and it is high to be catalyzed activity, has good prospects for commercial application.
Description
Technical field
The present invention relates to catalyst technical field, particularly relate to a kind of Schiff's base aluminum complex and preparation method thereof and answer
With.
Background technology
Schiff's base is the organic compound that a class contains C=N group, and Schiff's base is because of various easily and in structure of its preparation
Property, make one of of paramount importance spatial chemistry model in metal coordination chemistry.Since century more than one, existing have in a large number
Close the report of schiff base metal complex, but, from current report it can be seen that different schiff base metal complexes is to instead
The catalytic effect answered also differs greatly.
Along with the continuous progress of society, industrialized process is accelerated, more and more higher to the demand of macromolecular material, and passes
The material of system, such as polyethylene, polypropylene, polystyrene etc., owing to depending on petroleum resources unduly, and is not easily decomposed and makes
Become the factors such as white pollution, gradually by social cleaning.Therefore, synthesis has the material of degradable character becomes the heat nowadays studied
Point direction.Merlon and polyester polymer have degradable feature, can be respectively by epoxide and carbon dioxide or ring
Oxide is polymerized with cyclic acid anhydride and obtains.Wherein epoxide and cyclic acid anhydride are low-cost chemical products, and titanium dioxide
Carbon can reduce its greenhouse effect as carbon source and epoxide copolymerization;Meanwhile, the synthesis of this kind of degradation material has reaction
The advantages such as the polymer of condition preparation high molecular gentleer, easy and the polymer of different modifying group.Can be used for preparation can
Degradation biological material, and the material of difference in functionality is prepared by modification.
Additionally, epoxide can carry out cycloaddition reaction with carbon dioxide under the effect of catalyst, generate five-membered ring
Shape carbonic ester, this product has preferable stability, can be widely applied to weaving, printing and dyeing, Polymer Synthesizing and electrochemistry
In field.
Therefore, research with carbon dioxide or epoxide as reaction raw materials be synthesized cyclic carbonate, polyester,
Merlon and polycarbonate-polyester copolymer are the focuses of research at present.
Summary of the invention
In view of this, the technical problem to be solved there are provided a kind of Schiff's base aluminum complex and preparation thereof
Methods and applications, the present invention provide Schiff's base aluminum complex can catalytically synthesizing cyclic carbonate ester, polyester, Merlon and
Polycarbonate-polyester polymer, and catalytic efficiency is high.
The invention provides a kind of Schiff's base aluminum complex, there is structure shown in formula (I):
Wherein, R1And R2Independently selected from aliphatic group.
Preferably, described R1And R2Independently selected from the aliphatic group that carbon number is 1~30.
Present invention also offers the preparation method of a kind of Schiff's base aluminium compound, comprise the following steps:
React having the Schiff's base of structure shown in formula (II) in a solvent with aluminum source compound, obtain that there is formula (I) institute
Show the Schiff's base aluminum complex of structure;
In formula (II), R1And R2Independently selected from aliphatic group.
Preferably, there is described in the preparation method of the Schiff's base of structure shown in formula (II) comprise the following steps:
React having the tetraamine compound of structure shown in formula (III) with the substituted salicylic aldehydes with formula (IV) structure,
Obtain having the Schiff's base of structure shown in formula (II);
In formula (IV), R1And R2Independently selected from aliphatic group.
Present invention also offers the preparation method of a kind of cyclic carbonate, including:
By epoxide, carbon dioxide, catalyst and promoter hybrid reaction, obtain cyclic carbonate;
Described catalyst is of the present invention to have structure Schiff's base aluminum complex shown in formula (I);
Described epoxide is the substituted ring of aryl of the epoxide of the alkyl substituent of C1~C15, C6~C20
Oxygen compound or glycidyl ether.
Preferably, described epoxide be expoxy propane, oxirane, epoxychloropropane, 1,2-epoxypentane, second two
One or more in alcohol diglycidyl ether, butanediol diglycidyl ether and neopentylglycol diglycidyl ether
Present invention also offers the preparation method of a kind of Merlon, including:
By epoxide, carbon dioxide, catalyst and promoter hybrid reaction, obtain Merlon;
Described catalyst is of the present invention to have structure Schiff's base aluminum complex shown in formula (I);
Described epoxide be C5~C8 cycloolefin oxide.
Present invention also offers the preparation method of a kind of polyester, including:
By epoxide, cyclic acid anhydride, catalyst and promoter hybrid reaction, obtain polyester;
Described catalyst is of the present invention to have structure Schiff's base aluminum complex shown in formula (I).
Present invention also offers the preparation method of a kind of polycarbonate-polyester copolymer, including:
By carbon dioxide, epoxide, cyclic acid anhydride, catalyst and promoter hybrid reaction, obtain Merlon-
Polyester copolymer;
Described catalyst is of the present invention to have structure Schiff's base aluminum complex shown in formula (I).
Preferably, described promoter be double (dihalotriphenylphosphoranes base) ammonium chloride, DMAP, 1,8-diaza
Dicyclo [5.4.0] 11 carbon-7-alkene, 1,5,7-tri-azabicyclic [4.4.0] decyl-5-alkene, N-Methylimidazole., tricyclohexyl phosphine,
One or more in tetrabutylammonium chloride and tetrabutyl ammonium bromide etc..
Compared with prior art, the invention provides a kind of Schiff's base aluminum complex and its preparation method and application, this
The Schiff's base aluminum complex of bright offer has formula (I) structure, and the present invention provides complex-catalyzed activity high, and can be catalyzed system
Standby cyclic carbonate, polyester, Merlon and the reaction of polycarbonate-polyester, catalyst applied range, and it is catalyzed work
Property high, there is good prospects for commercial application, test result indicate that, the catalyst that the present invention provides is within the scope of wider temperature
It is respectively provided with preferable catalytic performance.
Detailed description of the invention
The invention provides a kind of Schiff's base aluminum complex, there is structure shown in formula (I):
Wherein, R1And R2Independently selected from aliphatic group.
Wherein, described R1Be preferably selected from the aliphatic group that carbon number is 1~30, more preferably carbon number be 2~
The aliphatic group of 20, most preferably carbon number be the aliphatic group of 3~15, most preferably carbon number be 5~10
Aliphatic group, more specifically, described R1Selected from methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, just
Amyl group, isopentyl, n-hexyl or n-heptyl;Described R2It is preferably selected from the aliphatic group that carbon number is 1~30, more preferably
Carbon number be the aliphatic group of 2~20, most preferably carbon number be that the aliphatic group of 3~15, most preferably carbon are former
Subnumber is the aliphatic group of 5~10, more specifically, and described R2Selected from methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, different
Butyl, the tert-butyl group, n-pentyl, isopentyl, n-hexyl or n-heptyl.
