CN107417739B - A kind of schiff bases iron compound, preparation method and its application as catalyst - Google Patents
A kind of schiff bases iron compound, preparation method and its application as catalyst Download PDFInfo
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- CN107417739B CN107417739B CN201710427802.4A CN201710427802A CN107417739B CN 107417739 B CN107417739 B CN 107417739B CN 201710427802 A CN201710427802 A CN 201710427802A CN 107417739 B CN107417739 B CN 107417739B
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- polylactic acid
- schiff bases
- lactide
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- 239000002262 Schiff base Substances 0.000 title claims abstract description 131
- -1 schiff bases iron compound Chemical class 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 116
- 239000004626 polylactic acid Substances 0.000 claims abstract description 116
- 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 66
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 61
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 55
- 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
- 239000003446 ligand Substances 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 35
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 20
- 240000000203 Salix gracilistyla Species 0.000 claims description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- 238000006482 condensation reaction Methods 0.000 claims description 13
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 13
- 150000002506 iron compounds Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 20
- 125000000217 alkyl group Chemical group 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 13
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 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
- 239000000243 solution Substances 0.000 description 57
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 35
- 238000004458 analytical method Methods 0.000 description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- 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
- 239000013558 reference substance Substances 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000012869 ethanol precipitation Methods 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
- 238000004090 dissolution Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003756 stirring Methods 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
- 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
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000006071 cream Substances 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid 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
- 239000000126 substance Substances 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-MDZDMXLPSA-N 2-[(e)-2-(2-aminophenyl)ethenyl]aniline Chemical compound NC1=CC=CC=C1\C=C\C1=CC=CC=C1N YJSATLBWFLERNZ-MDZDMXLPSA-N 0.000 description 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 229920001585 atactic polymer Polymers 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- 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 present invention provides a kind of schiff bases iron compound, preparation method and its as the application of catalyst, schiff bases iron compound provided by the invention has structure shown in formula (I), wherein Y is-CH2‑CH2‑CH2Or
Description
Technical field
The present invention relates to technical field of polymer more particularly to a kind of schiff bases iron compounds, preparation method and its work
For the application of catalyst.
Background technique
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 synthesis of polylactic acid generallys use two methods, i.e. lactide (cyclic dimer of lactic acid) is opened
Cyclopolymerization and direct polycondensation of lactic acid.The wherein method that 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 with polylactic acid is also using internal ester monomer ring-opening polymerisation
It obtains.
Lactide is divided into three kinds of optical isomers: levorotatory lactide (LLA), and dextrorotation lactide (DLA) and meso third are handed over
Ester, structure difference are as follows:
The spatial configuration of lactide has conclusive work to the machinery of obtained polylactic acid, processing and degradation property
With.In order to obtain the polylactic acid of better performances, the 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
Object is 180 DEG C of fusing point of crystalline polymer.But the product of rac-lactide ring-opening polymerisation under the same conditions is non-knot
Crystalline substance atactic polymer.Compared with amorphism polylactic acid, the use temperature range of crystalline polymer is wider, can be close to melting
Temperature.Since rac-lactide price is lower, it is therefore desirable to which developing a kind of pair of rac-lactide polymerization has stereoselectivity
Ring-opening polymerization catalyst, rac-lactide can be polymerize and obtain crystalline polylactic acid.
Currently, about the catalyst of lactide stereoselectivity ring-opening polymerisation, there are reports, such as Coates report
Schiff bases-Al catalysts (Salbinap) AlOMe be by a molecule 2,2'- diaminostilbene, 1'- connects dinaphthyl and two molecule bigcatkin willows
Aldehyde is condensed to yield schiff bases, then reacts to obtain with a molecule aluminium isopropoxide by a molecule schiff bases；The reports such as Zhong Zhiyuan
(cyclohexylsalen) AlOiPr catalyst is by a molecule 1,2- hexamethylene diamino and two molecules 3,5- di-t-butyl bigcatkin willow
Aldehyde is condensed to yield schiff bases, then reacts to obtain with a molecule aluminium isopropoxide by a molecule schiff bases.But the Schiff reported
For base catalyst in catalyzing ring-opening polymerization of lactide and catalysis caprolactone ring-opening polymerisation, the activity for being catalyzed reaction is lower, very
Hardly possible meets actual needs.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of schiff bases iron compound, preparation method
And its application as catalyst, schiff bases iron compound catalyzing ring-opening polymerization of lactide provided by the invention prepare polylactic acid
When, catalytic activity with higher；When catalysis caprolactone polymerization prepares polycaprolactone, it may have higher catalytic activity.
The present invention provides a kind of schiff bases iron compounds, have structure shown in formula (I):
Wherein, Y is-CH2-CH2-CH2Or
R is-H or alkyl.
