CN108610475A - A kind of preparation method of polylactic acid-polycaprolactone co-polymer - Google Patents
A kind of preparation method of polylactic acid-polycaprolactone co-polymer Download PDFInfo
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- CN108610475A CN108610475A CN201810915636.7A CN201810915636A CN108610475A CN 108610475 A CN108610475 A CN 108610475A CN 201810915636 A CN201810915636 A CN 201810915636A CN 108610475 A CN108610475 A CN 108610475A
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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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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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
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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Abstract
The present invention provides a kind of preparation methods of polylactic acid poly caprolactone copolymer, include the following steps：Under the effect of schiff bases iron catalyst, lactide and the reaction of caprolactone ring opening copolymer obtain polylactic acid poly caprolactone copolymer；The schiff bases iron catalyst has Formulas I structure.The catalyst that the present invention is reacted using the schiff bases iron compound with Formulas I structure as lactide and caprolactone ring opening copolymer, improves conversion ratio.The conversion ratio of lactide is 85~95%；The conversion ratio of caprolactone is 90~98%；The number-average molecular weight of polylactic acid poly caprolactone copolymer is 0.7~6.7 ten thousand g/mol.The schiff bases iron compound that the present invention utilizes has iron activated centre, can be catalyzed lactide and caprolactone ring opening copolymer, and the adjustable copolymer of each component content of monomer is made.
Description
Technical field
The invention belongs to technical field of polymer more particularly to a kind of preparation methods of polylactic acid-polycaprolactone co-polymer.
Background technology
Polylactic acid and polycaprolactone are chemical synthesis biodegradation material, in packaging material, biological medicine and pharmacy work
It has a wide range of applications in industry.The two methods of synthesis generally use of polylactic acid, i.e. lactide (cyclic dimer of lactic acid) are opened
Cyclopolymerization and direct polycondensation of lactic acid.The method that wherein high molecular polylactic acid generally uses lactide ring-opening polymerisation, and
There are lot of documents and patent to carry out relevant report to lactide ring-opening polymerisation, such as the United States Patent (USP) of Patent No. US5235031
With the United States Patent (USP) of Patent No. US5357034, polycaprolactone similar to polylactic acid is also to be obtained using internal ester monomer ring-opening polymerisation
It arrives.
In order to obtain the polylactic acid of better performances, the prior art is frequently with levorotatory lactide or dextrorotation lactide low
Poison tin compound, as stannic chloride and stannous octoate catalytic action under carry out ring-opening polymerisation.Under the effect of tin series catalysts,
Ring-opening polymerisation obtains isotactic poly- dextrorotation lactide and poly- levorotatory lactide respectively by optically pure DLA, LLA, this two kinds
Polymer is the crystalline polymer of 180 DEG C of fusing point.But such pure polylactic acid is widely applied in all fields, but its list
One structure causes its more crisp disadvantage and limits its application, and opposite polycaprolactone material flexibility is preferable, and two kinds of materials
Direct physical blend due to the consistency problem of two kinds of materials, affect its direct application.Therefore development and application are needed
A kind of environmental-friendly nontoxic cheap ring-opening polymerization catalyst can be catalyzed lactide and be copolymerized to obtain function admirable with caprolactone
Copolymer.
Currently, about lactide and caprolactone copolymerization catalyst there are reports, such as Nomura reports Schiff
Alkali-Al catalysts are by a molecule 1, and 3- propane diamine and two molecule salicylides are condensed to yield schiff bases, then by a molecule Schiff
Alkali is obtained by the reaction with a molecule aluminium isopropoxide.But the schiff bases Al catalysts reported are copolymerized in catalysis lactide and caprolactone
When, the activity for being catalyzed reaction is relatively low, highly toxic aluminum metal residual, it is difficult to meet actual needs.
Invention content
In view of this, the purpose of the present invention is to provide a kind of preparation method of polylactic acid-polycaprolactone co-polymer, the system
Preparation Method has higher conversion ratio.
The present invention provides a kind of preparation methods of polylactic acid-polycaprolactone co-polymer, include the following steps：
Under the effect of schiff bases iron catalyst, lactide and the reaction of caprolactone ring opening copolymer obtain polylactic acid-polycaprolactone
Copolymer；
The schiff bases iron catalyst has Formulas I structure：
The Y is selected from-CH2-CH2-CH2-、-CH2-CH2-、-CH(CH3)-CH2-、Or-CH2-C(CH3)2-CH2-；
The R is selected from the alkyl or halogen of-H, C1~C5.
Preferably, the R is selected from-H, tertiary butyl or-Cl.
Preferably, the schiff bases iron catalyst is made in accordance with the following methods：
Schiff base ligand with Formula II structure is reacted in a solvent with ferric trichloride, obtains the seat with Formulas I structure
Husband's alkali iron compound；
The Y is selected from-CH2-CH2-CH2-、-CH2-CH2-、-CH(CH3)-CH2-、Or-CH2-C(CH3)2-CH2-；
The R is selected from the alkyl or halogen of-H, C1~C5.
Preferably, the schiff base ligand with Formula II structure is made in accordance with the following methods：
Diamine compound with formula III structure with the bigcatkin willow aldehyde compound with formula IV structure be condensed instead
It answers, obtains the schiff base ligand with Formula II structure；
In formula III, Y is selected from-CH2-CH2-CH2-、-CH2-CH2-、-CH(CH3)-CH2-、Or-CH2-C(CH3)2-
CH2-；
In formula IV, R is selected from the alkyl or halogen of-H, C1~C5.
Preferably, the amount ratio of the substance of the schiff bases iron catalyst and lactide is 1:50~1000；
The amount ratio of the substance of the schiff bases iron catalyst and caprolactone is 1:50~1000.
Preferably, the amount ratio of the substance of the lactide and caprolactone is 1:0.05~20.