Present invention also offers the preparation method of a kind of Schiff's base aluminium compound, comprise the following steps:
To have the Schiff's base of structure shown in formula (II) and aluminum source compound hybrid reaction in a solvent, obtain that there is formula
(I) the Schiff's base aluminum complex of structure shown in;
In formula (II), R1And R2Independently selected from aliphatic group.
According to the present invention, it is the most anti-with aluminum source compound that the present invention will have the Schiff's base of structure shown in formula (II)
Should, obtain having the Schiff's base aluminum complex of structure shown in formula (I);Wherein, there is described in the Schiff's base of structure shown in formula (II)
In R1And R2The range of choice and aforementioned formula (I) compound in R1And R2The range of choice identical, source of aluminium compound is excellent
Elect diethyl aluminum chloride or the toluene solution of diethyl aluminum chloride solution, more preferably diethyl aluminum chloride as;Described reaction
Solvent is preferably one or more in ether, chloroform, pentane, normal hexane and toluene, more preferably ether or normal hexane;Institute
State that to have the mol ratio of aluminum in the Schiff's base of structure shown in formula (II) and source of aluminium compound be 1:(1.5~3), more preferably
1:2;The consumption of the organic solvent of described reaction preferably makes described Schiff's base mass concentration in organic solvent be 0.01g/mL
~0.05g/mL, more preferably 0.030g/mL~0.036g/mL.The temperature of described reaction is preferably as room temperature, it is not necessary to add
Heat or cooling;Reactive mode is preferably reacts under agitation, and it is special that the method for described stirring is not had by the present invention
Limit, use the technical scheme of stirring well known to those skilled in the art;The time of described reaction be preferably 10 hours~
18 hours, more preferably 15 hours~18 hours;After completion of the reaction, the present invention the most under nitrogen atmosphere, the reaction that will obtain
Product carries out sucking filtration, is dried by the solid obtained, and obtains having the Schiff's base aluminum complex of structure shown in formula (I).The present invention couple
The method of described sucking filtration does not has special restriction, uses the technical scheme of sucking filtration well known to those skilled in the art;This
Bright is to carry out under nitrogen atmosphere to described dry method;In the present invention, described being dried is preferably vacuum drying.
In the present invention, described in there is the Schiff's base of structure shown in formula (II) prepare the most in accordance with the following methods:
React having the tetraamine compound of structure shown in formula (III) with the substituted salicylic aldehydes with formula (IV) structure,
Obtain having the Schiff's base of 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 has formula (IV) structure
Substituted salicylic aldehydes reaction, obtain having the Schiff's base of structure shown in formula (II);Wherein, the replacement bigcatkin willow of described formula (IV) structure
In aldehyde, described R1And R2The range of choice and aforementioned formula (I) compound in R1And R2The range of choice identical, more specifically, institute
State that to have the substituted salicylic aldehydes of formula (IV) structure be 3,5-dimethyl salicylide, 3,5-diethyl salicylide, 3,5-diisopropyl
Salicylide or 3,5-di-tert-butyl salicylaldehyde;The solvent of described reaction is preferably in alcohol compound, dichloromethane and toluene
One or more, more preferably one or more in methanol, ethanol, dichloromethane and toluene;Described have formula (III) structure
Tetraamine compound there is the mol ratio of the substituted salicylic aldehydes of structure shown in formula (IV) be preferably 1:(4~15 with described), more
It is preferably 1:(4~10), most preferably 1:(4~6);The consumption of the solvent of reaction preferably makes tetraamine compound at organic solvent
In mass concentration be 0.01g/mL~0.1g/mL, more preferably 0.015g/mL~0.05g/mL;The temperature of described reaction is excellent
Elect room temperature~110 DEG C as, more preferably 110 DEG C;The time of described reaction is preferably 24h~72h, more preferably 36h~60h,
Most preferably 42h~54h, the most preferably 48h.
In the present invention, in order to make reaction be smoothed out, the present invention is additionally added catalyst, and described catalyst is preferably toluene
Sulfonic acid;Described tetraamine compound is preferably (15~30) with the mass ratio of p-methyl benzenesulfonic acid: 1, more preferably (20~25): 1.
After completion of the reaction, the organic solvent in the product that the present invention preferably will obtain removes, and the reaction removing organic solvent is produced
Thing dichloromethane dissolves, and is then joined in ethanol by the mixed solution obtained and settles, by dried for the solid obtained
Obtain having the Schiff's base of structure shown in formula (II).The present invention does not has special restriction to the method for described removing organic solvent,
Use the technical scheme of place to go well known to those skilled in the art organic solvent, as when use toluene be reaction dissolvent time,
The product obtained is spin-dried for by the present invention, removes organic solvent therein.The consumption of described dichloromethane is not had by the present invention
Special restriction, it is possible to the product obtained is dissolved;The present invention does not has special limit to the consumption of described ethanol yet
System, it is possible to product is settled completely.Described mixed solution is preferably added drop-wise in ethanol by the present invention, and stirring is sunk
Fall, then filters, is dried to obtain and has the Schiff's base of structure shown in formula (II).The present invention is the most special to the method for described stirring
Restriction, use the technical scheme of stirring well known to those skilled in the art, in the present invention, the time of described stirring is excellent
Elect 20min~50min as, more preferably 25min~40min, most preferably 30min~35min.The present invention to described filtration and
The method being dried does not has special restriction, uses filtration well known to those skilled in the art and dry technical scheme,
In the present invention, described being dried is preferably vacuum drying.
Present invention also offers the preparation method of a kind of cyclic carbonate, including:
By epoxide, carbon dioxide, catalyst and promoter hybrid reaction, obtain cyclic carbonate;
Described catalyst is for having structure Schiff's base aluminum complex shown in formula (I).