Preferably, the alkyl that the R is-H or carbon atom number is 1~5.
The present invention also provides a kind of preparation methods of schiff bases iron compound, comprising the following steps:
To there is the Schiff base ligand of structure shown in formula (II) to react in a solvent with ferric trichloride, obtain with formula (I)
The schiff bases iron compound of shown structure；
Wherein, Y is-CH2-CH2-CH2Or
R is-H or alkyl.
Preferably, the Schiff base ligand of structure shown in the formula (II) is prepared according to the following steps:
To have 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, the Schiff base ligand with structure shown in formula (II) is obtained；
Wherein, Y is-CH2-CH2-CH2Or
R is-H or alkyl.
Preferably, the amine compound with structure shown in formula (III) and described with structure shown in formula (IV)
The molar ratio of bigcatkin willow aldehyde compound is 1:(2~4).
Preferably, the condensation reaction carries out under reflux conditions；
The time of the condensation reaction is 8h~16h.
Preferably, the molar ratio of the Schiff base ligand with 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.
The present invention also provides a kind of preparation methods of polylactic acid, comprising the following steps:
Lactide is mixed with catalyst, ring-opening polymerization is carried out in a solvent, obtains polylactic acid；
The catalyst is above-mentioned schiff bases iron compound or the schiff bases iron compound that above-mentioned preparation method is prepared.
Preferably, molar ratio 1:(50~1000 of the catalyst and the lactide).
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.
The present invention also provides a kind of preparation methods of polycaprolactone, comprising the following steps:
Caprolactone is mixed with catalyst, ring-opening polymerization is carried out in a solvent, obtains polycaprolactone；
The catalyst is above-mentioned schiff bases iron compound or the schiff bases iron compound that above-mentioned preparation method is prepared.
Preferably, molar ratio 1:(50~1000 of the catalyst and the caprolactone).
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 present invention provides a kind of schiff bases iron compounds, have structure shown in formula (I),
Wherein, Y is-CH2-CH2-CH2OrR is-H or alkyl.
Schiff bases iron compound provided by the invention has NNOO quad-tree index ability, to be formed in a metal active
Heart binding site, available four-coordination schiff bases iron catalyst.The present invention is used for the schiff bases iron compound to be catalyzed third
The ring-opening polymerisation of lactide and caprolactone, schiff bases iron catalyst have the ring-opening polymerisation of lactide and the ring-opening polymerisation of caprolactone
Very high catalytic activity.The experimental results showed that the monomer conversion of method preparation polylactic acid provided by the invention can reach
90%, the monomer conversion of polycaprolactone can reach 99%.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of schiff bases iron compounds, have structure shown in formula (I):
Wherein, Y is-CH2-CH2-CH2Or
R is-H or alkyl.
Specifically, the alkyl that the R is preferably-H or carbon atom number is 1~5；More preferably-H, methyl or tert-butyl.
Schiff bases iron compound provided by the invention has the iron center of high activity, with schiff bases aluminium disclosed in the prior art
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, the polymerization of monomer can be realized in room temperature, while having comparable selection to rac-lactide
Property, improve the regularity of polymerizate microstructure of molecular chain.
The present invention also provides a kind of preparation methods of schiff bases iron compound, comprising the following steps:
To there is the Schiff base ligand of structure shown in formula (II) to react in a solvent with ferric trichloride, obtain with formula (I)
The schiff bases iron compound of shown structure；
Wherein, Y is-CH2-CH2-CH2Or
R is-H or alkyl.
The alkyl that the R is preferably-H or carbon atom number is 1~5；More preferably-H, methyl or tert-butyl.
The present invention using with structure shown in formula (II) schiff bases and ferric trichloride as raw material, reaction obtain with formula (I)
The schiff bases iron compound of shown structure.In the present invention, the Schiff base ligand with structure shown in formula (II) is preferably pressed
It is prepared according to following steps:
To have 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, the Schiff base ligand with structure shown in formula (II) is obtained；
Wherein, Y is-CH2-CH2-CH2Or
R is-H or alkyl.
The alkyl that the R is preferably-H or carbon atom number is 1~5；More preferably-H, methyl or tert-butyl.
