CN107417739A - A kind of schiff bases iron compound, its preparation method and its application as catalyst - Google Patents
A kind of schiff bases iron compound, its preparation method and its application as catalyst Download PDFInfo
- Publication number
- CN107417739A CN107417739A CN201710427802.4A CN201710427802A CN107417739A CN 107417739 A CN107417739 A CN 107417739A CN 201710427802 A CN201710427802 A CN 201710427802A CN 107417739 A CN107417739 A CN 107417739A
- Authority
- CN
- China
- Prior art keywords
- present
- schiff bases
- pla
- iron compound
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002262 Schiff base Substances 0.000 title claims abstract description 135
- -1 schiff bases iron compound Chemical class 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 60
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 53
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 49
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 49
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 37
- 240000000203 Salix gracilistyla Species 0.000 claims description 15
- 238000006482 condensation reaction Methods 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000178 monomer Substances 0.000 abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052742 iron Inorganic materials 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 110
- 239000004626 polylactic acid Substances 0.000 description 110
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 46
- 229920000642 polymer Polymers 0.000 description 39
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 36
- 238000004458 analytical method Methods 0.000 description 33
- 239000004793 Polystyrene Substances 0.000 description 24
- 238000005227 gel permeation chromatography Methods 0.000 description 24
- 239000011259 mixed solution Substances 0.000 description 24
- 229920002223 polystyrene Polymers 0.000 description 24
- 239000012925 reference material Substances 0.000 description 24
- 238000005303 weighing Methods 0.000 description 24
- 238000003756 stirring Methods 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000012869 ethanol precipitation Methods 0.000 description 18
- 239000001294 propane Substances 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 17
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- RRIQVLZDOZPJTH-UHFFFAOYSA-N 3,5-di-tert-butyl-2-hydroxybenzaldehyde Chemical class CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1 RRIQVLZDOZPJTH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 210000000481 breast Anatomy 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- SSJXIUAHEKJCMH-WDSKDSINSA-N (1s,2s)-cyclohexane-1,2-diamine Chemical compound N[C@H]1CCCC[C@@H]1N SSJXIUAHEKJCMH-WDSKDSINSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YJSATLBWFLERNZ-UHFFFAOYSA-N 2-[2-(2-aminophenyl)ethenyl]aniline Chemical class NC1=CC=CC=C1C=CC1=CC=CC=C1N YJSATLBWFLERNZ-UHFFFAOYSA-N 0.000 description 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229940008309 acetone / ethanol Drugs 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a kind of schiff bases iron compound, its preparation method and its application as catalyst, schiff bases iron compound provided by the invention, there is structure shown in formula (I), wherein, Y CH2‑CH2‑CH2Or
Description
Technical field
The present invention relates to technical field of polymer, more particularly to a kind of schiff bases iron compound, its preparation method and its work
For the application of catalyst.
Background technology
PLA and polycaprolactone are the biodegradation materials of chemical synthesis, in packaging material, biological medicine and pharmacy work
Had a wide range of applications in industry.The two methods of synthesis generally use of PLA, i.e. lactide (cyclic dimer of lactic acid) are opened
Cyclopolymerization and direct polycondensation of lactic acid.The method that wherein high molecular PLA typically 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 Patent No. US5235031 United States Patent (USP)
With Patent No. US5357034 United States Patent (USP).The polycaprolactone similar to PLA is also to use internal ester monomer ring-opening polymerisation
Obtain.
Lactide is divided into three kinds of optical isomers：Levorotatory lactide (LLA), dextrorotation lactide (DLA) and meso third are handed over
Ester, its structure difference are as follows：
Machinery, processing and the degraded property of PLA of the spatial configuration of lactide to obtaining have conclusive work
With.In order to obtain the PLA of better performances, prior art is frequently with levorotatory lactide or dextrorotation lactide nontoxic
Under the catalytic action of tin compound such as stannic chloride and stannous octoate, ring-opening polymerisation is carried out.Under the effect of tin series catalysts, optics
Ring-opening polymerisation obtains isotactic poly- dextrorotation lactide and poly- levorotatory lactide respectively by pure DLA, LLA, this two kinds polymerizations
Thing is the crystalline polymer of 180 DEG C of fusing point.But the product of rac-lactide ring-opening polymerisation under the same conditions is non-knot
Crystalline substance atactic polymer.Compared with amorphism PLA, the use temperature range of crystalline polymer is wider, can approach melting
Temperature.Because rac-lactide price is relatively low, it is therefore desirable to develop it is a kind of to rac-lactide polymerization have stereoselectivity
Ring-opening polymerization catalyst, rac-lactide can be polymerize and obtain crystalline polylactic acid.
At present, on the catalyst of lactide stereoselectivity ring-opening polymerisation, there are reports, such as Coates reports
Schiff bases-Al catalysts (Salbinap) AlOMe be that dinaphthyl and two molecule bigcatkin willows are connected by a molecule 2,2'- diaminostilbenes, 1'-
Aldehyde is condensed to yield schiff bases, then reacts to obtain by a molecule schiff bases and a molecule aluminium isopropoxide；The reports such as Zhong Zhiyuan
(cyclohexylsalen) AlOiPr catalyst, it is by a molecule 1,2- hexamethylenes diamino and two molecules 3,5- di-t-butyl bigcatkin willows
Aldehyde is condensed to yield schiff bases, then reacts to obtain by a molecule schiff bases and a molecule aluminium isopropoxide.But the Schiff reported
For base catalyst in catalyzing ring-opening polymerization of lactide and catalysis caprolactone ring-opening polymerisation, the activity of catalytic reaction is relatively low, very
Hardly possible meets to be actually needed.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of schiff bases iron compound, its preparation method
And its application as catalyst, schiff bases iron compound catalyzing ring-opening polymerization of lactide provided by the invention prepare PLA
When, there is higher catalytic activity；When catalysis caprolactone polymerization prepares polycaprolactone, it may have higher catalytic activity.
The invention provides a kind of schiff bases iron compound, has structure shown in formula (I)：
Wherein, Y is-CH2-CH2-CH2- or
R is-H or alkyl.
Preferably, the alkyl that the R is-H or carbon number is 1~5.
Present invention also offers a kind of preparation method of schiff bases iron compound, comprise the following steps：
To there is the Schiff base ligand of structure shown in formula (II) to be reacted in a solvent with ferric trichloride, obtain with formula (I)
The schiff bases iron compound of shown structure；
Wherein, Y is-CH2-CH2-CH2- or
R is-H or alkyl.
Preferably, the Schiff base ligand of structure is prepared according to following steps shown in the formula (II)：
Will be with the amine compound of structure shown in formula (III) and the bigcatkin willow aldehyde compound with structure shown in formula (IV)
Condensation reaction is carried out, obtains the Schiff base ligand with structure shown in formula (II)；
Wherein, Y is-CH2-CH2-CH2- or
R is-H or alkyl.
Preferably, it is described with the amine compound of structure shown in formula (III) and described with structure shown in formula (IV)
The mol ratio of bigcatkin willow aldehyde compound is 1:(2~4).