According to the present invention, the present invention, by epoxide, carbon dioxide, catalyst and promoter hybrid reaction, obtains
Cyclic carbonate;Described epoxide is preferably the aryl of the epoxide of the alkyl substituent of C2~C10, C7~C15
The epoxide of the alkyl substituent of substituted epoxide or glycidyl ether, more preferably C3~C7, C10~C12
The substituted epoxide of aryl or glycidyl ether, most preferably expoxy propane, oxirane, epoxychloropropane, oxidation
One in styrene, Ethylene glycol diglycidyl ether, butanediol diglycidyl ether and neopentylglycol diglycidyl ether or
Several;Described promoter is preferably double (dihalotriphenylphosphoranes base) ammonium chloride (PPNCl), DMAP (DMAP), N-
Methylimidazole., tricyclohexyl phosphine, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1,5,7-tri-azabicyclic [4.4.0]
One in one or more in decyl-5-alkene, tetrabutylammonium chloride and tetrabutyl ammonium bromide, more preferably PPNCl and DMAP
Or two kinds, most preferably PPNCl.In the present invention, the mol ratio of described catalyst and described promoter be preferably 1:(1~
2), more preferably 1:(1~1.5);The total mole number of described catalyst and promoter is excellent with the mol ratio of described epoxide
Elect 1:(300~2000 as): (1000~40000), more preferably 1:(300~1000): (1000~6000);Described titanium dioxide
The pressure of carbon is preferably 2MPa~5MPa, more preferably 2MPa~3MPa;The temperature of described catalytic 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 described copolyreaction is excellent
Elect 0.5h~24h as, more preferably 1h~21h, most preferably 3h~18h, the most preferably 6h~15h.
In the present invention, after having reacted, reaction system is preferably cooled down by the present invention, discharges residual gas, by obtain
Product dichloromethane dissolves, and then adds in ethanol by the solution obtained, stands, precipitation sedimentation obtained after stirring
It is again dissolved in dichloromethane, the solution obtained is settled in ethanol, then precipitation sedimentation obtained is dried, and is polymerized
Thing.Reactor is preferably placed in frozen water and lowers the temperature rapidly by the present invention, then slowly releases participation gas and is down to air to pressure
Pressure, then open reactor taking-up product.The present invention does not has special restriction, energy to the consumption of described dichloromethane and ethanol
Enough realize the dissolving to product and settle.In the present invention, the time of described stirring is preferably 10 minutes~25 points
Clock, more preferably 15 minutes~20 minutes;The time of described standing is preferably 20 minutes~40 minutes, more preferably 25 minutes~
35 minutes, most preferably 30 minutes;The described number of times by the resolution of precipitate obtained, sedimentation is preferably 2 times~5 times, and more preferably 3
Secondary~4 times.
Present invention also offers the preparation method of a kind of Merlon, including:
By epoxide, carbon dioxide, catalyst and promoter hybrid reaction, obtain Merlon;
Described catalyst is of the present invention to have structure Schiff's base aluminum complex shown in formula (I).
Described epoxide is epoxide or the glycidyl ether of the alkyl substituent containing C5~C8.
According to the present invention, the present invention, by epoxide, carbon dioxide, catalyst and promoter hybrid reaction, obtains
Merlon;Described epoxide be preferably C5~C8 cycloolefin oxide, more preferably C6~C7 cycloolefin
One or both in oxide, most preferably cyclohexene oxide and cyclopentene oxide;Described promoter is preferably double
(dihalotriphenylphosphoranes base) ammonium chloride (PPNCl), DMAP (DMAP), N-Methylimidazole., tricyclohexyl phosphine, 1,8-bis-
Azabicyclo [5.4.0] 11 carbon-7-alkene, 1,5,7-tri-azabicyclic [4.4.0] decyl-5-alkene, tetrabutylammonium chloride and four fourths
One or both in one or more in base ammonium bromide, more preferably PPNCl and DMAP, most preferably PPNCl.At this
In bright, described catalyst is preferably 1:(1~2 with the mol ratio of described promoter), more preferably 1:(1~1.5);Described urge
The mol ratio of the total mole number of agent and promoter and described epoxide is preferably 1:(300~2000): (1000~
40000), more preferably 1:(300~1000): (1000~6000);The pressure of described carbon dioxide is preferably 2MPa~5MPa,
More preferably 2MPa~3MPa;The temperature of described catalytic reaction is preferably 50 DEG C~90 DEG C, more preferably 60 DEG C~90 DEG C, optimum
Elect 70 DEG C~80 DEG C as, the most preferably 80 DEG C;The time of described copolyreaction is preferably 0.5h~24h, more preferably 1h~
21h, most preferably 3h~18h, the most preferably 6h~15h.
In the present invention, after having reacted, reaction system is preferably cooled down by the present invention, discharges residual gas, by obtain
Product dichloromethane dissolves, and then adds in ethanol by the solution obtained, stands, precipitation sedimentation obtained after stirring
It is again dissolved in dichloromethane, the solution obtained is settled in ethanol, then precipitation sedimentation obtained is dried, and is polymerized
Thing.Reactor is preferably placed in frozen water and lowers the temperature rapidly by the present invention, then slowly releases participation gas and is down to air to pressure
Pressure, then open reactor taking-up product.The present invention does not has special restriction, energy to the consumption of described dichloromethane and ethanol
Enough realize the dissolving to product and settle.In the present invention, the time of described stirring is preferably 10 minutes~25 points
Clock, more preferably 15 minutes~20 minutes;The time of described standing is preferably 20 minutes~40 minutes, more preferably 25 minutes~
35 minutes, most preferably 30 minutes;The described number of times by the resolution of precipitate obtained, sedimentation is preferably 2 times~5 times, and more preferably 3
Secondary~4 times.
The invention provides the preparation method of a kind of polyester, including:
By epoxide, cyclic acid anhydride, catalyst and promoter hybrid reaction, obtain polyester;
Described catalyst is of the present invention to have structure Schiff's base aluminum complex shown in formula (I).
According to the present invention, the present invention, by epoxide, cyclic acid anhydride, catalyst and promoter hybrid reaction, obtains
Polyester;Wherein, described epoxide is preferably the epoxide of alkyl substituent of C1~C15, the aryl of C6~C20 replaces
Epoxide, glycidyl ether or C3~C10 cycloolefin oxide, the alkyl substituent of more preferably C2~C10
Epoxide, C7~C15 the substituted epoxide of aryl, glycidyl ether or C5~C8 cycloolefin oxidation
The epoxide of the alkyl substituent of thing, most preferably C3~C7, the substituted epoxide of aryl of C10~C12, shrink
Glycerin ether or C6~C7 cycloolefin oxide, more specifically, described epoxide is expoxy propane, oxirane, ring
Oxygen chloropropane, styrene oxide, Ethylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol 2-glycidyl
One or more in ether, cyclohexene oxide and cyclopentene oxide.The energy that described anhydride is well known to those skilled in the art
Enough and epoxide reaction prepares the conventional cyclic acid anhydride of polyester, such as five-membered cyclic anhydride or six-membered cyclic anhydride, specifically
, described anhydride is preferably phthalic anhydride, maleic anhydride, dimethyl succinic acid acid anhydride, suitable succinic anhydride, carbic acid
One or several in acid anhydride, Tetramethylene .-1,2-dicarboxylic acid anhydride, cis-hexamethylene-1,2-dicarboxylic anhydride and 4-methyl hexahydrophthalic anhydride etc.