Specifically, the present invention will preferably have the diamine compound of structure shown in formula (III) and have knot shown in formula (IV)
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 ethyl alcohol, two aminations are obtained
Polymer solution；To there is the bigcatkin willow aldehyde compound of formula (IV) described structure to be dissolved in ethyl alcohol, 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 anti-
It answers, obtains the Schiff base ligand with structure shown in formula (II).In the present invention, two with structure shown in formula (III)
Amine compounds are 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
Measuring concentration is preferably 0.1g/mL~0.5g/mL, more preferably 0.2g/mL~0.4g/mL.In the present invention, 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, the amine compound with structure shown in formula (III) has knot shown in formula (IV) with described
The molar 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 be heated to reflux；The time of above-mentioned condensation reaction preferably adds
Time 8h~16h of heat reflux；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, to obtain the Schiff base ligand with 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, goes the method for solvent and recrystallization i.e. using well known to those skilled in the art
It can.The solution that the present invention preferably obtains the condensation reaction carries out revolving and removes solvent therein, and the reaction of solvent will be gone to produce
Object is recrystallized using ethyl alcohol, obtains the Schiff base ligand with structure shown in formula (II).
After obtaining the Schiff base ligand with structure shown in formula (II), the present invention will have 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 protecting gas, will have the Schiff base ligand solution of structure shown in formula (II) and liquor ferri trichloridi mixed
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 have the Schiff base ligand of structure and the molar ratio of the ferric trichloride shown in formula (II) be preferably 1:1.
The present invention to described there is the Schiff base ligand solution of structure shown in formula (II) and the preparation method of liquor ferri trichloridi to have no spy
Different limitation, using solution preparation method well known to those skilled in the art.The wishing with structure shown in formula (II)
The solvent of husband's aar ligand solution is preferably the mixed solvent of methanol either 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 mixed solvent of methanol either 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 the solvent
Limitation, it is preferred to use methanol either methanol and acetonitrile mixed solvent.
In the present invention, the temperature of the Schiff base ligand and ferric chloride reaction with structure shown in formula (II) is preferred
It is 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 shown in formula (II) and the time of ferric chloride reaction, 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, then the reaction product of solvent will be gone to recrystallize, and obtains the Schiff with structure shown in formula (I)
Alkali iron compound.The present invention goes the method for solvent and recrystallization not have special limitation to described, using those skilled in the art
The well known method for removing solvent and recrystallization.It is therein molten that the solution that reaction obtains preferably is filtered removing by the present invention
Agent will go the reaction product of solvent using methylene chloride/methanol, methylene chloride/methanol acetonitrile, acetonitrile/ethyl alcohol, acetone/ethanol
Mixed solvent is recrystallized, and the schiff bases iron compound with structure shown in formula (I) is obtained.
The present invention also provides a kind of preparation methods of polylactic acid, comprising the following steps:
Lactide is mixed with catalyst, ring-opening polymerization is carried out in a solvent, obtains polylactic acid；
The catalyst is above-mentioned schiff bases iron compound or the schiff bases iron compound that above-mentioned preparation method is prepared.
The schiff bases iron compound is used to be catalyzed the ring-opening polymerisation of lactide by the present invention, and schiff bases iron catalyst is to third
The ring-opening polymerisation of lactide has very high activity, and the polymerization of monomer can be realized in room temperature, while having to rac-lactide
Comparable selectivity improves the regularity of polymerizate microstructure of molecular chain.
Specifically, the present invention preferably under the conditions of anhydrous and oxygen-free, lactide and catalyst is mixed in a solvent, under stirring
Ring-opening polymerization is carried out, polylactic acid is obtained.Catalyst schiff bases iron compound catalysis with higher provided by the invention is lived
Property, the selectivity of catalyzing ring-opening polymerization of lactide is preferable, can not only be catalyzed rac-lactide and obtain polylactic acid, can also urge
Change levorotatory lactide and dextrorotation lactide mixture obtains polylactic acid.The present invention does not have special limit to the source of the lactide
System, using the commercial goods of lactide, the present invention preferably recrystallizes the lactide of purchase, then carries out ring-opening polymerisation
Reaction.The present invention has no special limitation 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 propylene oxide or 7-oxa-bicyclo[4.1.0.The present invention does not have 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, lower reaction temperature can be used in ring-opening polymerization.In the present invention, the molar ratio of the lactide and catalyst is preferred
For (50~1000): 1, more preferably (100~800): 1, most preferably (100~400): 1.The temperature of the ring-opening polymerization
Preferably 25 DEG C~140 DEG C of degree, more preferably 25 DEG C~60 DEG C, most preferably 25 DEG C；The time of the ring-opening polymerization is excellent
It is selected as 1h~48h, most preferably 12h.
After completing the ring-opening polymerization, the product of the ring-opening polymerization is preferably used chloroform by the present invention
Dissolution, adds excessive ethanol precipitation polymer, dry after filtering, obtains polylactic acid.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 dry technical solution.At this
In invention, the drying is preferably dried in vacuo, and the time of the drying is preferably for 24 hours~48h, most preferably 36h.