Preferably, the condensation reaction is carried out under reflux conditions；
The time of the condensation reaction is 8h~16h.
Preferably, the mol ratio with the Schiff base ligand of structure shown in formula (II) and the ferric trichloride is 1:1.
Preferably, the temperature of the reaction is 25 DEG C~60 DEG C；The time of the reaction is 8h~12h.
Present invention also offers a kind of preparation method of PLA, comprise the following steps：
Lactide is mixed with catalyst, ring-opening polymerization is carried out in a solvent, obtains PLA；
The schiff bases iron compound that the catalyst is above-mentioned schiff bases iron compound or above-mentioned preparation method is prepared.
Preferably, the mol ratio 1 of the catalyst and the lactide:(50~1000).
Preferably, the temperature of the ring-opening polymerization is 25 DEG C~140 DEG C；
The time of the ring-opening polymerization is 1h~48h.
Present invention also offers a kind of preparation method of polycaprolactone, comprise the following steps：
Caprolactone is mixed with catalyst, ring-opening polymerization is carried out in a solvent, obtains polycaprolactone；
The schiff bases iron compound that the catalyst is above-mentioned schiff bases iron compound or above-mentioned preparation method is prepared.
Preferably, the mol ratio 1 of the catalyst and the caprolactone:(50~1000).
Preferably, the temperature of the ring-opening polymerization is 25 DEG C~100 DEG C；
The time of the ring-opening polymerization is 1h~48h.
The invention provides a kind of schiff bases iron compound, has structure shown in formula (I),
Wherein, Y is-CH2-CH2-CH2- orR is-H or alkyl.
Schiff bases iron compound provided by the invention has NNOO quad-tree index abilities, so as to be formed in a metal active
Heart binding site, four-coordination schiff bases iron catalyst can be obtained.The schiff bases iron compound is used to be catalyzed third by the present invention
The ring-opening polymerisation of lactide and caprolactone, the ring-opening polymerisation of ring-opening polymerisation and caprolactone of the schiff bases iron catalyst to lactide have
Very high catalytic activity.Test result indicates that the monomer conversion that method provided by the invention prepares PLA can reach
90%, the monomer conversion of polycaprolactone can reach 99%.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention,
The every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, belongs to this hair
The scope of bright protection.
The invention provides a kind of schiff bases iron compound, has structure shown in formula (I)：
Wherein, Y is-CH2-CH2-CH2- or
R is-H or alkyl.
Specifically, the alkyl that the R is preferably-H or carbon number is 1~5；More preferably-H, methyl or the tert-butyl group.
Schiff bases iron compound provided by the invention has the iron center of high activity, with prior art disclosed in schiff bases aluminium
The catalyst at center is compared, and schiff bases iron compound provided by the invention is in catalysis lactide and caprolactone ring-opening polymerization
When, there is very high activity, room temperature is that the polymerization of monomer can be achieved, while has suitable selection to rac-lactide
Property, improve the regularity of polymerizate microstructure of molecular chain.
Present invention also offers a kind of preparation method of schiff bases iron compound, comprise the following steps：
To there is the Schiff base ligand of structure shown in formula (II) to be reacted in a solvent with ferric trichloride, obtain with formula (I)
The schiff bases iron compound of shown structure；
Wherein, Y is-CH2-CH2-CH2- or
R is-H or alkyl.
The alkyl that the R is preferably-H or carbon number is 1~5；More preferably-H, methyl or the tert-butyl group.
The present invention is so that with the schiff bases of structure and ferric trichloride shown in formula (II), as raw material, reaction is obtained with formula (I)
The schiff bases iron compound of shown structure.In the present invention, it is described that there is the Schiff base ligand of structure shown in formula (II) preferably to press
Prepared according to following steps：
Will be with the amine compound of structure shown in formula (III) and the bigcatkin willow aldehyde compound with structure shown in formula (IV)
Condensation reaction is carried out, obtains the Schiff base ligand with structure shown in formula (II)；
Wherein, Y is-CH2-CH2-CH2- or
R is-H or alkyl.
The alkyl that the R is preferably-H or carbon number is 1~5；More preferably-H, methyl or the tert-butyl group.
Specifically, the present invention preferably will be with the diamine compound of structure shown in formula (III) and with knot formula (IV) Suo Shi
The bigcatkin willow aldehyde compound of structure mixes in ethanol, is heated to reflux, and carries out condensation reaction, obtains having structure shown in formula (II)
Schiff base ligand.
It is furthermore preferred that will there is the present invention diamine compound of structure shown in formula (III) to be dissolved in ethanol, two aminations are obtained
Polymer solution；The bigcatkin willow aldehyde compound with formula (IV) described structure is dissolved in ethanol, it is molten to obtain bigcatkin willow aldehyde compound
Liquid；The bigcatkin willow aldehydes compound solution is slowly added dropwise to the diamine compound solution, is heated to reflux, be condensed instead
Should, obtain the Schiff base ligand with structure shown in formula (II).In the present invention, it is described with structure shown in formula (III) two
Amines is preferably 1,2 cyclohexanediamine (rac, (R, R), (S, S)) or 1,3- propane diamine；In the diamine compound solution,
The mass concentration of the diamine compound with formula (III) described structure is preferably 0.1g/mL~0.5g/mL, more preferably
0.15g/mL~0.3g/mL；The bigcatkin willow aldehyde compound with formula (IV) described structure is preferably 3,5- di-t-butyl water
Poplar aldehyde or salicylide；In the bigcatkin willow aldehydes compound solution, the matter of the bigcatkin willow aldehyde compound with formula (IV) structure
It is preferably 0.1g/mL~0.5g/mL to measure concentration, more preferably 0.2g/mL~0.4g/mL.In the present invention, it is described to be heated to reflux
Temperature be preferably 80 DEG C；The time being heated to reflux is preferably 8h~16h；More preferably 11h~13h；Most preferably
12h.In certain embodiments of the present invention, the temperature being heated to reflux is 80 DEG C, and the time being heated to reflux is 12h.
In the present invention, it is described with the amine compound of structure shown in formula (III) and described with knot formula (IV) Suo Shi
The mol ratio of the bigcatkin willow aldehyde compound of structure is 1:(2~4), more preferably 1:2.
The temperature of above-mentioned condensation reaction is preferably 80 DEG C of temperature being heated to reflux；The time of above-mentioned condensation reaction is preferably to add
Time 8h~16h of heat backflow；More preferably 11h~13h；Most preferably 12h.
After above-mentioned condensation reaction, the solution that the condensation reaction obtains preferably is removed solvent by the present invention, then will remove solvent
Reaction product recrystallized, so as to obtain that there is the Schiff base ligand of structure shown in formula (II).The present invention to it is described go it is molten
The method of agent and recrystallization does not have special limitation, and the method for solvent and recrystallization is gone i.e. using well known to those skilled in the art
Can.The solution that the present invention preferably obtains the condensation reaction carries out revolving and removes solvent therein, and the reaction for removing solvent is produced
Thing is recrystallized using ethanol, obtains the Schiff base ligand with structure shown in formula (II).