Preferably, the temperature of the ring opening copolymer reaction is 25~140 DEG C；
The time of ring opening copolymer reaction is 1~72h.
Preferably, the solvent is selected from propylene oxide and/or 7-oxa-bicyclo[4.1.0.
The present invention provides a kind of preparation methods of polylactic acid-polycaprolactone co-polymer, include the following steps：In schiff bases
Under iron catalyst effect, lactide and the reaction of caprolactone ring opening copolymer obtain polylactic acid-polycaprolactone co-polymer；The Schiff
Alkali iron catalyst has Formulas I structure.The present invention is opened using the schiff bases iron compound with Formulas I structure as lactide and caprolactone
The catalyst of ring copolyreaction, improves conversion ratio.The experimental results showed that：The conversion ratio of lactide is 85~95%；Caprolactone
Conversion ratio be 90~98%；The number-average molecular weight of polylactic acid-polycaprolactone co-polymer is 0.7~6.7 ten thousand g/mol.
Specific implementation mode
The present invention provides a kind of preparation methods of polylactic acid-polycaprolactone co-polymer, include the following steps：
Under the effect of schiff bases iron catalyst, lactide and the reaction of caprolactone ring opening copolymer obtain polylactic acid-polycaprolactone
Copolymer；
The schiff bases iron catalyst has Formulas I structure：
The Y is selected from-CH2-CH2-CH2-、-CH2-CH2-、-CH(CH3)-CH2-、Or-CH2-C(CH3)2-CH2-；
The R is selected from the alkyl or halogen of-H, C1~C5.
The present invention is urged using the schiff bases iron compound with Formulas I structure as what lactide and caprolactone ring opening copolymer reacted
Agent improves conversion ratio.
In the present invention, the schiff bases iron catalyst has Formulas I structure：
The Y is selected from-CH2-CH2-CH2-、-CH2-CH2-、-CH(CH3)-CH2-、Or-CH2-C(CH3)2-CH2-；
The R is selected from the alkyl or halogen of-H, C1~C5；Preferably, R is selected from-H, tertiary butyl or-Cl.
In the present invention, the schiff bases iron catalyst is preferably made in accordance with the following methods：
Schiff base ligand with Formula II structure is reacted in a solvent with ferric trichloride, obtains the seat with Formulas I structure
Husband's alkali iron compound；
The Y is selected from-CH2-CH2-CH2-、-CH2-CH2-、-CH(CH3)-CH2-、Or-CH2-C(CH3)2-CH2-；
The R is selected from the alkyl or halogen of-H, C1~C5.
In the present invention, the schiff base ligand with Formula II structure is made in accordance with the following methods：
Diamine compound with formula III structure with the bigcatkin willow aldehyde compound with formula IV structure be condensed instead
It answers, obtains the schiff base ligand with Formula II structure；
In formula III, Y is selected from-CH2-CH2-CH2-、-CH2-CH2-、-CH(CH3)-CH2-、Or-CH2-C(CH3)2-
CH2-；
In formula IV, R is selected from the alkyl or halogen of-H, C1~C5.
In specific example of the present invention, have the diamine compound of formula III structure for rac-1,2- cyclohexanediamine, R, R-1,
2- cyclohexanediamine, 1,2- ethylenediamines, 1- methyl-1s, 2- ethylenediamines, 1,3- propane diamine or 2,2- dimethyl -1,3- propane diamine.
The bigcatkin willow aldehyde compound with formula IV structure is specially 3,5- di-tert-butyl salicylaldehydes or salicylide.
Diamine compound with formula III structure is preferably dissolved in ethyl alcohol by the present invention, obtains diamine compound solution；It will
Bigcatkin willow aldehyde compound with formula IV structure is dissolved in ethyl alcohol, obtains bigcatkin willow aldehydes compound solution；By the bigcatkin willow aldehydes
Compound solution is slowly added dropwise into the diamine compound solution with formula III structure, is heated to reflux, and be condensed anti-
It answers, obtains the schiff base ligand with Formula II structure.In the present invention, two amine compounds with structure shown in formula (III)
Object is preferably 1,2 cyclohexanediamine (rac, (R, R), (S, S)) or 1,3- propane diamine；In the diamine compound solution, the tool
It is preferably 0.1g/mL~0.5g/mL to have the mass concentration of the diamine compound of formula III structure, and more preferably 0.15g/mL~
0.3g/mL；The bigcatkin willow aldehyde compound with formula IV structure is preferably 3,5- di-tert-butyl salicylaldehydes or salicylide；It is described
In bigcatkin willow aldehydes compound solution, with formula IV structure bigcatkin willow aldehyde compound mass concentration be preferably 0.1g/mL~
0.5g/mL, more preferably 0.2g/mL~0.4g/mL.In the present invention, the temperature being heated to reflux is preferably 80 DEG C；It is described
The time being heated to reflux is preferably 8h~16h；More preferably 11h~13h；Most preferably 12h.
In the present invention, the diamine compound with formula III structure and the bigcatkin willow aldehydes chemical combination with formula IV structure
The amount of the substance of object is than preferably 1:2~4, more preferably 1:2.
After condensation reaction, the solution that the present invention preferably obtains the condensation reaction removes solvent, then will remove solvent
Reaction product recrystallized, to obtain that there is the schiff base ligand of Formula II structure.The present invention is to the solvent and again of going
The method of crystallization does not have special limitation, using the method well known to those skilled in the art for removing solvent and recrystallization.This
The solution that invention preferably obtains the condensation reaction carries out revolving and removes solvent therein, and the reaction product of solvent will be gone to use
Ethyl alcohol is recrystallized, and the schiff base ligand with Formula II structure is obtained.