After obtaining polylactic acid, the present invention is using homonuclear decoupling hydrogen nuclear magnetic resonance spectrum analysis selectivity.It polymerize poly- third obtained
The backbone sequence distribution of lactide indicates that segment is connected together by the lactide of identical configuration using " mmm ", [mmr],
[rmm], [mrm], [rmr] indicate that the lactide that there is not identical configuration in segment connects together.According to level-one Markovian
Five kinds of sequence relative intensities of statistics, poly- rac-lactide can be indicated by a parameter Pm: Pm refers to catalyst point
After the lactide of sub- one configuration of ring-opening polymerisation, continue probability of the polymerization one with identical configuration lactide, [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.The result shows that schiff bases iron compound provided by the invention has stronger selection to lactide ring-opening polymerisation
Property, improve the regularity of polymerizate space structure.
The present invention also provides a kind of preparation methods of polycaprolactone, comprising the following steps:
Caprolactone is mixed with catalyst, ring-opening polymerization is carried out in a solvent, obtains polycaprolactone；
The catalyst is above-mentioned schiff bases iron compound or the schiff bases iron compound that above-mentioned preparation method is prepared.
The schiff bases iron compound is used to be catalyzed the ring-opening polymerisation of caprolactone by the present invention, and schiff bases iron catalyst is to oneself
The ring-opening polymerisation of lactone has very high activity, and the polymerization of monomer can be realized in room temperature.
Specifically, the present invention preferably under the conditions of anhydrous and oxygen-free, caprolactone and catalyst is mixed in a solvent, under stirring
Ring-opening polymerization polymer reaction is carried out, polycaprolactone is obtained.The present invention does not have special limitation to the source of the caprolactone, using oneself
The commercial goods of lactone, the present invention are preferably evaporated under reduced pressure the caprolactone of purchase, then carry 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 capable of dissolving
Solvent, the present invention are preferably propylene oxide 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, lower reaction temperature can be used in ring-opening polymerization.In the present invention, the molar ratio of the caprolactone and catalyst is preferred
For (50~1000): 1, more preferably (100~800): 1, most preferably (100~500): 1.The temperature of the ring-opening polymerization
Preferably 25 DEG C~100 DEG C of degree, more preferably 25 DEG C~60 DEG C, most preferably 25 DEG C；The time of the ring-opening polymerization is excellent
It is selected as 1h~48h, most preferably 12h~for 24 hours.
After completing the ring-opening polymerization, the product of the ring-opening polymerization is preferably used chloroform by the present invention
Dissolution, adds excessive ethanol precipitation polymer, dry 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 dry technical solution.In
In the present invention, the drying is preferably dried in vacuo, and the time of the drying is preferably for 24 hours~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 present invention provides a kind of schiff bases iron compounds, have structure shown in formula (I),
Wherein, Y is-CH2-CH2-CH2OrR is-H or alkyl.
Schiff bases iron compound provided by the invention has NNOO quad-tree index ability, to be formed in a metal active
Heart binding site, available four-coordination schiff bases iron catalyst.The present invention is used for the schiff bases iron compound to be catalyzed third
The ring-opening polymerisation of lactide and caprolactone, schiff bases iron catalyst have the ring-opening polymerisation of lactide and the ring-opening polymerisation of caprolactone
Very high catalytic activity, the polymerization of monomer can be realized in room temperature, while having comparable selectivity to rac-lactide, mentions
The high regularity of polymerizate microstructure of molecular chain.The experimental results showed that the monomer of method preparation polylactic acid provided by the invention
Conversion ratio can reach 90%, and the monomer conversion of polycaprolactone can reach 99%.When lactide is rac-lactide, obtain
Polylactic acid three-dimensional regularity (Pm) up to 0.60.
In order to further illustrate the present invention, below 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 cannot be interpreted as to the scope of the present invention
It limits.
Embodiment 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 it is mixed to obtain reaction in 80 DEG C of reflux 12h for obtained mixed solution
Close object.Obtained reaction product is obtained Schiff base ligand using ethyl alcohol recrystallization by the solvent being filtered to remove in reaction mixture.
Obtained schiff base compound is carried out elemental 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
Tert-butyl.
Embodiment 2
By 1.14g (S, S) -1,2 cyclohexanediamine are dissolved in 20mL ethyl alcohol, are obtained (S, S) -1,2 cyclohexanediamine solution；It will
4.7g 3,5- di-tert-butyl salicylaldehyde are dissolved in 30mL ethyl alcohol, obtain 3,5- di-tert-butyl salicylaldehyde solution, by the tertiary fourth of 3,5- bis-
Base salicylide solution is slowly added dropwise to (S, S) -1,2 cyclohexanediamine solution, and obtained mixed solution is obtained in 80 DEG C of reflux 12h
Reaction mixture.Obtained reaction product is obtained Schiff using ethyl alcohol recrystallization by the solvent being filtered to remove in reaction mixture
Aar ligand.Obtained schiff base compound is carried out elemental 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
Tert-butyl.