Kind, more preferably one or more in phthalic anhydride, maleic anhydride and carbic anhydride, the most adjacent benzene two
Formic anhydride and maleic anhydride.Described promoter is preferably double (dihalotriphenylphosphoranes base) ammonium chloride (PPNCl), 4-dimethylamino pyrrole
Pyridine (DMAP), N-Methylimidazole., tricyclohexyl phosphine, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1,5,7-tri-azepine
One or more in bicyclo-[4.4.0] decyl-5-alkene, tetrabutylammonium chloride and tetrabutyl ammonium bromide, more preferably PPNCl and
One or both in DMAP, most preferably PPNCl.In the present invention, described catalyst and the mol ratio of described promoter
It is preferably 1:(1~2), more preferably 1:(1~1.5);The total mole number of described catalyst and promoter and described ring-type acid
Acid anhydride, the mol ratio of epoxide are preferably 1:(300~2000): (1000~40000), more preferably 1:(300~1000):
(1000~6000).
In the present invention, the temperature of described reaction is preferably 50 DEG C~90 DEG C, more preferably 60 DEG C~90 DEG C, and most preferably 70
DEG C~80 DEG C, the most preferably 80 DEG C;The time of described reaction is preferably 0.5h~24h, more preferably 1h~21h, most preferably
For 3h~18h, the most preferably 6h~15h.
After completion of the reaction, reaction system is preferably cooled down by the present invention, discharges residual gas, the product obtained is used
Dichloromethane dissolves, and then adds in ethanol by the solution obtained, stands after stirring, and precipitation sedimentation obtained is again dissolved in two
In chloromethanes, the solution obtained is settled in ethanol, then precipitation sedimentation obtained is dried, and obtains polymer.The present invention is excellent
Reactor is placed in frozen water by choosing lowers the temperature rapidly, then slowly releases participation gas to pressure and is down to atmospheric pressure, then opens anti-
Still is answered to take out product.The present invention does not has special restriction to the consumption of described dichloromethane and ethanol, it is possible to realize instead
Answer the dissolving of product and settle.In the present invention, the time of described stirring is preferably 10 minutes~25 minutes, more preferably
15 minutes~20 minutes;The time of described standing is preferably 20 minutes~40 minutes, more preferably 25 minutes~35 minutes, optimum
Elect 30 minutes as;The described number of times by the resolution of precipitate obtained, sedimentation is preferably 2 times~5 times, more preferably 3 times~4 times.
Present invention also offers the preparation method of a kind of polycarbonate-polyester copolymer, including:
By carbon dioxide, epoxide, anhydride, catalyst and promoter hybrid reaction, obtain polycarbonate-polyester
Copolymer;
Described catalyst is of the present invention to have structure Schiff's base aluminum complex shown in formula (I).
According to the present invention, the present invention by carbon dioxide, epoxide, anhydride, catalyst and promoter hybrid reaction,
Obtain polycarbonate-polyester copolymer;Wherein, described epoxide is preferably the epoxy compound of alkyl substituent of C1~C15
Thing, C6~C20 the substituted epoxide of aryl, glycidyl ether or C3~C10 cycloolefin oxide, more preferably
The epoxide of the alkyl substituent of C2~C10, the substituted epoxide of aryl, glycidyl ether or the C5 of C7~C15
~C8 cycloolefin oxide, the epoxide of the alkyl substituent of most preferably C3~C7, the aryl of C10~C12 take
The epoxide in generation, glycidyl ether or C6~C7 cycloolefin oxide, more specifically, described epoxide is ring
Ethylene Oxide, oxirane, epoxychloropropane, styrene oxide, Ethylene glycol diglycidyl ether, butanediol diglycidyl ether,
One or more in neopentylglycol diglycidyl ether, cyclohexene oxide and cyclopentene oxide.Described anhydride is ability
The conventional cyclic acid anhydride of polyester can be prepared with epoxide reaction known to field technique personnel, such as five-membered cyclic anhydride or
Six-membered cyclic anhydride, concrete, described anhydride is preferably phthalic anhydride, maleic anhydride, dimethyl succinic acid acid anhydride, suitable fourth two
Anhydride, carbic anhydride, Tetramethylene .-1,2-dicarboxylic acid anhydride, cis-hexamethylene-1,2-dicarboxylic anhydride and 4-methyl hexahydrobenzene
One or several in one or more in acid anhydride etc., more preferably phthalic anhydride, maleic anhydride and carbic anhydride
Kind, most preferably phthalic anhydride and maleic anhydride.Described promoter is preferably double (dihalotriphenylphosphoranes base) ammonium chloride
(PPNCl), DMAP (DMAP), N-Methylimidazole., tricyclohexyl phosphine, 1,8-diazabicyclo [5.4.0] 11
One or many in carbon-7-alkene, 1,5,7-tri-azabicyclic [4.4.0] decyl-5-alkene, tetrabutylammonium chloride and tetrabutyl ammonium bromide
Kind, one or both in more preferably PPNCl and DMAP, most preferably PPNCl.The pressure of described carbon dioxide is preferably
2MPa~5MPa, more preferably 2MPa~3MPa.In the present invention, described catalyst is preferred with the mol ratio of described promoter
For 1:(1~2), more preferably 1:(1~1.5);The total mole number of described catalyst and promoter and described cyclic acid anhydride, ring
The mol ratio of oxide is preferably 1:(300~2000): (1000~40000), more preferably 1:(300~1000): (1000~
6000)。
In the present invention, the temperature of described reaction is preferably 50 DEG C~90 DEG C, more preferably 60 DEG C~90 DEG C, and most preferably 70
DEG C~80 DEG C, the most preferably 80 DEG C;The time of described reaction is preferably 0.5h~24h, more preferably 1h~21h, most preferably
For 3h~18h, the most preferably 6h~15h.