Obtain after there is the Schiff base ligand of structure shown in formula (II), the present invention there will be the Schiff of structure shown in formula (II)
Aar ligand reacts in a solvent with ferric trichloride, obtains the schiff bases iron compound with structure shown in formula (I).Specifically, this
Invention preferably under conditions of gas is protected will there is the Schiff base ligand solution of structure shown in formula (II) to be mixed with liquor ferri trichloridi
Stirring is closed, the schiff bases iron compound with structure shown in formula (I) is obtained after reaction.The protection gas is preferably high pure nitrogen.
It is in the present invention, described that to have the Schiff base ligand of structure shown in formula (II) and the mol ratio of the ferric trichloride be preferably 1:1.
The present invention to described there is the Schiff base ligand solution of structure shown in formula (II) and the compound method of liquor ferri trichloridi to have no spy
Different limitation, using solution compound method well known to those skilled in the art.It is described uncommon with structure shown in formula (II)
The solvent of husband's aar ligand solution is preferably the methanol either mixed solvent of methanol and acetonitrile；It is described that there is structure shown in formula (II)
The molar concentration of Schiff base ligand solution be preferably 0.5mol/L~2mol/L, more preferably 1mol/L~2mol/L.It is described
Solvent in liquor ferri trichloridi is preferably the methanol either mixed solvent of methanol and acetonitrile；The liquor ferri trichloridi rubs
Your concentration is preferably 0.5mol/L~2mol/L, more preferably 1mol/L~2mol/L.It is special that the present invention has no to the solvent
Limitation, it is preferred to use the mixed solvent of methanol either methanol and acetonitrile.
In the present invention, it is described to have the Schiff base ligand of structure shown in formula (II) and the temperature of ferric chloride reaction preferred
For 25 DEG C~60 DEG C；More preferably 25 DEG C.When the reaction dissolvent is methanol, the temperature of the reaction is preferably 25 DEG C.It is described
It is preferably 8h~12h with the Schiff base ligand of structure and the time of ferric chloride reaction shown in formula (II), more preferably 9h~
10h。
After the reaction of the Schiff base ligand and ferric trichloride with formula (II) structure, the present invention is preferably by the reaction
Obtained solution removes solvent, is then recrystallized the reaction product for removing solvent, obtains the Schiff with structure shown in formula (I)
Alkali iron compound.The present invention goes solvent and the method for recrystallization not to have special limitation to described, using those skilled in the art
The well known method for removing solvent and recrystallization.The present invention will preferably react obtained solution be filtered to remove it is therein molten
Agent, the reaction product of solvent will be gone using methylene chloride/methanol, methylene chloride/methanol acetonitrile, acetonitrile/ethanol, acetone/ethanol
Mixed solvent is recrystallized, and obtains the schiff bases iron compound with structure shown in formula (I).
Present invention also offers a kind of preparation method of PLA, comprise the following steps：
Lactide is mixed with catalyst, ring-opening polymerization is carried out in a solvent, obtains PLA；
The schiff bases iron compound that the catalyst is above-mentioned schiff bases iron compound or above-mentioned preparation method is prepared.
The schiff bases iron compound is used for the ring-opening polymerisation for being catalyzed lactide by the present invention, and schiff bases iron catalyst is to third
The ring-opening polymerisation of lactide has very high activity, and room temperature is that the polymerization of monomer can be achieved, while is had to rac-lactide
Suitable selectivity, improve the regularity of polymerizate microstructure of molecular chain.
Specifically, the present invention mixes lactide and catalyst, under stirring in a solvent preferably under the conditions of anhydrous and oxygen-free
Ring-opening polymerization is carried out, obtains PLA.There is catalyst schiff bases iron compound provided by the invention higher catalysis to live
Property, the selectivity of catalyzing ring-opening polymerization of lactide is preferable, can not only be catalyzed rac-lactide and obtain PLA, can also urge
Change levorotatory lactide and dextrorotation lactide mixture obtains PLA.The present invention does not have special limit to the source of the lactide
System, using the commercial goods of lactide, the lactide of preferred pair purchase of the present invention is recrystallized, then carries out ring-opening polymerisation
Reaction.The present invention special limitation is had no to the solvent, using it is well known to those skilled in the art can dissolve lactide and
The solvent of catalyst, the present invention are preferably expoxy propane or 7-oxa-bicyclo[4.1.0.The present invention does not have to the mode of the stirring
Special limitation, by the way of stirring well known to those skilled in the art.
Schiff bases iron compound reactivity provided by the invention is higher, the dosage in catalyzing ring-opening polymerization of lactide compared with
Few, ring-opening polymerization can use relatively low reaction temperature.In the present invention, the mol ratio of the lactide and catalyst is preferred
For (50~1000):1, more preferably (100~800):1, be most preferably (100~400):1.The temperature of the ring-opening polymerization
Degree is preferably 25 DEG C~140 DEG C, more preferably 25 DEG C~60 DEG C, most preferably 25 DEG C；The time of the ring-opening polymerization is excellent
Elect 1h~48h, most preferably 12h as.
After completing the ring-opening polymerization, the product of the ring-opening polymerization is preferably used chloroform by the present invention
Dissolving, adds excessive ethanol precipitation polymer, is dried after filtering, obtains PLA.The present invention is to the chloroform
Dosage does not have special limitation, can dissolve the product of the ring-opening polymerization.The present invention is to the filtering and does
Dry method does not have special limitation, using filtering well known to those skilled in the art and the technical scheme dried.At this
In invention, the drying is preferably to be dried in vacuo, and the time of the drying is preferably 24h~48h, most preferably 36h.
After obtaining PLA, the present invention is using homonuclear decoupling proton nmr spectra analysis selectivity.It polymerize poly- third obtained
The backbone sequence distribution of lactide represents that segment is connected together by the lactide of identical configuration using " mmm ", [mmr],
[rmm], [mrm], [rmr] represent that the lactide for differing configuration in segment be present connects together.According to one-level Markovian
Statistics, five kinds of sequence relative intensities of poly- rac-lactide can be represented by a parameter Pm：Pm refers to a catalyst point
After the lactide of sub- one configuration of ring-opening polymerisation, continue polymerization one have identical configuration lactide probability, [mmm]=
Pm2+ (1-Pm) Pm/2, [rmm]=[mmr]=(1-Pm) Pm/2, [mrm]=[(1-Pm)2+ Pm (1-Pm)]/2, [rmr]=
[(1-Pm)2]/2.As a result show, schiff bases iron compound provided by the invention has stronger selection to lactide ring-opening polymerisation
Property, improve the regularity of polymerizate space structure.
Present invention also offers a kind of preparation method of polycaprolactone, comprise the following steps：
Caprolactone is mixed with catalyst, ring-opening polymerization is carried out in a solvent, obtains polycaprolactone；
The schiff bases iron compound that the catalyst is above-mentioned schiff bases iron compound or above-mentioned preparation method is prepared.