Embodiment 3
By 1.5g 1,3- propane diamine is dissolved in 20mL ethyl alcohol, obtains 1,3- propane diamine solution；5g salicylide is dissolved in 20mL
In ethyl alcohol, salicylide solution is obtained, salicylide solution is slowly added dropwise to 1,3- propane diamine solution, obtained mixed solution is 80
DEG C reflux 12h, obtain reaction mixture.Obtained reaction product is used ethyl alcohol by the solvent being filtered to remove in reaction mixture
It is recrystallized to give Schiff base ligand.Obtained schiff base compound is carried out elemental 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 ethyl alcohol, obtains 1,3- propane diamine solution；4.7g salicylide is dissolved in
In 30mL ethyl alcohol, salicylide solution is obtained, salicylide solution is slowly added dropwise to 1,3- propane diamine solution, obtained mixed solution
In 80 DEG C of reflux 12h, reaction mixture is obtained.The solvent being filtered to remove in reaction mixture uses obtained reaction product
Ethyl alcohol recrystallization obtains Schiff base ligand.Obtained schiff base compound is carried out elemental 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 tert-butyl.
Embodiment 5
Under conditions of high pure nitrogen protection, the Schiff base ligand that 1g embodiment 1 obtains is mixed with 0.4g ferric trichloride
Afterwards, 20mL methanol is added to be mixed, by obtained mixed solution in 25 DEG C of reaction 2h, filters reaction system after completing reaction
Remove solvent, methylene chloride/methanol recrystallization；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, the Schiff base ligand that the present embodiment obtains have structure shown in formula (II), wherein Y isR is
Tert-butyl.
Embodiment 6
Under conditions of high pure nitrogen protection, the Schiff base ligand that 1g embodiment 2 obtains is mixed with 0.4g ferric trichloride
Afterwards, 20mL methanol is added to be mixed, by obtained mixed solution in 25 DEG C of reaction 2h, filters reaction system after completing reaction
Remove solvent, methylene chloride/methanol recrystallization；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 67.73, 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
Tert-butyl.
Embodiment 7
Under conditions of high pure nitrogen protection, the Schiff base ligand that 1g embodiment 3 obtains is mixed with 0.3g ferric trichloride
Afterwards, 15mL methanol is added and 25mL acetonitrile is mixed, by obtained mixed solution in 60 DEG C of reaction 2h, 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 elemental 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 embodiment 4 obtains is mixed with 0.4g ferric trichloride
Afterwards, 15mL methanol is added and 25mL acetonitrile is mixed, by obtained mixed solution in 25 DEG C of reaction 2h, 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 elemental 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 tert-butyl.
Embodiment 9
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.2mmol embodiment 5 are obtained
Schiff bases iron compound mixed with 20mL propylene oxide, obtained mixed solution is stirred to react for 24 hours at 60 DEG C, to what is obtained
10mL chloroform is added in reaction solution and dissolves polymer, then excessive ethanol precipitation polymer is added thereto, filters, very
The dry 48h of sky, obtains polylactic acid.
The quality that the present invention weighs to obtain polylactic acid is 2.4g；The monomer conversion of polylactic acid is 89%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 1.9 ten thousand.
Embodiment 10
Polylactic acid is prepared using the technical solution of embodiment 9 in the present invention, unlike, the present embodiment uses dextrorotation third
The levorotatory lactide that lactide replaces embodiment 9 to use.
The quality that the present invention weighs to obtain polylactic acid is 2.5g；The monomer conversion of polylactic acid is 90%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 1.95 ten thousand.
Embodiment 11
Polylactic acid is prepared using the technical solution of embodiment 9 in the present invention, unlike, the present embodiment uses racemic
The levorotatory lactide that lactide replaces embodiment 9 to use.
The quality that the present invention weighs to obtain polylactic acid is 2.4g；The monomer conversion of polylactic acid is 89%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 1.88 ten thousand.
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- cream
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 embodiment 5 are obtained
Schiff bases iron compound is mixed with 20mL propylene oxide, and obtained mixed solution is stirred to react 18h at 60 DEG C, anti-to what is obtained
It answers and 10mL chloroform dissolution polymer is added in solution, then excessive ethanol precipitation polymer is added thereto, filter, vacuum
Dry 48h, obtains polycaprolactone.
The quality that the present invention weighs to obtain polycaprolactone is 2.2g；The monomer conversion of polycaprolactone is 99%.
The present invention carries out the polycaprolactone that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining caprolactone is 1.8 ten thousand.