After completion of the reaction, reaction system is preferably cooled down by the present invention, discharges residual gas, the product obtained is used
Dichloromethane dissolves, and then adds in ethanol by the solution obtained, stands after stirring, and precipitation sedimentation obtained is again dissolved in two
In chloromethanes, the solution obtained is settled in ethanol, then precipitation sedimentation obtained is dried, and obtains polymer.The present invention is excellent
Reactor is placed in frozen water by choosing lowers the temperature rapidly, then slowly releases participation gas to pressure and is down to atmospheric pressure, then opens anti-
Still is answered to take out product.The present invention does not has special restriction to the consumption of described dichloromethane and ethanol, it is possible to realize instead
Answer the dissolving of product and settle.In the present invention, the time of described stirring is preferably 10 minutes~25 minutes, more preferably
15 minutes~20 minutes;The time of described standing is preferably 20 minutes~40 minutes, more preferably 25 minutes~35 minutes, optimum
Elect 30 minutes as;The described number of times by the resolution of precipitate obtained, sedimentation is preferably 2 times~5 times, more preferably 3 times~4 times.
The invention provides a kind of Schiff's base aluminum complex and its preparation method and application, the Schiff's base aluminum that the present invention provides
Coordination compound has formula (I) structure, and the present invention provides complex-catalyzed activity high, and can catalytic preparation of cyclic carbonic ester, poly-
The reaction of ester, Merlon and polycarbonate-polyester, catalyst applied range, and also it is high to be catalyzed activity, the use of catalyst
Amount can as little as monomer consumption 0.3 ‰, and in reaction, feed stock conversion is high, and the time of reaction is short, the performance of the polymer obtained
Good, there is good prospects for commercial application, test result indicate that, the catalyst that the present invention provides is equal within the scope of wider temperature
There is preferable catalytic performance.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
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, obtains Tan solid or dope after toluene vacuum being drained;
The Tan solid obtained or dope 50mL dichloromethane are dissolved, is added drop-wise in 1000mL ethanol, stirring
Yellow solid it is filtrated to get after 30min, vacuum drying, obtain the Schiff's base with formula (II) structure.
It is 80% that the present invention is calculated the productivity of the Schiff's base with formula (II) structure.
The present invention utilizes nuclear magnetic resonance, NMR to be analyzed the Schiff's base with formula (II) structure obtained in the present embodiment,
Composing to its hydrogen, result shows:1H 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 Schiff's base with formula (II) structure that the present invention utilizes mass spectrograph to obtain the present embodiment is analyzed, result table
Bright: MALDI-TOF (CHCl3), m/z=1079.8;
The Schiff's base (II) that the present invention utilizes elementary analysis to obtain the present embodiment is analyzed, and obtains its each atom and contains
Amount: Elem.Anal. (%): Calcd.C 80.11;H 8.78;N 5.19.Found:C78.63;H 9.17;N 6.68;
By above proton nmr spectra, mass spectral analysis and elementary analysis result it can be seen that the Schiff prepared of the present embodiment
Alkali has structure, wherein R shown in formula (II)1And R2It is the tert-butyl group.
Embodiment 2
The present invention uses the technical scheme of embodiment 1 to prepare Schiff's base, and except for the difference that, the present embodiment uses 3,5-dimethyl
Salicylide replaces the 3,5-di-tert-butyl salicylaldehyde in embodiment 1.
The product obtained is carried out hydrogen nuclear magnetic resonance analysis of spectrum, mass spectral analysis and elementary analysis, result table by the present invention
Bright, Schiff's base prepared by the present embodiment has structure, wherein R shown in formula (II)1And R2It is methyl.
Embodiment 3
The present invention uses the technical scheme of embodiment 1 to prepare Schiff's base, and except for the difference that, the present embodiment uses 3,5-diethyl
Salicylide replaces the 3,5-di-tert-butyl salicylaldehyde in embodiment 1.
The product obtained is carried out hydrogen nuclear magnetic resonance analysis of spectrum, mass spectral analysis and elementary analysis, result table by the present invention
Bright, Schiff's base prepared by the present embodiment has structure, wherein R shown in formula (II)1And R2It is ethyl.
Embodiment 4
The present invention uses the technical scheme of embodiment 1 to prepare Schiff's base, and except for the difference that, the present embodiment uses 3,5-diisopropyl
Base salicylide replaces the 3,5-di-tert-butyl salicylaldehyde in embodiment 1.
The product obtained is carried out hydrogen nuclear magnetic resonance analysis of spectrum, mass spectral analysis and elementary analysis, result table by the present invention
Bright, Schiff's base prepared by the present embodiment has structure, wherein R shown in formula (II)1And R2It is isopropyl.
Embodiment 5
Under nitrogen atmosphere, Schiff's base prepared by 0.5g embodiment 1 is dissolved in 15ml normal hexane, is slowly added dropwise
The toluene solution (0.9mol/L) of 1.03ml diethyl aluminum chloride, under nitrogen atmosphere after stirring reaction 18h, the product obtained exists
Sucking filtration under nitrogen atmosphere, is dried under vacuum the product obtained, obtains yellow solid, and this solid is Schiff's base aluminum complex.
The present invention is calculated the productivity 83% of schiff bases complex.
The present invention utilizes nuclear magnetic resonance, NMR to be analyzed the Schiff's base obtained in the present embodiment, obtains its hydrogen spectrum, result table
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 Schiff's base aluminum compound that the present invention utilizes mass spectrograph to obtain the present embodiment is analyzed, and result shows: ESI-MS
(CHCl3), m/z=1146.7 (-2Cl+H2O)。
Being shown by above analysis result, the schiff bases complex that the present embodiment prepares has structure shown in formula (I), its
Middle R1And R2It is the tert-butyl group.
Embodiment 6
The technical scheme using embodiment 5 prepares schiff bases complex, and except for the difference that, the present embodiment uses embodiment 2 to obtain
To Schiff's base replace the Schiff's base for preparing of embodiment 1 that embodiment 5 uses.
The product obtained is carried out nuclear magnetic resonance spectroscopy, mass spectral analysis by the present invention, and result shows, the present embodiment obtains
Schiff bases complex there is structure, wherein R shown in formula (I)1And R2It is methyl.
Embodiment 7
The technical scheme using embodiment 5 prepares schiff bases complex, and except for the difference that, the present embodiment uses embodiment 3 to obtain
To Schiff's base replace the Schiff's base for preparing of embodiment 1 that embodiment 5 uses.
The product obtained is carried out nuclear magnetic resonance spectroscopy, mass spectral analysis by the present invention, and result shows, the present embodiment obtains
Schiff bases complex there is structure, wherein R shown in formula (I)1And R2It is ethyl.
Embodiment 8
The technical scheme using embodiment 5 prepares schiff bases complex, and except for the difference that, the present embodiment uses embodiment 4 to obtain
To Schiff's base replace the Schiff's base for preparing of embodiment 1 that embodiment 5 uses.