After obtaining the schiff base ligand with Formula II structure, the present invention reacts it with ferric trichloride in a solvent, obtains
Schiff bases iron compound with Formulas I structure.Specifically, the present invention preferably under conditions of protecting gas, will have Formula II structure
Schiff base ligand solution and liquor ferri trichloridi be mixed, the schiff bases iron compound with Formulas I structure is obtained after reaction.
The protection gas is preferably high pure nitrogen.In the present invention, the schiff base ligand with Formula II structure and the tri-chlorination
The molar ratio of iron is preferably 1:1.The present invention is to the schiff base ligand solution with Formula II structure and liquor ferri trichloridi
Preparation method has no special limitation, using solution preparation method well known to those skilled in the art.It is described that there is Formula II
The solvent of the schiff base ligand solution of structure is preferably the mixed solvent of methanol either methanol and acetonitrile；It is described that there is Formula II knot
The molar concentration of the schiff base ligand solution of structure is preferably 0.5mol/L~2mol/L, more preferably 1mol/L~2mol/L.Institute
State the mixed solvent that the solvent in liquor ferri trichloridi is preferably methanol either methanol and acetonitrile；The liquor ferri trichloridi
Molar concentration is preferably 0.5mol/L~2mol/L, more preferably 1mol/L~2mol/L.The present invention has no spy to the solvent
Different limitation, it is preferred to use the mixed solvent of methanol either methanol and acetonitrile.
In the present invention, the temperature of the schiff base ligand and ferric chloride reaction is preferably 25 DEG C~60 DEG C, more preferably
It is 25~30 DEG C；The time of reaction is preferably 8h~12h, more preferably 9~10h.
After the reaction of the schiff base ligand and ferric trichloride with Formula II structure, the present invention is preferably reacted described
To solution remove solvent, then the reaction product of solvent will be gone to recrystallize, obtains the schiff bases iron chemical combination with Formulas I structure
Object.The present invention goes the method for solvent and recrystallization not have special limitation to described, is gone using well known to those skilled in the art
The method of solvent and recrystallization.Solution obtained by the reaction is preferably filtered and removes solvent therein by the present invention, will go
The reaction product of solvent is using methylene chloride/methanol, methylene chloride/methanol acetonitrile, acetonitrile/ethyl alcohol, acetone/ethanol mixed solvent
It is recrystallized, obtains the schiff bases iron compound with Formulas I structure.
The schiff bases iron compound that the present invention applies has iron atom center, with schiff bases aluminium center disclosed in the prior art
Catalyst compare, the schiff bases iron compound that the present invention applies can be catalyzed lactide and caprolactone ring opening copolymer, have it is honest and clean
Valence, catalyst metals remain nontoxic advantage.
In the present invention, the lactide is preferably selected from levorotatory lactide, dextrorotation lactide, levorotatory lactide and dextrorotation third
Lactide mixture.
The present invention preferably carries out ring opening copolymer reaction under the conditions of anhydrous and oxygen-free.The present invention can be by caprolactone and catalyst
It mixes in a solvent, stirs lower progress ring-opening polymerization polymer reaction, obtain polycaprolactone, the lactide list of corresponding amount is added later
Body continues to polymerize, obtains copolymer；The present invention can also mix caprolactone and lactide in a solvent with catalyst, stirring
Lower progress ring-opening polymerization polymer reaction, obtains the random copolymer of polylactic acid-polycaprolactone.Catalyst schiff bases iron compound is being opened
Higher catalytic activity is shown in ring copolyreaction.The present invention does not have the source of the lactide special limitation, uses
The commercial goods of lactide, the present invention preferably recrystallize the lactide of purchase, then carry out ring-opening polymerization.This
Invention is preferably first evaporated under reduced pressure caprolactone, then goes to carry out ring-opening polymerisation.
The present invention preferably carries out ring opening copolymer reaction in the presence of propylene oxide or 7-oxa-bicyclo[4.1.0.
The schiff bases iron compound reactivity that the present invention applies is higher, the dosage in catalyzing ring-opening polymerization of lactide compared with
Few, lower reaction temperature can be used in ring-opening polymerization.In the present invention, the object of the schiff bases iron catalyst and lactide
The amount of matter is than preferably 1:50~1000, more preferably 1：100~800, most preferably 1：100~400；The schiff bases iron is urged
The amount ratio of the substance of agent and caprolactone is preferably 1:50~1000, more preferably 1：100~800, most preferably 1：100~
400.The amount ratio of the substance of the lactide and caprolactone is preferably 1:0.05~20, more preferably 1:0.2~5, most preferably
1:0.5~2.
The temperature of the ring opening copolymer reaction is preferably 25~140 DEG C, more preferably 60 DEG C~100 DEG C, most preferably 60
℃；The time of ring opening copolymer reaction is preferably 1~72h, more preferably 15~30h, more preferably for 24 hours.
After reaction, the present invention is preferably added to chloroform dissolving polymer to ring opening copolymer, adds excessive ethyl alcohol
Precipitation polymers filter, and vacuum drying obtains polylactic acid-polycaprolactone co-polymer.Dosage of the present invention to the chloroform
There is no special limitation, obtained reaction product can be dissolved；The present invention does not have the filtering and dry method
Special limitation, using known to those skilled in the art and dry technical solution；The drying is preferred in the present invention
Time for vacuum drying, the drying is preferably for 24 hours~48h, most preferably 36h.
In order to further illustrate the present invention, with reference to embodiment to a kind of polylactic acid-polycaprolactone provided by the invention
The preparation method of copolymer is described in detail, but cannot they be interpreted as limiting the scope of the present invention.