Embodiment 13
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.1mmol embodiment 6 are obtained
Schiff bases iron compound mixed with 20mL propylene oxide, obtained mixed solution is stirred to react 30h at 60 DEG C, to what is obtained
10mL chloroform is added in reaction solution and dissolves polymer, then excessive ethanol precipitation polymer is added thereto, filters, very
The dry 48h of sky, obtains polylactic acid.
The quality that the present invention weighs to obtain polylactic acid is 2.3g；The monomer conversion of polylactic acid is 87%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 3.1 ten thousand.
Embodiment 14
Polylactic acid is prepared using the technical solution of embodiment 13 in the present invention, unlike, the present embodiment uses dextrorotation
The levorotatory lactide that lactide replaces embodiment 13 to use.
The quality that the present invention weighs to obtain polylactic acid is 2.2g；The monomer conversion of polylactic acid is 85%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 3.07 ten thousand.
Embodiment 15
Polylactic acid is prepared using the technical solution of embodiment 13 in the present invention, unlike, the present embodiment uses to disappear outside
Revolve the levorotatory lactide that lactide replaces embodiment 13 to use.
The quality that the present invention weighs to obtain polylactic acid is 2.4g；The monomer conversion of polylactic acid is 88%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 3.16 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- cream
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 embodiment 6 are obtained
Schiff bases iron compound is mixed with 20mL propylene oxide, and obtained mixed solution is stirred to react 30h at 60 DEG C, anti-to what is obtained
It answers and 10mL chloroform dissolution polymer is added in solution, then excessive ethanol precipitation polymer is added thereto, filter, vacuum
Dry 48h, obtains polycaprolactone.
The quality that the present invention weighs to obtain polycaprolactone is 2.0g；The monomer conversion of polycaprolactone is 94%.
The present invention carries out the polycaprolactone that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polycaprolactone is 2.8 ten thousand.
Embodiment 17
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.1mmol embodiment 7 are obtained
Schiff bases iron compound mixed with 20mL propylene oxide, obtained mixed solution is stirred to react 8h at 60 DEG C, to what is obtained
10mL chloroform is added in reaction solution and dissolves polymer, then excessive ethanol precipitation polymer is added thereto, filters, very
The dry 48h of sky, obtains polylactic acid.
The quality that the present invention weighs to obtain polylactic acid is 2.4g；The monomer conversion of polylactic acid is 88%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 3.7 ten thousand.
Embodiment 18
Polylactic acid is prepared using the technical solution of embodiment 17 in the present invention, unlike, the present embodiment uses dextrorotation
The levorotatory lactide that lactide replaces embodiment 17 to use.
The quality that the present invention weighs to obtain polylactic acid is 2.5g；The monomer conversion of polylactic acid is 90%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 3.75 ten thousand.
Embodiment 19
Polylactic acid is prepared using the technical solution of embodiment 17 in the present invention, unlike, the present embodiment uses to disappear outside
Revolve the levorotatory lactide that lactide replaces embodiment 17 to use.
The quality that the present invention weighs to obtain polylactic acid is 2.2g；The monomer conversion of polylactic acid is 85%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 3.60 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- cream
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 embodiment 7 are obtained
Schiff bases iron compound is mixed with 20mL propylene oxide, and obtained mixed solution is stirred to react 4h at 60 DEG C, anti-to what is obtained
It answers and 10mL chloroform dissolution polymer is added in solution, then excessive ethanol precipitation polymer is added thereto, filter, vacuum
Dry 48h, obtains polycaprolactone.
The quality that the present invention weighs to obtain polycaprolactone is 1.8g；The monomer conversion of polycaprolactone is 95%.
The present invention carries out the polycaprolactone that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polycaprolactone is 5.6 ten thousand.
Embodiment 21
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.2mmol embodiment 8 are obtained
Schiff bases iron compound mixed with 20mL propylene oxide, obtained mixed solution is stirred to react 3h at 60 DEG C, to what is obtained
10mL chloroform is added in reaction solution and dissolves polymer, then excessive ethanol precipitation polymer is added thereto, filters, very
The dry 48h of sky, obtains polylactic acid.
The quality that the present invention weighs to obtain polylactic acid is 2.1g；The monomer conversion of polylactic acid is 84%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 2.1 ten thousand.
Embodiment 22
Polylactic acid is prepared using the technical solution of embodiment 21 in the present invention, unlike, the present embodiment uses dextrorotation
The levorotatory lactide that lactide replaces embodiment 21 to use.
The quality that the present invention weighs to obtain polylactic acid is 2.1g；The monomer conversion of polylactic acid is 84%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 2.2 ten thousand.
Embodiment 23
Polylactic acid is prepared using the technical solution of embodiment 21 in the present invention, unlike, the present embodiment uses to disappear outside
Revolve the levorotatory lactide that lactide replaces embodiment 21 to use.