The product obtained is carried out nuclear magnetic resonance spectroscopy, mass spectral analysis by the present invention, and result shows, the present embodiment obtains
Schiff bases complex there is structure, wherein R shown in formula (I)1And R2It is isopropyl.
Embodiment 9
The Schiff's base aluminium compound and the 0.0052gPPNCl that 1.50g expoxy propane, 0.0150g embodiment 5 are obtained help and urge
Agent is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity carbon dioxide gas wherein, pressurization
To 2MPa, control temperature and be stirred at 60 DEG C, react 2h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, complete in the product that the present embodiment obtains
Portion is cyclic carbonate, and conversion ratio is 55%.
Embodiment 10
The Schiff's base aluminium compound that 2g expoxy propane, 0.0110g embodiment 5 are obtained and 0.0119gPPNCl promoter
It is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity carbon dioxide gas wherein, is forced into
2MPa, controls temperature and stirs at 80 DEG C, react 2h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio is 92%.
Embodiment 11
The Schiff's base aluminium compound that 2g expoxy propane, 0.0220g embodiment 5 are obtained and 0.0206gPPNCl promoter
It is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity carbon dioxide gas wherein, is forced into
2MPa, controls temperature and stirs at 50 DEG C, react 6h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 40%.
Embodiment 12
The Schiff's base aluminium compound that 1.8g expoxy propane, 0.0186g embodiment 6 are obtained and 0.0103gPPNCl co-catalysis
Agent is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity carbon dioxide gas wherein, is forced into
4MPa, controls temperature and stirs at 60 DEG C, react 2h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 23%.
Embodiment 13
The Schiff's base aluminium compound that 2.0g expoxy propane, 0.0198g embodiment 6 are obtained and 0.0110g tetrabutyl phosphonium bromide
Ammonium promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity carbon dioxide gas wherein
Body, is forced into 2MPa, controls temperature and stirs at 60 DEG C, reacts 2.5h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 34%.
Embodiment 14
The Schiff's base aluminium compound that 1.7g expoxy propane, 0.0164g embodiment 5 are obtained and 0.0122g tetrabutyl chlorination
Ammonium promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity carbon dioxide gas wherein
Body, is forced into 3MPa, controls temperature and stirs at 60 DEG C, reacts 6h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 91%.
Embodiment 15
The Schiff's base aluminium compound that 1.7g expoxy propane, 0.0186g embodiment 5 are obtained and 0.0148g tetrabutyl chlorination
Ammonium promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity carbon dioxide gas wherein
Body, is forced into 3MPa, controls temperature and stirs at 80 DEG C, reacts 4h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 86%.
Embodiment 16
The Schiff's base aluminium compound that 1.6g expoxy propane, 0.0150g embodiment 7 are obtained and 0.0061g1,5,7-tri-nitrogen
Miscellaneous bicyclo-[4.4.0] decyl-5-alkene promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, leads to wherein
Enter high-purity carbon dioxide gas, be forced into 4MPa, control temperature and stir at 80 DEG C, react 5h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 45%.
Embodiment 17
The Schiff's base aluminium compound that 1.3g expoxy propane, 0.0117g embodiment 8 are obtained and 0.0054g4-dimethyl pyrazole
Pyridine promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity carbon dioxide gas wherein
Body, is forced into 4MPa, controls temperature and stirs at 75 DEG C, reacts 6h;
Reacting in reactor is placed in after terminating frozen water and lower the temperature rapidly, the most slowly release residual gas drops to greatly to pressure
Air pressure.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 42%.
Embodiment 18
The Schiff's base aluminium compound that 1.8g styrene oxide, 0.0150g embodiment 5 are obtained and 0.0108g tetrabutyl bromine
Change ammonium promoter to be mixed to join in high temperature removes the autoclave of water deoxygenation, be passed through high-purity carbon dioxide gas wherein
Body, is forced into 4MPa, controls temperature and stirs at 70 DEG C, reacts 3h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the product that the present embodiment obtains is whole
For cyclic carbonate, conversion ratio 68%.
Embodiment 19
The Schiff's base aluminium compound and the 0.0119gPPNCl that 2.3g 7-oxa-bicyclo[4.1.0,0.0269g embodiment 5 are obtained help and urge
Agent is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity carbon dioxide gas wherein, pressurization
To 2MPa, control temperature and stir at 80 DEG C, react 6h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure, dissolves the product 15mL dichloromethane obtained, is slowly added dropwise to 200mL ethanol by the solution obtained,
Static 30min after stirring 15min;Polymer after precipitation is dissolved with dichloromethane again, settles in ethanol, be repeated 3 times,
Product vacuum drying sedimentation obtained, obtains product.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, in the product that the present embodiment obtains
All Merlon, conversion ratio is 51%;
The Merlon that the present invention utilizes gel permeation chromatography to obtain the present embodiment is analyzed, and obtains Merlon
Number-average molecular weight is 1.5 ten thousand.
Embodiment 20
The Schiff's base aluminium compound that 2g 7-oxa-bicyclo[4.1.0,0.0269g embodiment 5 are prepared and 0.0238g PPNCl
Promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity carbon dioxide gas wherein,
It is forced into 2MPa, controls temperature at 80 DEG C of stirrings, reaction 6h;
After reaction terminates, lowering the temperature rapidly in reactor is placed in frozen water, the most slowly release residual gas drops to pressure
Atmospheric pressure, dissolves the product 15mL dichloromethane obtained, is slowly added dropwise to 200mL ethanol by the solution obtained,
Static 30min after stirring 15min;Polymer after precipitation is dissolved with dichloromethane again, settles in ethanol, be repeated 3 times,
Solid vacuum drying sedimentation obtained, obtains product.
The polymer obtained is carried out by the present invention1H-NMR analyzes, and result shows, in the product that the present embodiment obtains
All Merlon, conversion ratio about 68%;
The Merlon that the present invention utilizes gel permeation chromatography to obtain the present embodiment is analyzed, and obtains Merlon
Number-average molecular weight is 1.2 ten thousand.
Embodiment 21
Schiff's base aluminium compound prepared by 1.8g 7-oxa-bicyclo[4.1.0,0.84g phthalic anhydride, 0.0214g example 5 and
0.0114g PPNCl promoter is mixed to join in high temperature removes the reactor of water deoxygenation, and control temperature, at 80 DEG C, is reacted
2h。
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly.Product 15ml dichloromethane dissolves, by obtain
Solution is slowly added dropwise to 200ml ethanol, static 30min after stirring 15min;Polymer after precipitation is used dichloromethane again
Dissolve, settle in ethanol, be repeated 3 times.Solid vacuum drying sedimentation obtained, obtains product.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the reaction obtained at the present embodiment is produced
The all polyester of thing, in the present embodiment, the reaction conversion ratio of phthalic anhydride reaches 97%.