Preparation example 1
By 1.14g rac-1,2 cyclohexanediamine are dissolved in 20mL ethyl alcohol, obtain rac-1,2 cyclohexanediamine solution；By 4.7g
3,5- di-tert-butyl salicylaldehydes are dissolved in 30mL ethyl alcohol, obtain 3,5- di-tert-butyl salicylaldehyde solution, by 3,5- di-t-butyl water
Poplar aldehyde solution is slowly added dropwise to rac-1,2 cyclohexanediamine solution, and obtained mixed solution flows back 12h at 80 DEG C, and it is mixed to obtain reaction
Close object；Obtained reaction product is obtained Schiff base ligand by the solvent being filtered to remove in reaction mixture using ethyl alcohol recrystallization；
Under conditions of high pure nitrogen is protected, after 1g Schiff base ligands are mixed with 0.4g ferric trichlorides, 20mL first is added
Alcohol is mixed, and obtained mixed solution is reacted 2h at 25 DEG C, completes that reaction system is filtered to remove solvent, dichloro after reacting
Methane/recrystallizing methanol；Obtain schiff bases iron compound.
Obtained schiff bases iron compound is carried out elemental analysis by the present invention, obtains the content of wherein each atom, as a result such as
Under：Elem.Anal. (%)：C 67.97, H 8.24, N 5.57；Found C 67.85, H 8.06, N 5.52.This explanation, this
The schiff bases iron compound that embodiment obtains has Formulas I structure, wherein Y isR is tertiary butyl.
Preparation example 2
1.14g R, R-1,2 cyclohexanediamine is dissolved in 20mL ethyl alcohol, rac-1,2 cyclohexanediamine solution are obtained；By 4.7g
3,5- di-tert-butyl salicylaldehydes are dissolved in 30mL ethyl alcohol, obtain 3,5- di-tert-butyl salicylaldehyde solution, by 3,5- di-t-butyl water
Poplar aldehyde solution is slowly added dropwise to rac-1,2 cyclohexanediamine solution, and obtained mixed solution flows back 12h at 80 DEG C, and it is mixed to obtain reaction
Close object；Obtained reaction product is obtained Schiff base ligand by the solvent being filtered to remove in reaction mixture using ethyl alcohol recrystallization；
Under conditions of high pure nitrogen is protected, after 1g Schiff base ligands are mixed with 0.4g ferric trichlorides, 20mL first is added
Alcohol is mixed, and obtained mixed solution is reacted 2h at 25 DEG C, completes that reaction system is filtered to remove solvent, dichloro after reacting
Methane/recrystallizing methanol；Obtain schiff bases iron compound.
Preparation example 3
1,2 ethylenediamines of 0.6g are dissolved in 20mL ethyl alcohol；5.0g 3,5- di-tert-butyl salicylaldehydes are dissolved in 30mL ethyl alcohol
In, 3,5- di-tert-butyl salicylaldehyde solution is obtained, 3,5- di-tert-butyl salicylaldehyde solution is slowly added dropwise molten to 1,2 ethylenediamine
Liquid, obtained mixed solution flow back 12h at 80 DEG C, obtain reaction mixture；The solvent being filtered to remove in reaction mixture, will
To reaction product Schiff base ligand is obtained using ethyl alcohol recrystallization；
Under conditions of high pure nitrogen is protected, after 1g Schiff base ligands are mixed with 0.45g ferric trichlorides, 20mL first is added
Alcohol is mixed, and obtained mixed solution is reacted 2h at 25 DEG C, completes that reaction system is filtered to remove solvent, dichloro after reacting
Methane/recrystallizing methanol；Obtain schiff bases iron compound.
Preparation example 4
By 0.75g 1- methyl-1s, 2 ethylenediamines are dissolved in 20mL ethyl alcohol；5.0g 3,5- di-tert-butyl salicylaldehydes are dissolved in
In 30mL ethyl alcohol, 3,5- di-tert-butyl salicylaldehyde solution is obtained, 3,5- di-tert-butyl salicylaldehyde solution is slowly added dropwise to 1- first
Base -1,2 ethylenediamine solution, obtained mixed solution flow back 12h at 80 DEG C, obtain reaction mixture；It is filtered to remove reaction mixing
Obtained reaction product is obtained Schiff base ligand by the solvent in object using ethyl alcohol recrystallization；
Under conditions of high pure nitrogen is protected, after 1g Schiff base ligands are mixed with 0.45g ferric trichlorides, 20mL first is added
Alcohol is mixed, and obtained mixed solution is reacted 2h at 25 DEG C, completes that reaction system is filtered to remove solvent, dichloro after reacting
Methane/recrystallizing methanol；Obtain schiff bases iron compound.
Preparation example 5
By 0.75g 1,3- propane diamine is dissolved in 20mL ethyl alcohol, obtains 1,3- propane diamine solution；5g salicylides are dissolved in
In 20mL ethyl alcohol, salicylide solution is obtained, salicylide solution is slowly added dropwise to 1,3- propane diamine solution, obtained mixed solution
Flow back 12h at 80 DEG C, obtains reaction mixture.The solvent being filtered to remove in reaction mixture uses obtained reaction product
Ethyl alcohol recrystallization obtains Schiff base ligand.
Under conditions of high pure nitrogen is protected, after 1g Schiff base ligands are mixed with 0.45g ferric trichlorides, 15mL first is added
Alcohol and 25mL acetonitriles are mixed, and obtained mixed solution is reacted 2h at 60 DEG C, reaction system is crossed after completion reaction and filters out
Go solvent, methylene chloride/methanol/recrystallized from acetonitrile；Obtain the schiff bases iron compound with Formulas I structure, wherein Y is-CH2-
CH2-CH2-；R is-H.