The quality that the present invention weighs to obtain polylactic acid is 2.2g；The monomer conversion of polylactic acid is 86%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 2.1 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- cream
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 embodiment 8 are obtained
Schiff bases iron compound is mixed with 20mL propylene oxide, and obtained mixed solution is stirred to react 4h at 60 DEG C, anti-to what is obtained
It answers and 10mL chloroform dissolution polymer is added in solution, then excessive ethanol precipitation polymer is added thereto, filter, vacuum
Dry 48h, obtains polycaprolactone.
The quality that the present invention weighs to obtain polycaprolactone is 2.1g；The monomer conversion of polycaprolactone is 99%.
The present invention carries out the polycaprolactone that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polycaprolactone is 5.3 ten thousand.
Embodiment 25
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.1mmol embodiment 8 are obtained
Schiff bases iron compound mixed with 20mL propylene oxide, obtained mixed solution is stirred to react 20h at 25 DEG C, to what is obtained
10mL chloroform is added in reaction solution and dissolves polymer, then excessive ethanol precipitation polymer is added thereto, filters, very
The dry 48h of sky, obtains polylactic acid.
The quality that the present invention weighs to obtain polylactic acid is 2.0g；The monomer conversion of polylactic acid is 85%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 0.9 ten thousand.
Embodiment 26
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.2mmol embodiment 5 are obtained
Schiff bases iron compound mixed with 20mL propylene oxide, obtained mixed solution is stirred to react 8h at 100 DEG C, to what is obtained
10mL chloroform is added in reaction solution and dissolves polymer, then excessive ethanol precipitation polymer is added thereto, filters, very
The dry 48h of sky, obtains polylactic acid.
The quality that the present invention weighs to obtain polylactic acid is 2.3g；The monomer conversion of polylactic acid is 88%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 1.6 ten thousand.
Embodiment 27
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.1mmol embodiment 6 are obtained
Schiff bases iron compound mixed with 20mL propylene oxide, obtained mixed solution is stirred to react 1h at 140 DEG C, to what is obtained
10mL chloroform is added in reaction solution and dissolves polymer, then excessive ethanol precipitation polymer is added thereto, filters, very
The dry 48h of sky, obtains polylactic acid.
The quality that the present invention weighs to obtain polylactic acid is 2.1g；The monomer conversion of polylactic acid is 87%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 1.9 ten thousand.
Embodiment 28
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.04mmol embodiment 8 are obtained
Schiff bases iron compound mixed with 20mL propylene oxide, obtained mixed solution is stirred to react 10h at 80 DEG C, to what is obtained
10mL chloroform is added in reaction solution and dissolves polymer, then excessive ethanol precipitation polymer is added thereto, filters, very
The dry 48h of sky, obtains polylactic acid.
The quality that the present invention weighs to obtain polylactic acid is 2.5g；The monomer conversion of polylactic acid is 90%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 8.4 ten thousand.
Embodiment 29
Under conditions of anhydrous and oxygen-free, caprolactone that 20.0mmol was evaporated under reduced pressure, 0.1mmol embodiment 7 are obtained
Schiff bases iron compound is mixed with 20mL propylene oxide, and obtained mixed solution is stirred to react 48h at 25 DEG C, anti-to what is obtained
It answers and 10mL chloroform dissolution polymer is added in solution, then excessive ethanol precipitation polymer is added thereto, filter, vacuum
Dry 48h, obtains polycaprolactone.
The quality that the present invention weighs to obtain polycaprolactone is 2.0g；The monomer conversion of polycaprolactone is 96%.
The present invention carries out the polycaprolactone that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polycaprolactone is 1.7 ten thousand.
Embodiment 30
Under conditions of anhydrous and oxygen-free, caprolactone that 20.0mmol was evaporated under reduced pressure, 0.02mmol embodiment 8 are obtained
Schiff bases iron compound is mixed with 20mL propylene oxide, and obtained mixed solution is stirred to react for 24 hours at 60 DEG C, anti-to what is obtained
It answers and 10mL chloroform dissolution polymer is added in solution, then excessive ethanol precipitation polymer is added thereto, filter, vacuum
Dry 48h, obtains polycaprolactone.
The quality that the present invention weighs to obtain polycaprolactone is 1.9g；The monomer conversion of polycaprolactone is 95%.
The present invention carries out the polycaprolactone that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polycaprolactone is 6.7 ten thousand.
Embodiment 31
Under conditions of anhydrous and oxygen-free, levorotatory lactide that 20.0mmol was recrystallized, 0.2mmol embodiment 8 are obtained
Schiff bases iron compound mixed with 20mL propylene oxide, obtained mixed solution is stirred to react 12h at 25 DEG C, to what is obtained
10mL chloroform is added in reaction solution and dissolves polymer, then excessive ethanol precipitation polymer is added thereto, filters, very
The dry 48h of sky, obtains polylactic acid.