The schiff bases iron compound is used for the ring-opening polymerisation for being catalyzed caprolactone by the present invention, and schiff bases iron catalyst is to oneself
The ring-opening polymerisation of lactone has very high activity, and room temperature is that the polymerization of monomer can be achieved.
Specifically, the present invention mixes caprolactone and catalyst, under stirring in a solvent preferably under the conditions of anhydrous and oxygen-free
Ring-opening polymerization polymer reaction is carried out, obtains polycaprolactone.The present invention does not have special limitation to the source of the caprolactone, using oneself
The commercial goods of lactone, the caprolactone of preferred pair purchase of the present invention is evaporated under reduced pressure, then carries out ring-opening polymerization.This
Invention has no special limitation to the solvent, using caprolactone and the catalyst well known to those skilled in the art of can dissolving
Solvent, the present invention are preferably expoxy propane or 7-oxa-bicyclo[4.1.0.The present invention does not have special limit to the mode of the stirring
System, using agitating mode well known to those skilled in the art.
Schiff bases iron compound reactivity provided by the invention is higher, the dosage when being catalyzed caprolactone ring-opening polymerisation compared with
Few, ring-opening polymerization can use relatively low reaction temperature.In the present invention, the mol ratio of the caprolactone and catalyst is preferred
For (50~1000):1, more preferably (100~800):1, be most preferably (100~500):1.The temperature of the ring-opening polymerization
Degree is preferably 25 DEG C~100 DEG C, more preferably 25 DEG C~60 DEG C, most preferably 25 DEG C；The time of the ring-opening polymerization is excellent
Elect 1h~48h, most preferably 12h~24h as.
After completing the ring-opening polymerization, the product of the ring-opening polymerization is preferably used chloroform by the present invention
Dissolving, adds excessive ethanol precipitation polymer, is dried after filtering, obtains polycaprolactone.The present invention is to the chloroform
Dosage there is no special limitation, the product of the ring-opening polymerization can be dissolved.The present invention to it is described filtering and
Dry method does not have special limitation, using filtering well known to those skilled in the art and the technical scheme dried.
In the present invention, the drying is preferably to be dried in vacuo, and the time of the drying is preferably 24h~48h, most preferably 36h.
The present invention has no special limitation to the source of above-mentioned used raw material, can be general commercially available.
The invention provides a kind of schiff bases iron compound, has structure shown in formula (I),
Wherein, Y is-CH2-CH2-CH2- orR is-H or alkyl.
Schiff bases iron compound provided by the invention has NNOO quad-tree index abilities, so as to be formed in a metal active
Heart binding site, four-coordination schiff bases iron catalyst can be obtained.The schiff bases iron compound is used to be catalyzed third by the present invention
The ring-opening polymerisation of lactide and caprolactone, the ring-opening polymerisation of ring-opening polymerisation and caprolactone of the schiff bases iron catalyst to lactide have
Very high catalytic activity, room temperature is that the polymerization of monomer can be achieved, while has suitable selectivity to rac-lactide, is carried
The high regularity of polymerizate microstructure of molecular chain.Test result indicates that method provided by the invention prepares the monomer of PLA
Conversion ratio can reach 90%, and the monomer conversion of polycaprolactone can reach 99%.When lactide is rac-lactide, obtain
PLA three-dimensional regularity (Pm) up to 0.60.
In order to further illustrate the present invention, with reference to embodiment to schiff bases iron compound provided by the invention, its system
Preparation Method and its application as catalyst are described in detail, but they can not be interpreted as to the scope of the present invention
Limit.
Embodiment 1
By 1.14g rac-1,2 cyclohexanediamine are dissolved in 20mL ethanol, obtain rac-1,2 cyclohexanediamine solution；By 4.7g
3,5- di-tert-butyl salicylaldehydes are dissolved in 30mL ethanol, 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
Compound.The solvent being filtered to remove in reactant mixture, obtained reaction product is obtained into Schiff base ligand using ethyl alcohol recrystallization.
Obtained schiff base compound is carried out elementary analysis by the present invention, obtains the content of wherein each atom, as a result as follows：
Elem.Anal. (%)：Calcd.C 79.07, H 9.95, N 5.12；Found：C 78.65, H 10.31, N 4.99.
This explanation, the Schiff base ligand that the present embodiment obtains have structure shown in formula (II), wherein, Y isR is uncle
Butyl.
Embodiment 2
By 1.14g (S, S) -1,2 cyclohexanediamine are dissolved in 20mL ethanol, obtain (S, S) -1,2 cyclohexanediamine solution；Will
4.7g 3,5- di-tert-butyl salicylaldehyde are dissolved in 30mL ethanol, obtain 3,5- di-tert-butyl salicylaldehyde solution, by 3,5-, bis- tertiary fourths
Base salicylide solution is slowly added dropwise to (S, S) -1,2 cyclohexanediamine solution, obtained mixed solution 80 DEG C flow back 12h, obtain
Reactant mixture.The solvent being filtered to remove in reactant mixture, obtained reaction product is obtained into Schiff using ethyl alcohol recrystallization
Aar ligand.Obtained schiff base compound is carried out elementary analysis by the present invention, obtains the content of wherein each atom, as a result as follows：
Elem.Anal. (%)：Calcd.C 79.07, H 9.95, N 5.12；Found：C 78.71, H 9.85, N 4.77.
This explanation, the Schiff base ligand that the present embodiment obtains have structure shown in formula (II), wherein, Y isR is uncle
Butyl.
Embodiment 3
By 1.5g 1,3- propane diamine is dissolved in 20mL ethanol, obtains 1,3- propane diamine solution；5g salicylides are dissolved in 20mL
In ethanol, salicylide solution is obtained, salicylide solution is slowly added dropwise to 1,3- propane diamine solution, obtained mixed solution is 80
DEG C backflow 12h, obtain reactant mixture.The solvent being filtered to remove in reactant mixture, obtained reaction product is used into ethanol
It is recrystallized to give Schiff base ligand.Obtained schiff base compound is carried out elementary analysis by the present invention, obtains wherein each atom
Content is as a result as follows：Elem.Anal. (%)：Calcd.C 72.32, H 6.43, N 9.92；Found：C 72.16, H
6.28, N 9.64.
This explanation, the Schiff base ligand that the present embodiment obtains have structure shown in formula (II), wherein, Y is-CH2-CH2-
CH2-；R is-H.
Embodiment 4
By 0.75g 1,3- propane diamine is dissolved in 20mL ethanol, obtains 1,3- propane diamine solution；4.7g salicylides are dissolved in
In 30mL ethanol, 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 reactant mixture.The solvent being filtered to remove in reactant mixture, obtained reaction product is used
Ethyl alcohol recrystallization obtains Schiff base ligand.Obtained schiff base compound is carried out elementary analysis by the present invention, obtains wherein each original
The content of son is as a result as follows：Elem.Anal. (%)：Calcd.C 78.21, H 9.94, N 5.53；Found：C 78.49, H
10.43 N 5.37.
This explanation, the Schiff base ligand that the present embodiment obtains have structure shown in formula (II), wherein, Y is-CH2-CH2-
CH2-；R is the tert-butyl group.