Preparation example 6
1.02g 2,2- dimethyl -1,3- propane diamine is dissolved in 20mL ethyl alcohol；By 5.0g 3,5- di-tert-butyl salicylaldehydes
Be dissolved in 30mL ethyl alcohol, obtain 3,5- di-tert-butyl salicylaldehyde solution, by 3,5- di-tert-butyl salicylaldehyde solution be slowly added dropwise to
2,2- dimethyl -1,3- propane diamine solution, obtained mixed solution flow back 12h at 80 DEG C, obtain reaction mixture；It is filtered to remove
Obtained reaction product is obtained Schiff base ligand by the solvent in reaction mixture using ethyl alcohol recrystallization；
Under conditions of high pure nitrogen is protected, after 1g Schiff base ligands are mixed with 0.35g ferric trichlorides, 20mL first is added
Alcohol is mixed, and obtained mixed solution is reacted 2h at 25 DEG C, completes that reaction system is filtered to remove solvent, dichloro after reacting
Methane/recrystallizing methanol；Obtain schiff bases iron compound.
Preparation example 7
0.75g 1,3- propane diamine is dissolved in 20mL ethyl alcohol；3.0g salicylides are dissolved in 30mL ethyl alcohol, bigcatkin willow is obtained
Salicylide solution is slowly added dropwise to 1,3- propane diamine solution aldehyde solution, and obtained mixed solution flows back 12h at 80 DEG C, obtains
Reaction mixture；Obtained reaction product is obtained Schiff by the solvent being filtered to remove in reaction mixture using ethyl alcohol recrystallization
Aar ligand；
Under conditions of high pure nitrogen is protected, after 1g Schiff base ligands are mixed with 0.6g ferric trichlorides, 20mL first is added
Alcohol is mixed, and obtained mixed solution is reacted 2h at 25 DEG C, completes that reaction system is filtered to remove solvent, dichloro after reacting
Methane/recrystallizing methanol；Obtain schiff bases iron compound.
Preparation example 8
By 0.75g 1- methyl-1s, 2 ethylenediamines are dissolved in 20mL ethyl alcohol；4.0g 3,5- dichloro-salicylaldehydes are dissolved in 30mL
In ethyl alcohol, 3,5- dichloro-salicylaldehyde's solution is obtained, 3,5- di-tert-butyl salicylaldehyde solution is slowly added dropwise to 1- methyl-1s, 2 second
Diamine solution, obtained mixed solution flow back 12h at 80 DEG C, obtain reaction mixture；It is filtered to remove molten in reaction mixture
Obtained reaction product is obtained Schiff base ligand by agent using ethyl alcohol recrystallization；
Under conditions of high pure nitrogen is protected, after 1g Schiff base ligands are mixed with 0.5g ferric trichlorides, 20mL first is added
Alcohol is mixed, and obtained mixed solution is reacted 2h at 25 DEG C, completes that reaction system is filtered to remove solvent, dichloro after reacting
Methane/recrystallizing methanol；Obtain schiff bases iron compound.
Embodiment 1
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 20.0mmol were evaporated under reduced pressure
Caprolactone, 0.2mmol preparations example 1 prepare catalyst mixed with 20mL propylene oxide, by obtained mixed solution at 80 DEG C
It is stirred to react for 24 hours, 10mL chloroforms is added into obtained reaction solution and dissolve polymer, then excessive ethyl alcohol is heavy thereto
Shallow lake polymer, filtering are dried in vacuo 48h, obtain polylactic acid and polycaprolactone co-polymer.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.2g；The conversion ratio of lactide is
93%；The conversion ratio of caprolactone is 96%；
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 48 to the molar ratio of lactide in copolymer and caprolactone:52；
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.8 ten thousand.
Embodiment 2
The copolymer of polylactic acid and polycaprolactone is prepared using the technical solution of embodiment 1 by the present invention, unlike,
The schiff bases iron compound prepared using preparation example 2 is as catalyst.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.3g；The conversion ratio of lactide is
93%；The conversion ratio of caprolactone is 95%；
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 49 to the molar ratio of lactide in copolymer and caprolactone:51；
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.8 ten thousand；
Embodiment 3
The copolymer of polylactic acid and polycaprolactone is prepared using the technical solution of embodiment 1 by the present invention, unlike,
The schiff bases iron compound that the present embodiment is prepared using preparation example 3 is as catalyst.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.0g；The conversion ratio of lactide is
93%；The conversion ratio of caprolactone is 95%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 50 to the molar ratio of lactide in copolymer and caprolactone:50；
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.6 ten thousand；
Embodiment 4
The copolymer of polylactic acid and polycaprolactone is prepared using the technical solution of embodiment 1 by the present invention, unlike,
The schiff bases iron compound that the present embodiment is prepared using preparation example 4 is as catalyst.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.0g；The conversion ratio of lactide is
94%；The conversion ratio of caprolactone is 96%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 53 to the molar ratio of lactide in copolymer and caprolactone:47；
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.9 ten thousand.
Embodiment 5
The copolymer of polylactic acid and polycaprolactone is prepared using the technical solution of embodiment 1 by the present invention, unlike,
The schiff bases iron compound that the present embodiment is prepared using preparation example 5 is as catalyst.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.5g；The conversion ratio of lactide is
95%；The conversion ratio of caprolactone is 98%.
This present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition,
It is 50 to obtain the molar ratio of lactide and caprolactone in copolymer:50；
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 2.0 ten thousand.
Embodiment 6
The copolymer of polylactic acid and polycaprolactone is prepared using the technical solution of embodiment 1 by the present invention, unlike,
The schiff bases iron compound that the present embodiment is prepared using preparation example 6 is as catalyst.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 3.8g；The conversion ratio of lactide is
90%；The conversion ratio of caprolactone is 94%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 47 to the molar ratio of lactide in copolymer and caprolactone:53；
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.8 ten thousand.
Embodiment 7
The copolymer of polylactic acid and polycaprolactone is prepared using the technical solution of embodiment 1 by the present invention, unlike,
The schiff bases iron compound that the present embodiment is prepared using preparation example 7 is as catalyst.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.2g；The conversion ratio of lactide is
93%；The conversion ratio of caprolactone is 91%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 54 to the molar ratio of lactide in copolymer and caprolactone:46.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.7 ten thousand.