The polyester utilizing gel permeation chromatography to obtain the present embodiment is analyzed, and the number-average molecular weight obtaining polyester is
2.1 ten thousand.
Embodiment 22
Schiff's base aluminium compound prepared by 2.5g expoxy propane, 0.84g phthalic anhydride, 0.0214g example 5 and
0.0114g PPNCl promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, and control temperature is at 80 DEG C, instead
Answer 1.5h.
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly.Product 15ml dichloromethane dissolves, by obtain
Solution is slowly added dropwise to 200ml ethanol, static 30min after stirring 15min;Polymer after precipitation is used dichloromethane again
Dissolve, settle in ethanol, be repeated 3 times.Solid vacuum drying sedimentation obtained, obtains product.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the reaction obtained at the present embodiment is produced
The all polyester of thing, in the present embodiment, the reaction conversion ratio of phthalic anhydride reaches 100%.
The present invention is with polystyrene as reference material, and the polyester utilizing gel permeation chromatography to obtain the present embodiment is carried out point
Analysis, the number-average molecular weight obtaining polyester is 1.5 ten thousand.
Embodiment 23
Schiff's base aluminium compound prepared by 1.9g 7-oxa-bicyclo[4.1.0,0.62g phthalic anhydride, 0.0197g example 5 and
0.0108g PPNCl promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, and control temperature is at 60 DEG C, instead
Answer 4h.
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly.Product 5ml dichloromethane dissolves, by obtain
Solution is slowly added dropwise to 200ml ethanol, static 30min after stirring 15min;Polymer after precipitation is used dichloromethane again
Dissolve, settle in ethanol, be repeated 3 times.Solid vacuum drying sedimentation obtained, obtains product.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the reaction obtained at the present embodiment is produced
The all polyester of thing, in the present embodiment, the reaction conversion ratio of phthalic anhydride reaches 64%.
The present invention is with polystyrene as reference material, and the polyester utilizing gel permeation chromatography to obtain the present embodiment is carried out point
Analysis, the number-average molecular weight obtaining polyester is 0.9 ten thousand.
Embodiment 24
Schiff's base aluminium compound prepared by 2.0g 7-oxa-bicyclo[4.1.0,0.56g phthalic anhydride, 0.0198g example 5 and
0.0074g PPNCl promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through carbon dioxide 2MPa,
Control temperature, at 80 DEG C, reacts 5h.
After reaction terminates, being placed in frozen water by reactor and lower the temperature rapidly, the most slowly release residual gas drops to pressure
Atmospheric pressure, a small amount of sample is used for1H-NMR analyzes.Product with 15ml dichloromethane dissolve, the solution obtained is slowly added dropwise to
In 200ml ethanol, static 30min after stirring 15min;Polymer after precipitation is dissolved, in ethanol with dichloromethane again
Sedimentation, is repeated 3 times.Solid vacuum drying sedimentation obtained, obtains product.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the present embodiment obtains polyester-poly-carbonic acid
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 utilizing gel permeation chromatography to obtain the present embodiment is analyzed, and obtains the number of polymer
Average molecular weight is 2.4 ten thousand.
Embodiment 25
Schiff's base aluminium compound prepared by 1.7g expoxy propane, 0.74g phthalic anhydride, 0.0184g example 5 and
0.0162g PPNCl promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through carbon dioxide 3MPa,
Control temperature, at 70 DEG C, reacts 5h.
After reaction terminates, being placed in frozen water by reactor and lower the temperature rapidly, the most slowly release residual gas drops to pressure
Atmospheric pressure.Product 15ml dichloromethane dissolves, and is slowly added dropwise to 200ml ethanol by the solution obtained, quiet after stirring 15min
Only 30min;Polymer after precipitation is dissolved with dichloromethane again, settles in ethanol, be repeated 3 times.Sedimentation is obtained
Solid is vacuum dried, and obtains product.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the present embodiment obtains expoxy propane-neighbour
Phthalate anhydride polyester and Allyl carbonate, wherein the reaction conversion ratio of phthalic anhydride reaches 100%, turning of expoxy propane
The rate of changing is 84%.
The polyester utilizing gel permeation chromatography to obtain the present embodiment is analyzed, and the number-average molecular weight obtaining polymer is
1.2 ten thousand.
Embodiment 26
Schiff's base aluminium compound prepared by 1.5g expoxy propane, 0.45g maleic anhydride, 0.0124g example 5 and
0.0098g PPNCl promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, and control temperature is at 60 DEG C, instead
Answer 5h.
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly.Product 15ml dichloromethane dissolves, by obtain
Solution is slowly added dropwise to 200ml ethanol, static 30min after stirring 15min;Polymer after precipitation is used dichloromethane again
Dissolve, settle in ethanol, be repeated 3 times.Solid vacuum drying sedimentation obtained, obtains product.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the present embodiment obtains expoxy propane-horse
Carrying out anhydride polyester, wherein the reaction conversion ratio of maleic anhydride reaches 100%.
The polyester utilizing gel permeation chromatography to obtain the present embodiment is analyzed, and the number-average molecular weight obtaining polymer is
1.1 ten thousand.
Embodiment 27
Schiff's base aluminium compound prepared by 1.8g styrene oxide, 0.48g maleic anhydride, 0.0154g example 6 and
0.0112g PPNCl promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, and control temperature is at 50 DEG C, instead
Answer 7h.
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly.Product 15ml dichloromethane dissolves, by obtain
Solution is slowly added dropwise to 200ml ethanol, static 30min after stirring 15min;Polymer after precipitation is used dichloromethane again
Dissolve, settle in ethanol, be repeated 3 times.Solid vacuum drying sedimentation obtained, obtains product.
The product obtained is carried out by the present invention1H-NMR analyze, result shows, the present embodiment obtain styrene oxide-
Maleic anhydride polyester, wherein the reaction conversion ratio of maleic anhydride reaches 87%.
The polyester utilizing gel permeation chromatography to obtain the present embodiment is analyzed, and the number-average molecular weight obtaining polymer is
0.8 ten thousand.