Embodiment 5
Under conditions of high pure nitrogen protection, the Schiff base ligand that 1g embodiments 1 obtain is mixed with 0.4g ferric trichlorides
Afterwards, add 20mL methanol to mix, obtained mixed solution is reacted into 2h at 25 DEG C, filtered reaction system after completing reaction
Remove solvent, methylene chloride/methanol recrystallization；Obtain schiff bases iron compound.
Obtained schiff bases iron compound is carried out elementary 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, the Schiff base ligand that the present embodiment obtains have structure shown in formula (II), wherein, Y isR is uncle
Butyl.
Embodiment 6
Under conditions of high pure nitrogen protection, the Schiff base ligand that 1g embodiments 2 obtain is mixed with 0.4g ferric trichlorides
Afterwards, add 20mL methanol to mix, obtained mixed solution is reacted into 2h at 25 DEG C, filtered reaction system after completing reaction
Remove solvent, methylene chloride/methanol recrystallization；Obtain schiff bases iron compound.
Obtained schiff bases iron compound is carried out elementary 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 67.73, H 8.11, N 5.32.
This explanation, the Schiff base ligand that the present embodiment obtains have structure shown in formula (II), wherein, Y isR is uncle
Butyl.
Embodiment 7
Under conditions of high pure nitrogen protection, the Schiff base ligand that 1g embodiments 3 obtain is mixed with 0.3g ferric trichlorides
Afterwards, add 15mL methanol and 25mL acetonitriles mix, obtained mixed solution is reacted into 2h at 60 DEG C, completing will be anti-after reacting
System is answered to be filtered to remove solvent, methylene chloride/methanol recrystallized from acetonitrile；Obtain schiff bases iron compound.
Obtained schiff bases iron compound is carried out elementary analysis by the present invention, obtains the content of wherein each atom, as a result such as
Under：Elem.Anal. (%)：C 54.94, H 4.34, N 7.54；Found C 54.73, H 4.69, N 7.38.
This explanation, the Schiff base ligand that the present embodiment obtains have structure shown in formula (II), wherein, Y is-CH2-CH2-
CH2-；R is-H.
Embodiment 8
Under conditions of high pure nitrogen protection, the Schiff base ligand that 1g embodiments 4 obtain is mixed with 0.4g ferric trichlorides
Afterwards, add 15mL methanol and 25mL acetonitriles mix, obtained mixed solution is reacted into 2h at 25 DEG C, completing will be anti-after reacting
System is answered to be filtered to remove solvent, methylene chloride/methanol recrystallized from acetonitrile；Obtain schiff bases iron compound.
Obtained schiff bases iron compound is carried out elementary analysis by the present invention, obtains the content of wherein each atom, as a result such as
Under：Elem.Anal. (%)：C 66.50, H 8.12, N 4.70；Found C 66.82, H 8.34, N 4.37.
This explanation, the Schiff base ligand that the present embodiment obtains have structure shown in formula (II), wherein, Y is-CH2-CH2-
CH2-；R is the tert-butyl group.
Embodiment 9
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.2mmol embodiments 5 obtain
Schiff bases iron compound mixed with 20mL expoxy propane, by obtained mixed solution in 60 DEG C of stirring reaction 24h, to what is obtained
10mL chloroforms dissolving polymer is added in reaction solution, then adds excessive ethanol precipitation polymer thereto, is filtered, very
Sky dries 48h, obtains PLA.
The quality that present invention weighing obtains PLA is 2.4g；The monomer conversion of PLA is 89%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 1.9 ten thousand.
Embodiment 10
PLA is prepared using the technical scheme of embodiment 9 in the present invention, unlike, the present embodiment uses dextrorotation third
Lactide replaces the levorotatory lactide that embodiment 9 uses.
The quality that present invention weighing obtains PLA is 2.5g；The monomer conversion of PLA is 90%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 1.95 ten thousand.
Embodiment 11
PLA is prepared using the technical scheme of embodiment 9 in the present invention, unlike, the present embodiment uses racemic
Lactide replaces the levorotatory lactide that embodiment 9 uses.
The quality that present invention weighing obtains PLA is 2.4g；The monomer conversion of PLA is 89%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 1.88 ten thousand.
The present invention is analyzed the PLA that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.80.
Embodiment 12
Under conditions of anhydrous and oxygen-free, caprolactone that 20.0mmol was evaporated under reduced pressure, 0.2mmol embodiments 5 obtain
Schiff bases iron compound mixes with 20mL expoxy propane, anti-to what is obtained by obtained mixed solution in 60 DEG C of stirring reaction 18h
Answer and 10mL chloroforms dissolving polymer is added in solution, then add excessive ethanol precipitation polymer thereto, filter, vacuum
48h is dried, obtains polycaprolactone.
The quality that present invention weighing obtains polycaprolactone is 2.2g；The monomer conversion of polycaprolactone is 99%.
Using polystyrene as reference material, the polycaprolactone obtained using gel permeation chromatography to the present embodiment is carried out the present invention
Analysis, the number-average molecular weight for obtaining caprolactone are 1.8 ten thousand.
Embodiment 13
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.1mmol embodiments 6 obtain
Schiff bases iron compound mixed with 20mL expoxy propane, by obtained mixed solution in 60 DEG C of stirring reaction 30h, to what is obtained
10mL chloroforms dissolving polymer is added in reaction solution, then adds excessive ethanol precipitation polymer thereto, is filtered, very
Sky dries 48h, obtains PLA.
The quality that present invention weighing obtains PLA is 2.3g；The monomer conversion of PLA is 87%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 3.1 ten thousand.
Embodiment 14
PLA is prepared using the technical scheme of embodiment 13 in the present invention, unlike, the present embodiment uses dextrorotation
Lactide replaces the levorotatory lactide that embodiment 13 uses.
The quality that present invention weighing obtains PLA is 2.2g；The monomer conversion of PLA is 85%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 3.07 ten thousand.
Embodiment 15
PLA is prepared using the technical scheme of embodiment 13 in the present invention, unlike, the present embodiment uses outer disappear
Revolve the levorotatory lactide that lactide replaces embodiment 13 to use.
The quality that present invention weighing obtains PLA is 2.4g；The monomer conversion of PLA is 88%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 3.16 ten thousand；
The present invention is analyzed the PLA that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.78.
Embodiment 16
Under conditions of anhydrous and oxygen-free, caprolactone that 20.0mmol was evaporated under reduced pressure, 0.1mmol embodiments 6 obtain
Schiff bases iron compound mixes with 20mL expoxy propane, anti-to what is obtained by obtained mixed solution in 60 DEG C of stirring reaction 30h
Answer and 10mL chloroforms dissolving polymer is added in solution, then add excessive ethanol precipitation polymer thereto, filter, vacuum
48h is dried, obtains polycaprolactone.