Embodiment 8
The copolymer of polylactic acid and polycaprolactone is prepared using the technical solution of embodiment 1 by the present invention, unlike,
The schiff bases iron compound that the present embodiment is prepared using preparation example 8 is as catalyst.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.3g；The conversion ratio of lactide is
89%；The conversion ratio of caprolactone is 93%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 48 to the molar ratio of lactide in copolymer and caprolactone:52.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.9 ten thousand.
Embodiment 9
Polylactic acid and polycaprolactone co-polymer is prepared using the technical solution of embodiment 1 in the present invention, unlike, this
Embodiment replaces the levorotatory lactide that embodiment 1 uses using dextrorotation lactide.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.2g；The conversion ratio of lactide is
93%；The conversion ratio of caprolactone is 95%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 49 to the molar ratio of lactide in copolymer and caprolactone:51.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.8 ten thousand.
Embodiment 10
Polylactic acid and polycaprolactone co-polymer is prepared using the technical solution of embodiment 1 in the present invention, unlike, this
Embodiment replaces the left-handed of the use of embodiment 1 using the mixture of 10.0mmol dextrorotation lactide and 10.0mmol levorotatory lactides
Lactide.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.1g；The conversion ratio of lactide is
92%；The conversion ratio of caprolactone is 96%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 47 to the molar ratio of lactide in copolymer and caprolactone:53.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 0.8 ten thousand.
Embodiment 11
Polylactic acid and polycaprolactone co-polymer is prepared using the technical solution of embodiment 1 in the present invention, unlike, this
Embodiment replaces the propylene oxide that embodiment 1 uses using 7-oxa-bicyclo[4.1.0.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.0g；The conversion ratio of lactide is
91%；The conversion ratio of caprolactone is 95%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 48 to the molar ratio of lactide in copolymer and caprolactone:52.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.7 ten thousand.
Embodiment 12
The schiff bases iron catalyst of the present embodiment application has Formulas I structure, and wherein Y is 1,3- propane diamine and R is tertiary butyl.
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 10.0mmol was recrystallized, 10.0mmol were evaporated under reduced pressure
Caprolactone, 0.2mmol catalyst mixes with 20mL propylene oxide, and obtained mixed solution is stirred to react 72h at 25 DEG C, to
10mL chloroforms are added in obtained reaction solution and dissolve polymer, then excessive ethanol precipitation polymer thereto, filter,
It is dried in vacuo 48h, obtains polylactic acid and polycaprolactone co-polymer.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 1.8g；The conversion ratio of lactide is
85%；The conversion ratio of caprolactone is 90%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 46 to the molar ratio of lactide in copolymer and caprolactone:54.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 0.7 ten thousand.
Embodiment 13
The copolymer of polylactic acid and polycaprolactone is prepared using the technical solution of embodiment 12 by the present invention, different
It is that the present embodiment is stirred to react 48h using 60 DEG C and is stirred to react 72h instead of 25 DEG C of the use of embodiment 12.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 1.7g；The conversion ratio of lactide is
92%；The conversion ratio of caprolactone is 90%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 51 to the molar ratio of lactide in copolymer and caprolactone:49.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 0.9 ten thousand.
Embodiment 14
The schiff bases iron catalyst of the present embodiment application has Formulas I structure, and wherein Y is 1,3- propane diamine and R is tertiary butyl.
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 20.0mmol were evaporated under reduced pressure
Caprolactone, 0.2mmol catalyst mixes with 20mL propylene oxide, and obtained mixed solution is stirred to react 12h at 100 DEG C,
10mL chloroforms are added into obtained reaction solution and dissolve polymer, then excessive ethanol precipitation polymer thereto, mistake
Filter is dried in vacuo 48h, obtains polylactic acid and polycaprolactone co-polymer.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 3.7g；The conversion ratio of lactide is
94%；The conversion ratio of caprolactone is 96%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 51 to the molar ratio of lactide in copolymer and caprolactone:49.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.6 ten thousand.
Embodiment 15
The schiff bases iron catalyst of the present embodiment application has Formulas I structure, and wherein Y is 1,3- propane diamine and R is tertiary butyl.
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 10.0mmol was recrystallized, 10.0mmol were evaporated under reduced pressure
Caprolactone, 0.2mmol catalyst mixes with 20mL propylene oxide, and obtained mixed solution is stirred to react 1h at 140 DEG C, to
10mL chloroforms are added in obtained reaction solution and dissolve polymer, then excessive ethanol precipitation polymer thereto, filter,
It is dried in vacuo 48h, obtains polylactic acid and polycaprolactone co-polymer.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 1.6g；The conversion ratio of lactide is
94%；The conversion ratio of caprolactone is 97%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 43 to the molar ratio of lactide in copolymer and caprolactone:57.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 0.7 ten thousand.
Embodiment 16
The schiff bases iron catalyst of the present embodiment application has Formulas I structure, and wherein Y is 1,3- propane diamine and R is tertiary butyl.
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 20.0mmol were evaporated under reduced pressure
Caprolactone, 0.1mmol catalyst mixes with 20mL propylene oxide, and obtained mixed solution is stirred to react 48h at 80 DEG C, to
10mL chloroforms are added in obtained reaction solution and dissolve polymer, then excessive ethanol precipitation polymer thereto, filter,
It is dried in vacuo 48h, obtains polylactic acid and polycaprolactone co-polymer.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 4.2g；The conversion ratio of lactide is
94%；The conversion ratio of caprolactone is 96%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 50 to the molar ratio of lactide in copolymer and caprolactone:50.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 3.2 ten thousand.