Embodiment 28
Schiff's base aluminium compound prepared by 1.8g 7-oxa-bicyclo[4.1.0,0.84g carbic anhydride, 0.0244g example 8
With 0.0164g PPNCl promoter be mixed to join through high temperature except water deoxygenation autoclave in, control temperature at 80 DEG C,
Reaction 2h.
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly.Product 15ml dichloromethane dissolves, by obtain
Solution is slowly added dropwise to 200ml ethanol, static 30min after stirring 15min;Polymer after precipitation is used dichloromethane again
Dissolve, settle in ethanol, be repeated 3 times.Solid vacuum drying sedimentation obtained, obtains product.
The product obtained is carried out by the present invention1H-NMR analyze, result shows, the present embodiment obtain 7-oxa-bicyclo[4.1.0-
Carbic anhydride polyester, wherein the reaction conversion ratio of carbic anhydride reaches 94%.
The polyester utilizing gel permeation chromatography to obtain the present embodiment is analyzed, and the number-average molecular weight obtaining polymer is
1.4 ten thousand.
Embodiment 29
Schiff's base aluminium compound prepared by 2.1g 7-oxa-bicyclo[4.1.0,0.41g maleic anhydride, 0.0195g example 5 and
0.0156g PPNCl promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, is passed through high-purity two wherein
Carbon oxide gas, is forced into 2MPa, and control temperature, at 75 DEG C, reacts 5h.
After reaction terminates, being placed in frozen water by reactor and lower the temperature rapidly, the most slowly release residual gas drops to pressure
Atmospheric pressure.Product 15ml dichloromethane dissolves, and is slowly added dropwise to 200ml ethanol by the solution obtained, quiet after stirring 15min
Only 30min;Polymer after precipitation is dissolved with dichloromethane again, settles in ethanol, be repeated 3 times.Sedimentation is obtained
Solid is vacuum dried, and obtains product.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, the present embodiment obtains polyester-poly-carbonic acid
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 utilizing gel permeation chromatography to obtain the present embodiment is analyzed, and obtains the number of polymer
Average molecular weight is 1.8 ten thousand.
Embodiment 30
Schiff's base aluminium compound prepared by 2.6g 7-oxa-bicyclo[4.1.0,1.2g phthalic anhydride, 0.01g embodiment 5 and
0.0048g PPNCl promoter is mixed to join in high temperature removes the autoclave of water deoxygenation, and control temperature is at 80 DEG C, instead
Answer 5h.
After reaction terminates, reactor is placed in frozen water and lowers the temperature rapidly.Product 15ml dichloromethane dissolves, by obtain
Solution is slowly added dropwise to 200ml ethanol, static 30min after stirring 15min;Polymer after precipitation is used dichloromethane again
Dissolve, settle in ethanol, be repeated 3 times.Solid vacuum drying sedimentation obtained, obtains product.
The product obtained is carried out by the present invention1H-NMR analyzes, and result shows, being entirely that the present embodiment obtains is poly-
Ester.The polyester utilizing gel permeation chromatography to obtain the present embodiment is analyzed, and the number-average molecular weight obtaining polymer is 2.4
Ten thousand.The glass transition temperature utilizing differential scanning calorimeter to record polymer is 142.9 DEG C.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out
Some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. a Schiff's base aluminum complex, has a structure shown in formula (I):
Wherein, R1And R2Independently selected from aliphatic group.
Schiff's base aluminium compound the most according to claim 1, it is characterised in that described R1And R2Independently selected from carbon atom
Number is the aliphatic group of 1~30.
3. a preparation method for Schiff's base aluminium compound, comprises the following steps:
React having the Schiff's base of structure shown in formula (II) in a solvent with aluminum source compound, obtain having knot shown in formula (I)
The Schiff's base aluminum complex of structure;
In formula (II), R1And R2Independently selected from aliphatic group.
Preparation method the most according to claim 3, it is characterised in that described in there is the Schiff's base of structure shown in formula (II)
Preparation method comprises the following steps:
React having the tetraamine compound of structure shown in formula (III) with the substituted salicylic aldehydes with formula (IV) structure, obtain
There is the Schiff's base of structure shown in formula (II);
In formula (IV), R1And R2Independently selected from aliphatic group.
5. a preparation method for cyclic carbonate, including:
By epoxide, carbon dioxide, catalyst and promoter hybrid reaction, obtain cyclic carbonate;
Described catalyst is to have structure Schiff's base aluminum complex or power shown in formula (I) described in claim 1~2 any one
Profit requires that prepared by the preparation method described in 3~4 any one has structure Schiff's base aluminum complex shown in formula (I);
Described epoxide is the substituted epoxidation of aryl of the epoxide of the alkyl substituent of C1~C15, C6~C20
Compound or glycidyl ether.
Preparation method the most according to claim 5, it is characterised in that described epoxide is expoxy propane, epoxy second
Alkane, epoxychloropropane, 1,2-epoxypentane, styrene oxide, Ethylene glycol diglycidyl ether, butanediol diglycidyl ether and
One or more in neopentylglycol diglycidyl ether.
7. a preparation method for Merlon, including:
By epoxide, carbon dioxide, catalyst and promoter hybrid reaction, obtain Merlon;
Described catalyst is to have structure Schiff's base aluminum complex or power shown in formula (I) described in claim 1~2 any one
Profit requires that prepared by the preparation method described in 3~4 any one has structure Schiff's base aluminum complex shown in formula (I);
Described epoxide is the cycloolefin oxide of C5~C8.
8. a preparation method for polyester, including:
By epoxide, cyclic acid anhydride, catalyst and promoter hybrid reaction, obtain polyester;
Described catalyst is to have structure Schiff's base aluminum complex or power shown in formula (I) described in claim 1~2 any one
Profit requires that prepared by the preparation method described in 3~4 any one has structure Schiff's base aluminum complex shown in formula (I).
9. a preparation method for polycarbonate-polyester copolymer, including:
By carbon dioxide, epoxide, cyclic acid anhydride, catalyst and promoter hybrid reaction, obtain polycarbonate-polyester
Copolymer;
Described catalyst is to have structure Schiff's base aluminum complex or power shown in formula (I) described in claim 1~2 any one
Profit requires that prepared by the preparation method described in 3~4 any one has structure Schiff's base aluminum complex shown in formula (I).
Preparation method the most according to claim 9, it is characterised in that described promoter is double (dihalotriphenylphosphoranes base)
Ammonium chloride, DMAP, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1,5,7-tri-azabicyclic
One or many in [4.4.0] decyl-5-alkene, N-Methylimidazole., tricyclohexyl phosphine, tetrabutylammonium chloride and tetrabutyl ammonium bromide etc.
Kind.
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