The quality that present invention weighing obtains polycaprolactone is 2.0g；The monomer conversion of polycaprolactone is 94%.
Using polystyrene as reference material, the polycaprolactone obtained using gel permeation chromatography to the present embodiment is carried out the present invention
Analysis, the number-average molecular weight for obtaining polycaprolactone are 2.8 ten thousand.
Embodiment 17
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.1mmol embodiments 7 obtain
Schiff bases iron compound mixed with 20mL expoxy propane, by obtained mixed solution in 60 DEG C of stirring reaction 8h, to what is obtained
10mL chloroforms dissolving polymer is added in reaction solution, then adds excessive ethanol precipitation polymer thereto, is filtered, very
Sky dries 48h, obtains PLA.
The quality that present invention weighing obtains PLA is 2.4g；The monomer conversion of PLA is 88%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 3.7 ten thousand.
Embodiment 18
PLA is prepared using the technical scheme of embodiment 17 in the present invention, unlike, the present embodiment uses dextrorotation
Lactide replaces the levorotatory lactide that embodiment 17 uses.
The quality that present invention weighing obtains PLA is 2.5g；The monomer conversion of PLA is 90%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 3.75 ten thousand.
Embodiment 19
PLA is prepared using the technical scheme of embodiment 17 in the present invention, unlike, the present embodiment uses outer disappear
Revolve the levorotatory lactide that lactide replaces embodiment 17 to use.
The quality that present invention weighing obtains PLA is 2.2g；The monomer conversion of PLA is 85%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 3.60 ten thousand；
The present invention is analyzed the PLA that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.60.
Embodiment 20
Under conditions of anhydrous and oxygen-free, caprolactone that 20.0mmol was evaporated under reduced pressure, 0.04mmol embodiments 7 obtain
Schiff bases iron compound mixes with 20mL expoxy propane, anti-to what is obtained by obtained mixed solution in 60 DEG C of stirring reaction 4h
Answer and 10mL chloroforms dissolving polymer is added in solution, then add excessive ethanol precipitation polymer thereto, filter, vacuum
48h is dried, obtains polycaprolactone.
The quality that present invention weighing obtains polycaprolactone is 1.8g；The monomer conversion of polycaprolactone is 95%.
Using polystyrene as reference material, the polycaprolactone obtained using gel permeation chromatography to the present embodiment is carried out the present invention
Analysis, the number-average molecular weight for obtaining polycaprolactone are 5.6 ten thousand.
Embodiment 21
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.2mmol embodiments 8 obtain
Schiff bases iron compound mixed with 20mL expoxy propane, by obtained mixed solution in 60 DEG C of stirring reaction 3h, to what is obtained
10mL chloroforms dissolving polymer is added in reaction solution, then adds excessive ethanol precipitation polymer thereto, is filtered, very
Sky dries 48h, obtains PLA.
The quality that present invention weighing obtains PLA is 2.1g；The monomer conversion of PLA is 84%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 2.1 ten thousand.
Embodiment 22
PLA is prepared using the technical scheme of embodiment 21 in the present invention, unlike, the present embodiment uses dextrorotation
Lactide replaces the levorotatory lactide that embodiment 21 uses.
The quality that present invention weighing obtains PLA is 2.1g；The monomer conversion of PLA is 84%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 2.2 ten thousand.
Embodiment 23
PLA is prepared using the technical scheme of embodiment 21 in the present invention, unlike, the present embodiment uses outer disappear
Revolve the levorotatory lactide that lactide replaces embodiment 21 to use.
The quality that present invention weighing obtains PLA is 2.2g；The monomer conversion of PLA is 86%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 2.1 ten thousand；
The present invention is analyzed the PLA that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.70.
Embodiment 24
Under conditions of anhydrous and oxygen-free, caprolactone that 20.0mmol was evaporated under reduced pressure, 0.04mmol embodiments 8 obtain
Schiff bases iron compound mixes with 20mL expoxy propane, anti-to what is obtained by obtained mixed solution in 60 DEG C of stirring reaction 4h
Answer and 10mL chloroforms dissolving polymer is added in solution, then add excessive ethanol precipitation polymer thereto, filter, vacuum
48h is dried, obtains polycaprolactone.
The quality that present invention weighing obtains polycaprolactone is 2.1g；The monomer conversion of polycaprolactone is 99%.
Using polystyrene as reference material, the polycaprolactone obtained using gel permeation chromatography to the present embodiment is carried out the present invention
Analysis, the number-average molecular weight for obtaining polycaprolactone are 5.3 ten thousand.
Embodiment 25
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.1mmol embodiments 8 obtain
Schiff bases iron compound mixed with 20mL expoxy propane, by obtained mixed solution in 25 DEG C of stirring reaction 20h, to what is obtained
10mL chloroforms dissolving polymer is added in reaction solution, then adds excessive ethanol precipitation polymer thereto, is filtered, very
Sky dries 48h, obtains PLA.
The quality that present invention weighing obtains PLA is 2.0g；The monomer conversion of PLA is 85%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 0.9 ten thousand.
Embodiment 26
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.2mmol embodiments 5 obtain
Schiff bases iron compound mixed with 20mL expoxy propane, by obtained mixed solution in 100 DEG C of stirring reaction 8h, to what is obtained
10mL chloroforms dissolving polymer is added in reaction solution, then adds excessive ethanol precipitation polymer thereto, is filtered, very
Sky dries 48h, obtains PLA.
The quality that present invention weighing obtains PLA is 2.3g；The monomer conversion of PLA is 88%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 1.6 ten thousand.
Embodiment 27
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.1mmol embodiments 6 obtain
Schiff bases iron compound mixed with 20mL expoxy propane, by obtained mixed solution in 140 DEG C of stirring reaction 1h, to what is obtained
10mL chloroforms dissolving polymer is added in reaction solution, then adds excessive ethanol precipitation polymer thereto, is filtered, very
Sky dries 48h, obtains PLA.
The quality that present invention weighing obtains PLA is 2.1g；The monomer conversion of PLA is 87%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 1.9 ten thousand.
Embodiment 28
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.04mmol embodiments 8 obtain
Schiff bases iron compound mixed with 20mL expoxy propane, by obtained mixed solution in 80 DEG C of stirring reaction 10h, to what is obtained
10mL chloroforms dissolving polymer is added in reaction solution, then adds excessive ethanol precipitation polymer thereto, is filtered, very
Sky dries 48h, obtains PLA.
The quality that present invention weighing obtains PLA is 2.5g；The monomer conversion of PLA is 90%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 8.4 ten thousand.
Embodiment 29
Under conditions of anhydrous and oxygen-free, caprolactone that 20.0mmol was evaporated under reduced pressure, 0.1mmol embodiments 7 obtain
Schiff bases iron compound mixes with 20mL expoxy propane, anti-to what is obtained by obtained mixed solution in 25 DEG C of stirring reaction 48h
Answer and 10mL chloroforms dissolving polymer is added in solution, then add excessive ethanol precipitation polymer thereto, filter, vacuum
48h is dried, obtains polycaprolactone.