Embodiment 17
The schiff bases iron catalyst of the present embodiment application has structure shown in Formulas I, and wherein Y is 1,3- propane diamine and R is uncle
Butyl.
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 20.0mmol were evaporated under reduced pressure
Caprolactone, 0.04mmol catalyst mixes with 20mL propylene oxide, and obtained mixed solution is stirred to react 48h at 80 DEG C,
10mL chloroforms are added into obtained reaction solution and dissolve polymer, then excessive ethanol precipitation polymer thereto, mistake
Filter is dried in vacuo 48h, obtains polylactic acid and polycaprolactone co-polymer.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 3.6g；The conversion ratio of lactide is
85%；The conversion ratio of caprolactone is 90%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 42 to the molar ratio of lactide in copolymer and caprolactone:58.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 6.7 ten thousand.
Embodiment 18
The schiff bases iron catalyst of the present embodiment application has structure shown in Formulas I, and wherein Y is 1,3- propane diamine and R is uncle
Butyl.
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 2.0mmol were evaporated under reduced pressure
Caprolactone, 0.2mmol catalyst are mixed with 20mL propylene oxide, obtained mixed solution are stirred to react for 24 hours at 60 DEG C, Xiang get
To reaction solution in 10mL chloroforms be added dissolve polymer, then excessive ethanol precipitation polymer thereto, filtering, very
The dry 48h of sky, obtains polylactic acid and polycaprolactone co-polymer.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 2.2g；The conversion ratio of lactide is
88%；The conversion ratio of caprolactone is 97%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 88 to the molar ratio of lactide in copolymer and caprolactone:12.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.1 ten thousand.
Embodiment 19
Polylactic acid and polycaprolactone co-polymer is prepared using the technical solution of embodiment 18 in the present invention, unlike,
The 2.0mmol that the caprolactone that the present embodiment was evaporated under reduced pressure using 4.0mmol replaces embodiment 18 to use be evaporated under reduced pressure oneself
Lactone.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 2.6g；The conversion ratio of lactide is
90%；The conversion ratio of caprolactone is 95%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 81 to the molar ratio of lactide in copolymer and caprolactone:19.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.1 ten thousand.
Embodiment 20
Polylactic acid and polycaprolactone co-polymer is prepared using the technical solution of embodiment 18 in the present invention, unlike,
The 2.0mmol that the caprolactone that the present embodiment was evaporated under reduced pressure using 6.6mmol replaces embodiment 18 to use be evaporated under reduced pressure oneself
Lactone.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 3.0g；The conversion ratio of lactide is
90%；The conversion ratio of caprolactone is 96%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 70 to the molar ratio of lactide in copolymer and caprolactone:30.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.3 ten thousand.
Embodiment 21
Polylactic acid and polycaprolactone co-polymer is prepared using the technical solution of embodiment 18 in the present invention, unlike,
The 2.0mmol that the caprolactone that the present embodiment was evaporated under reduced pressure using 10.0mmol replaces embodiment 18 to use be evaporated under reduced pressure oneself
Lactone.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 3.2g；The conversion ratio of lactide is
93%；The conversion ratio of caprolactone is 96%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 62 to the molar ratio of lactide in copolymer and caprolactone:38.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.4 ten thousand.
Embodiment 22
The schiff bases iron catalyst of the present embodiment application has Formulas I structure, and wherein Y is 1,3- propane diamine and R is tertiary butyl.
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 2.0mmol was recrystallized, 20.0mmol were evaporated under reduced pressure
Caprolactone, 0.2mmol catalyst are mixed with 20mL propylene oxide, obtained mixed solution are stirred to react for 24 hours at 60 DEG C, Xiang get
To reaction solution in 10mL chloroforms be added dissolve polymer, then excessive ethanol precipitation polymer thereto, filtering, very
The dry 48h of sky, obtains polylactic acid and polycaprolactone co-polymer.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 1.7g；The conversion ratio of lactide is
93%；The conversion ratio of caprolactone is 90%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 8 to the molar ratio of lactide in copolymer and caprolactone:92.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 0.7 ten thousand.
Embodiment 23
Polylactic acid and polycaprolactone co-polymer is prepared using the technical solution of embodiment 22 in the present invention, unlike,
The left side that the 2.0mmol that the levorotatory lactide that the present embodiment was recrystallized using 4.0mmol replaces embodiment 22 to use was recrystallized
Revolve lactide.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 2.4g；The conversion ratio of lactide is
94%；The conversion ratio of caprolactone is 94%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 15 to the molar ratio of lactide in copolymer and caprolactone:85.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 0.8 ten thousand.
Embodiment 24
Polylactic acid and polycaprolactone co-polymer is prepared using the technical solution of embodiment 22 in the present invention, unlike,
The left side that the 2.0mmol that the levorotatory lactide that the present embodiment was recrystallized using 6.6mmol replaces embodiment 22 to use was recrystallized
Revolve lactide.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 2.9g；The conversion ratio of lactide is
95%；The conversion ratio of caprolactone is 96%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 22 to the molar ratio of lactide in copolymer and caprolactone:78.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 0.8 ten thousand.
Embodiment 25
Polylactic acid and polycaprolactone co-polymer is prepared using the technical solution of embodiment 22 in the present invention, unlike,
The left side that the 2.0mmol that the levorotatory lactide that the present embodiment was recrystallized using 10.0mmol replaces embodiment 22 to use was recrystallized
Revolve lactide.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone co-polymer to be 3.2g；The conversion ratio of lactide is
94%；The conversion ratio of caprolactone is 97%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 29 to the molar ratio of lactide in copolymer and caprolactone:71.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 0.9 ten thousand.
Embodiment 26
The schiff bases iron catalyst of the present embodiment application has Formulas I structure, and wherein Y is 1,3- propane diamine and R is tertiary butyl.