The quality that the present invention weighs to obtain polylactic acid is 1.9g；The monomer conversion of polylactic acid is 82%.
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid is 2.1 ten thousand.
Embodiment 32
Under conditions of anhydrous and oxygen-free, caprolactone that 20.0mmol was evaporated under reduced pressure, 0.2mmol embodiment 8 are obtained
Schiff bases iron compound is mixed with 20mL propylene oxide, and obtained mixed solution is stirred to react 10h at 25 DEG C, anti-to what is obtained
It answers and 10mL chloroform dissolution polymer is added in solution, then excessive ethanol precipitation polymer is added thereto, filter, vacuum
Dry 48h, obtains polycaprolactone.
The quality that the present invention weighs to obtain polycaprolactone is 1.9g；The monomer conversion of polycaprolactone is 83%.
The present invention carries out the polycaprolactone that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polycaprolactone is 2.5 ten thousand.
As seen from the above embodiment, the present invention provides a kind of schiff bases iron compound, preparation method and its as urging
The application of agent, schiff bases iron compound provided by the invention have 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 ability, to form one
A metal active centres binding site, available four-coordination schiff bases iron catalyst.The present invention is by the schiff bases iron chemical combination
Object is used to be catalyzed the ring-opening polymerisation of lactide and caprolactone, and schiff bases iron catalyst is to the ring-opening polymerisation of lactide and caprolactone
Ring-opening polymerisation has very high catalytic activity, and the polymerization of monomer can be realized in room temperature, while having phase to rac-lactide
When selectivity, improve the regularity of polymerizate microstructure of molecular chain.The experimental results showed that method preparation provided by the invention
The monomer conversion of polylactic acid can reach 90%, and the monomer conversion of polycaprolactone can reach 99%.When lactide is racemic
When lactide, the three-dimensional regularity (Pm) of obtained polylactic acid is up to 0.60.
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, comprising the following steps:
Lactide is mixed with catalyst, ring-opening polymerization is carried out in propylene oxide, obtains polylactic acid；
The catalyst is the schiff bases iron compound with structure shown in formula (I):
(I)；
Wherein, Y is-CH2-CH2-CH2-；R is tert-butyl；
Molar ratio 1:50 ~ 1000 of the catalyst and the lactide；
The temperature of the ring-opening polymerization is 25 DEG C ~ 140 DEG C, and the time of the ring-opening polymerization is 1h ~ 48h.
2. a kind of preparation method of polycaprolactone, comprising the following steps:
Caprolactone is mixed with catalyst, ring-opening polymerization is carried out in propylene oxide, obtains polycaprolactone；
The catalyst is the schiff bases iron compound with structure shown in formula (I):
(I)；
Wherein, Y is-CH2-CH2-CH2-；R is tert-butyl；
Molar ratio 1:50 ~ 1000 of the catalyst and the caprolactone；
The temperature of the ring-opening polymerization is 25 DEG C ~ 100 DEG C；The time of the ring-opening polymerization is 1h ~ 48h.
3. preparation method according to claim 1 or 2, which is characterized in that the schiff bases with structure shown in formula (I)
The preparation method of iron compound the following steps are included:
Schiff base ligand with structure shown in formula (II) is reacted in a solvent with ferric trichloride, is obtained with shown in formula (I)
The schiff bases iron compound of structure；
(II)；(I)；
Wherein, Y is-CH2-CH2-CH2-；
R is tert-butyl.
4. preparation method according to claim 3, which is characterized in that the Schiff base ligand of structure shown in the formula (II) is pressed
It is prepared according to following steps:
Amine compound with structure shown in formula (III) is carried out with the bigcatkin willow aldehyde compound with structure shown in formula (IV)
Condensation reaction obtains the Schiff base ligand with structure shown in formula (II)；
(III)(IV)；
Wherein, Y is-CH2-CH2-CH2-；
R is tert-butyl.
5. the preparation method according to claim 4, which is characterized in that described with the aminated of structure shown in formula (III)
The molar ratio for closing object and the bigcatkin willow aldehyde compound with structure shown in formula (IV) is 1:(2 ~ 4).
6. the preparation method according to claim 4, which is characterized in that the condensation reaction carries out under reflux conditions；
The time of the condensation reaction is the h of 8 h ~ 16.
7. preparation method according to claim 3, which is characterized in that the schiff bases with structure shown in formula (II) are matched
The molar ratio of body and the ferric trichloride is 1:1.
8. preparation method according to claim 3, which is characterized in that the temperature of the reaction is 25 DEG C ~ 60 DEG C；It is described anti-
The time answered is the h of 8 h ~ 12.
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