The quality that present invention weighing obtains polycaprolactone is 2.0g；The monomer conversion of polycaprolactone is 96%.
Using polystyrene as reference material, the polycaprolactone obtained using gel permeation chromatography to the present embodiment is carried out the present invention
Analysis, the number-average molecular weight for obtaining polycaprolactone are 1.7 ten thousand.
Embodiment 30
Under conditions of anhydrous and oxygen-free, caprolactone that 20.0mmol was evaporated under reduced pressure, 0.02mmol embodiments 8 obtain
Schiff bases iron compound mixes with 20mL expoxy propane, anti-to what is obtained by obtained mixed solution in 60 DEG C of stirring reaction 24h
Answer and 10mL chloroforms dissolving polymer is added in solution, then add excessive ethanol precipitation polymer thereto, filter, vacuum
48h is dried, obtains polycaprolactone.
The quality that present invention weighing obtains polycaprolactone is 1.9g；The monomer conversion of polycaprolactone is 95%.
Using polystyrene as reference material, the polycaprolactone obtained using gel permeation chromatography to the present embodiment is carried out the present invention
Analysis, the number-average molecular weight for obtaining polycaprolactone are 6.7 ten thousand.
Embodiment 31
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.2mmol embodiments 8 obtain
Schiff bases iron compound mixed with 20mL expoxy propane, by obtained mixed solution in 25 DEG C of stirring reaction 12h, to what is obtained
10mL chloroforms dissolving polymer is added in reaction solution, then adds excessive ethanol precipitation polymer thereto, is filtered, very
Sky dries 48h, obtains PLA.
The quality that present invention weighing obtains PLA is 1.9g；The monomer conversion of PLA is 82%.
The present invention is divided the PLA that the present embodiment obtains using polystyrene as reference material using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining PLA are 2.1 ten thousand.
Embodiment 32
Under conditions of anhydrous and oxygen-free, caprolactone that 20.0mmol was evaporated under reduced pressure, 0.2mmol embodiments 8 obtain
Schiff bases iron compound mixes with 20mL expoxy propane, anti-to what is obtained by obtained mixed solution in 25 DEG C of stirring reaction 10h
Answer and 10mL chloroforms dissolving polymer is added in solution, then add excessive ethanol precipitation polymer thereto, filter, vacuum
48h is dried, obtains polycaprolactone.
The quality that present invention weighing obtains polycaprolactone is 1.9g；The monomer conversion of polycaprolactone is 83%.
Using polystyrene as reference material, the polycaprolactone obtained using gel permeation chromatography to the present embodiment is carried out the present invention
Analysis, the number-average molecular weight for obtaining polycaprolactone are 2.5 ten thousand.
As seen from the above embodiment, the invention provides a kind of schiff bases iron compound, its preparation method and its conduct to urge
The application of agent, schiff bases iron compound provided by the invention, there is structure shown in formula (I), wherein, Y is-CH2-CH2-CH2-
OrR is-H or alkyl.Schiff bases iron compound provided by the invention has NNOO quad-tree index abilities, so as to form one
Metal active centres binding site, four-coordination schiff bases iron catalyst can be obtained.The present invention is by the schiff bases iron compound
For being catalyzed the ring-opening polymerisation of lactide and caprolactone, ring-opening polymerisation and caprolactone of the schiff bases iron catalyst to lactide are opened
Cyclopolymerization has very high catalytic activity, and room temperature is that the polymerization of monomer can be achieved, while is had to rac-lactide suitable
Selectivity, improve the regularity of polymerizate microstructure of molecular chain.Gather test result indicates that prepared by method provided by the invention
The monomer conversion of lactic acid can reach 90%, and the monomer conversion of polycaprolactone can reach 99%.When lactide is racemic third
During lactide, the three-dimensional regularity (Pm) of obtained PLA is up to 0.60.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (14)
1. a kind of schiff bases iron compound, there is structure shown in formula (I)：
Wherein, Y is-CH2-CH2-CH2- or
R is-H or alkyl.
2. schiff bases iron compound according to claim 1, it is characterised in that the R is-H or carbon number is 1~5
Alkyl.
3. a kind of preparation method of schiff bases iron compound, comprises the following steps：
To there is the Schiff base ligand of structure shown in formula (II) to be reacted in a solvent with ferric trichloride, obtain with formula (I) Suo Shi
The schiff bases iron compound of structure；
Wherein, Y is-CH2-CH2-CH2- or
R is-H or alkyl.
4. preparation method according to claim 3, it is characterised in that the Schiff base ligand of structure is pressed shown in the formula (II)
Prepared according to following steps：
It will be carried out with the amine compound of structure shown in formula (III) and the bigcatkin willow aldehyde compound with structure shown in formula (IV)
Condensation reaction, obtain the Schiff base ligand with structure shown in formula (II)；
Wherein, Y is-CH2-CH2-CH2- or
R is-H or alkyl.
5. preparation method according to claim 4, it is characterised in that described aminated with structure shown in formula (III)
Compound is 1 with the mol ratio with the bigcatkin willow aldehyde compound of structure shown in formula (IV):(2~4).
6. preparation method according to claim 4, it is characterised in that the condensation reaction is carried out under reflux conditions；
The time of the condensation reaction is 8h~16h.
7. preparation method according to claim 3, it is characterised in that described that there are the schiff bases of structure shown in formula (II) to match somebody with somebody
The mol ratio of body and the ferric trichloride is 1:1.
8. preparation method according to claim 3, it is characterised in that the temperature of the reaction is 25 DEG C~60 DEG C；It is described
The time of reaction is 8h~12h.
9. a kind of preparation method of PLA, comprises the following steps：
Lactide is mixed with catalyst, ring-opening polymerization is carried out in a solvent, obtains PLA；
The catalyst is schiff bases iron compound described in claim 1~2 any one or claim 3~8 any one
The schiff bases iron compound that methods described is prepared.
10. preparation method according to claim 9, it is characterised in that the mol ratio of the catalyst and the lactide
1:(50~1000).
11. preparation method according to claim 9, it is characterised in that the temperature of the ring-opening polymerization be 25 DEG C~
140℃；
The time of the ring-opening polymerization is 1h~48h.
12. a kind of preparation method of polycaprolactone, comprises the following steps：
Caprolactone is mixed with catalyst, ring-opening polymerization is carried out in a solvent, obtains polycaprolactone；
The catalyst is schiff bases iron compound described in claim 1~2 any one or claim 3~8 any one
The schiff bases iron compound that methods described is prepared.
13. preparation method according to claim 12, it is characterised in that the mol ratio of the catalyst and the caprolactone
1:(50~1000).