Under conditions of anhydrous and oxygen-free, the caprolactone that 20.0mmol was evaporated under reduced pressure, 0.2mmol catalyst and 20mL epoxies
Propane mixes, and obtained mixed solution is stirred to react 12h at 60 DEG C, recrystallizes 20.0mmol into obtained reaction solution
The levorotatory lactide crossed is stirred to react 12h at 60 DEG C again, and 10mL chloroforms are added and dissolve polymer, then excessive second thereto
Alcohol precipitation polymers, filtering are dried in vacuo 48h, obtain polylactic acid and polycaprolactone co-polymer.
The present invention weighs to obtain polylactic acid and the quality of polycaprolactone block polymer to be 4.0g；The conversion ratio of lactide is
94%；The conversion ratio of caprolactone is 97%.
The present invention utilizes1H NMR analyze the polylactic acid that the present embodiment obtains with polycaprolactone co-polymer composition, obtain
It is 47 to the molar ratio of lactide in copolymer and caprolactone:53.
The present invention using polystyrene as reference substance, the present embodiment is obtained using gel permeation chromatography polylactic acid with gather oneself
Lactone copolymers are analyzed, and the number-average molecular weight for obtaining copolymer is 1.7 ten thousand.
As seen from the above embodiment, the present invention provides a kind of preparation methods of polylactic acid-polycaprolactone co-polymer, including
Following steps：Under the effect of schiff bases iron catalyst, lactide and the reaction of caprolactone ring opening copolymer obtain polylactic acid-and gather in oneself
Ester copolymer；The schiff bases iron catalyst has Formulas I structure.The present invention is made with the schiff bases iron compound with Formulas I structure
For the catalyst that lactide and caprolactone ring opening copolymer react, conversion ratio is improved.The experimental results showed that：The conversion ratio of lactide
It is 85~95%；The conversion ratio of caprolactone is 90%~98%；The number-average molecular weight of polylactic acid-polycaprolactone co-polymer is 0.7
~6.7 ten thousand g/mol.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of polylactic acid-polycaprolactone co-polymer, includes the following steps：
Under the effect of schiff bases iron catalyst, ring opening copolymer reacts in a solvent for lactide and caprolactone, obtains polylactic acid-and gathers oneself
Lactone copolymers；
The schiff bases iron catalyst has Formulas I structure：
The Y is selected from-CH2-CH2-CH2-、-CH2-CH2-、-CH(CH3)-CH2-、Or-CH2-C(CH3)2-CH2-；
The R is selected from the alkyl or halogen of-H, C1~C5.
2. preparation method according to claim 1, which is characterized in that the R is selected from-H, tertiary butyl or-Cl.
3. preparation method according to claim 1, which is characterized in that the schiff bases iron catalyst is made in accordance with the following methods
：
Schiff base ligand with Formula II structure is reacted in a solvent with ferric trichloride, obtains the schiff bases with Formulas I structure
Iron compound；
The Y is selected from-CH2-CH2-CH2-、-CH2-CH2-、-CH(CH3)-CH2-、Or-CH2-C(CH3)2-CH2-；
The R is selected from the alkyl or halogen of-H, C1~C5.
4. preparation method according to claim 3, which is characterized in that the schiff base ligand with Formula II structure according to
Following methods are made：
Diamine compound with formula III structure is subjected to condensation reaction with the bigcatkin willow aldehyde compound with formula IV structure, is obtained
To the schiff base ligand with Formula II structure；
In formula III, Y is selected from-CH2-CH2-CH2-、-CH2-CH2-、-CH(CH3)-CH2-、Or-CH2-C(CH3)2-CH2-；
In formula IV, R is selected from the alkyl or halogen of-H, C1~C5.
5. preparation method according to claim 1, which is characterized in that the substance of the schiff bases iron catalyst and lactide
Amount ratio be 1:50~1000；
The amount ratio of the substance of the schiff bases iron catalyst and caprolactone is 1:50~1000.
6. preparation method according to claim 1, which is characterized in that the amount ratio of the substance of the lactide and caprolactone is
1:0.05~20.
7. preparation method according to claim 1, which is characterized in that the temperature of the ring opening copolymer reaction is 25~140
℃；
The time of ring opening copolymer reaction is 1~72h.
8. preparation method according to claim 1, which is characterized in that the solvent is selected from propylene oxide and/or epoxide ring
Hexane.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827200A (en) * | 2012-09-18 | 2012-12-19 | 华东理工大学 | Nitrogenous bisphenol oxygroup ligand titanium compound and preparation method thereof and application thereof |
| CN107033193A (en) * | 2017-06-08 | 2017-08-11 | 中国科学院长春应用化学研究所 | A kind of schiff bases iron compound, its preparation method and its application as catalyst |
| CN107417739A (en) * | 2017-06-08 | 2017-12-01 | 中国科学院长春应用化学研究所 | A kind of schiff bases iron compound, its preparation method and its application as catalyst |
-
2018
- 2018-08-13 CN CN201810915636.7A patent/CN108610475A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827200A (en) * | 2012-09-18 | 2012-12-19 | 华东理工大学 | Nitrogenous bisphenol oxygroup ligand titanium compound and preparation method thereof and application thereof |
| CN107033193A (en) * | 2017-06-08 | 2017-08-11 | 中国科学院长春应用化学研究所 | A kind of schiff bases iron compound, its preparation method and its application as catalyst |
| CN107417739A (en) * | 2017-06-08 | 2017-12-01 | 中国科学院长春应用化学研究所 | A kind of schiff bases iron compound, its preparation method and its application as catalyst |
Non-Patent Citations (1)
| Title |
|---|
| RANLONG DUAN ET AL.: "Air-Stable Salen−Iron Complexes:Stereoselective Catalysts for Lactide and ε‑Caprolactone Polymerization through in Situ Initiation", 《MACROMOLECULES》 * |
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