14. preparation method according to claim 12, it is characterised in that the temperature of the ring-opening polymerization be 25 DEG C~
100℃；
The time of the ring-opening polymerization is 1h~48h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710427802.4A CN107417739B (en) | 2017-06-08 | 2017-06-08 | A kind of schiff bases iron compound, preparation method and its application as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710427802.4A CN107417739B (en) | 2017-06-08 | 2017-06-08 | A kind of schiff bases iron compound, preparation method and its application as catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107417739A true CN107417739A (en) | 2017-12-01 |
| CN107417739B CN107417739B (en) | 2019-11-15 |
Family
ID=60428579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710427802.4A Active CN107417739B (en) | 2017-06-08 | 2017-06-08 | A kind of schiff bases iron compound, preparation method and its application as catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107417739B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108610475A (en) * | 2018-08-13 | 2018-10-02 | 中国科学院长春应用化学研究所 | A kind of preparation method of polylactic acid-polycaprolactone co-polymer |
| CN108912010A (en) * | 2018-08-01 | 2018-11-30 | 中国科学院长春应用化学研究所 | A kind of schiff bases manganese compound, preparation method and its application |
| CN109054011A (en) * | 2018-07-16 | 2018-12-21 | 中国科学院长春应用化学研究所 | A kind of preparation method of schiff bases cobalt compound, preparation method and polycarbonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003064174A (en) * | 2001-08-24 | 2003-03-05 | Nagoya Industrial Science Research Inst | Lactone ring-opening polymerization catalyst, method for producing polyester, and method for producing block copolymer |
| CN103097432A (en) * | 2010-06-17 | 2013-05-08 | 日立造船株式会社 | Method for producing polylactic acid |
| CN105712889A (en) * | 2014-12-17 | 2016-06-29 | 日名国际药品有限公司 | Method for preparing (1R,2S) -2- (3, 4-difluorophenyl) cyclopropylamine |
-
2017
- 2017-06-08 CN CN201710427802.4A patent/CN107417739B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003064174A (en) * | 2001-08-24 | 2003-03-05 | Nagoya Industrial Science Research Inst | Lactone ring-opening polymerization catalyst, method for producing polyester, and method for producing block copolymer |
| CN103097432A (en) * | 2010-06-17 | 2013-05-08 | 日立造船株式会社 | Method for producing polylactic acid |
| CN105712889A (en) * | 2014-12-17 | 2016-06-29 | 日名国际药品有限公司 | Method for preparing (1R,2S) -2- (3, 4-difluorophenyl) cyclopropylamine |
Non-Patent Citations (2)
| Title |
|---|
| B.B. IDAGE等: "Ring opening polymerization of dilactide using salen complex as catalyst", 《MATERIALS SCIENCE AND ENGINEERING B》 * |
| CHEMICAL ABSTRACT SERVICE: "CAS RN：1962923-60-9等", 《CA 网络版 STN REGISTRY数据库》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054011A (en) * | 2018-07-16 | 2018-12-21 | 中国科学院长春应用化学研究所 | A kind of preparation method of schiff bases cobalt compound, preparation method and polycarbonate |
| CN108912010A (en) * | 2018-08-01 | 2018-11-30 | 中国科学院长春应用化学研究所 | A kind of schiff bases manganese compound, preparation method and its application |
| CN108912010B (en) * | 2018-08-01 | 2021-04-06 | 中国科学院长春应用化学研究所 | Schiff base manganese compound, and preparation method and application thereof |
| CN108610475A (en) * | 2018-08-13 | 2018-10-02 | 中国科学院长春应用化学研究所 | A kind of preparation method of polylactic acid-polycaprolactone co-polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107417739B (en) | 2019-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Bis (imino) aryl NCN pincer aluminum and zinc complexes: synthesis, characterization, and catalysis on l-Lactide polymerization | |
| Samantaray et al. | Silver N-heterocyclic carbene complexes as initiators for bulk ring-opening polymerization (ROP) of l-lactides | |
| Amgoune et al. | Controlled ring-opening polymerization of lactide by group 3 metal complexes | |
| Hung et al. | Preparation, characterization, and catalytic studies of magnesium complexes supported by NNO-tridentate Schiff-base ligands | |
| Bouyahyi et al. | Aluminum complexes of fluorinated dialkoxy-diimino salen-like ligands: Syntheses, structures, and use in ring-opening polymerization of cyclic esters | |
| Tang et al. | Synthesis and structural characterization of magnesium ketiminate complexes: efficient initiators for the ring-opening polymerization of L-lactide | |
| Yi et al. | Magnesium and calcium complexes containing biphenyl-based tridentate Iminophenolate Ligands for ring-opening polymerization of rac-Lactide | |
| Gao et al. | Stereoselective ring-opening polymerization of rac-lactides catalyzed by aluminum hemi-salen complexes | |
| Tsai et al. | Tridentate anilido‐aldimine magnesium and zinc complexes as efficient catalysts for ring‐opening polymerization of ε‐caprolactone and l‐lactide | |
| Huang et al. | Well-defined sterically hindered zinc aryloxides: Excellent catalysts for ring-opening polymerization of ɛ-caprolactone and l-lactide | |
| Eckert et al. | Simple is best: Diamine zinc complexes as unexpected catalysts in lactide polymerisation | |
| CN107417739A (en) | A kind of schiff bases iron compound, its preparation method and its application as catalyst | |
| CN103421034A (en) | Chiral aluminum compound and preparation method thereof and preparation method of polylactic acid | |
| Alkarekshi et al. | Phenolate Substituent Effects on Ring-Opening Polymerization of ε-caprolactone by Aluminum complexes bearing 2-(Phenyl-2-olate)-6-(1-amidoalkyl) pyridine Pincers | |
| CN107033193B (en) | A kind of schiff bases iron compound, preparation method and its application as catalyst | |
| Ghosh et al. | Heterolepic β‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide | |
| Daneshmand et al. | Catalytic-site-mediated chain-end control in the polymerization of rac-lactide with copper iminopyrrolide complexes | |
| Chuang et al. | Synthesis, characterization, and catalytic activity of sodium ketminiate complexes toward the ring-opening polymerization of l-lactide | |
| Steiniger et al. | Synthesis, Structures, and Catalytic Activity of Homo‐and Heteroleptic Ketoiminate Zinc Complexes in Lactide Polymerization | |
| Obuah et al. | (Ferrocenylpyrazolyl) zinc (II) benzoates as catalysts for the ring opening polymerization of ε-caprolactone | |
| Wei et al. | Aluminum complexes with Schiff base bridged bis (indolyl) ligands: synthesis, structure, and catalytic activity for polymerization of rac-lactide | |
| Jiang et al. | Phenoxy-imine/-amide aluminum complexes with pendant or coordinated pyridine moieties: Solvent effects on structural type and catalytic capability for the ROP of cyclic esters | |
| CN104311582B (en) | Schiff base zinc compound, preparation method of schiff base zinc compound, and preparation method of polylactic acid | |
| Lee et al. | Structurally diverse dysprosium and yttrium complexes containing an amine-bis (benzotriazole phenolate) ligand: Synthesis, characterization and catalysis for lactide polymerization | |
| CN108912010A (en) | A kind of schiff bases manganese compound, preparation method and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |