CN105541892B - Contain two kinds of preparation method and application of the aluminum complex of nitrogen oxygen multidentate ligand - Google Patents
Contain two kinds of preparation method and application of the aluminum complex of nitrogen oxygen multidentate ligand Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 112
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000003446 ligand Substances 0.000 title claims abstract description 109
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 178
- 238000006243 chemical reaction Methods 0.000 claims abstract description 140
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 112
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 153
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 99
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 66
- 239000002904 solvent Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 39
- 239000012065 filter cake Substances 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 238000000710 polymer precipitation Methods 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 37
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 62
- 238000004458 analytical method Methods 0.000 description 37
- 229920000642 polymer Polymers 0.000 description 35
- 239000007787 solid Substances 0.000 description 33
- 238000001291 vacuum drying Methods 0.000 description 32
- 238000005481 NMR spectroscopy Methods 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229920001244 Poly(D,L-lactide) Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- DOLVFFGLNYMIPV-UHFFFAOYSA-N 2,4-ditert-butyl-6-[3-[(3,5-ditert-butyl-2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C=NCCCN=CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O DOLVFFGLNYMIPV-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- BWRRWBIBNBVHQF-UHFFFAOYSA-N 4-(3-pyridin-2-yl-1,2,4-oxadiazol-5-yl)butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2N=CC=CC=2)=N1 BWRRWBIBNBVHQF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical group [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical group NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229940102001 zinc bromide Drugs 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- 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
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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
Contain two kinds of preparation method and application of the aluminum complex of nitrogen oxygen multidentate ligand, the present invention relates to a kind of synthesis and application of metal aluminum complex, it is relatively low in order to solve the problems, such as the activity of aluminum complex catalyst that is used in existing lactide ring-opening polymerization and stereoselectivity.By asymmetrical N2O2Part, symmetrical NO3Part and Al (OiPr)3Reacted in toluene, obtain containing two kinds of aluminum complexes of nitrogen oxygen multidentate ligand.The toluene solution of the aluminum complex and LA is placed in reaction bulb, polymerisation is carried out at a temperature of 70 DEG C~110 DEG C, obtain polylactide.The present invention adjusts the property of central metal by changing ligand substituting based structures, improves its catalytic performance and stereoselectivity.The larger substitution base of structure is introduced on part, utilization space steric protection metal center reduces side reaction and occurs.
Description
Technical field
The present invention relates to a kind of synthesis of metal aluminum complex, and such complex is in lactide ring-opening polymerization
Application.
Background technology
Biodegradated polymer materal is in medicine such as environmental protection, organizational project, drug controlled release and skeleton fixations
Field has a wide range of applications.Chemosynthetic organism degraded macromolecular material particularly with polylactide (PLA) as representative, by
In having the advantages that excellent performance, can mass produce and cost is relatively low, and receive significant attention.Polylactide, is also named
PLA, is a kind of good biocompatibility, biodegradable Environmentally-friepolymer polymer material, with commodity polymer material
Fundamental characteristics, can be competent at the purposes of most of synthetic plastics.In addition, in pharmaceutical sanitary field, can be widely applied to " human body group
Weaver's journey " material, internal suture, surgery bonesetting material etc..Polylactide study on the synthesis starts from the fifties in last century, early stage
The polymer molecular weight that obtains is relatively low, bad mechanical property, only is used as a kind of intermediate.To the seventies in last century, poly- third hands over
The tight security of degradability and catabolite of the ester in human body is confirmed, with the fermentation work with corncob etc. as raw material
The maturation of skill, the production cost of polylactide is significantly reduced, and it starts as a kind of macromolecular material of novel biodegradable
Receive much concern.The raw material sources of polylactide, can be degradable by the microorganism in soil after discarding in renewable resource, generation
CO2And water, these final products can be converted into the initial feed of synthetic starch by photosynthesis.The degraded of polylactide can be seen
Work is the part of nature carbon cycle.So, polylactide is a kind of environment-friendly, renewable circulation low carbon materials.
The large-scale production and application of polylactide can substitute the Non-biodegradable plastic with oil as raw material, be provided for saving oil
Source, reduction environmental pollution are significant.
Aluminum complex catalyst is widely used in lactide ring-opening polymerization.Study at present it is more for salan and
Salen type ligand aluminum composition catalysts.Gibson to be reported and carry different substituents on ethylenediamine skeleton and fragrant oxygen ring
Salan parts aluminum complex (J.Am.Chem.Soc., 2004,126,2688-2689), Haiyan Ma report a class the third two
The salen ligand binuclears aluminum complex (Chem.Commun., 2012,48,6729-6731) of amine skeleton, Bo Gao report one
Class cyclohexanediamine skeleton salen parts aluminum complex (New J.Chem., 2015,39,4670-4675), have studied part virtue oxygen
Influence of the different substituents to polymerization is carried on ring.Xuan Pang report the salen type aluminum complex catalyst of a class half
(Organometallics,2013,32,5435-5444).From the point of view of the lactide open-ring polymerization catalyst of existing document report,
Catalyst containing chiral ligand needs to use expensive chiral ligand, and the catalyst for containing achiral ligand is conformation mapping
Body, its stereoselectivity is difficult prediction in LA ring-opening polymerizations, and stereoselectivity is influenceed by factors such as solvents,
It is whard to control.Consider from practical application, it is necessary to develop the catalyst of new high activity, highly-solid selectively.
The content of the invention
The invention aims to the aluminum complex catalyst that solves to be used in existing lactide ring-opening polymerization
Activity and stereoselectivity are relatively low, uppity problem, and provide and a kind of contain two kinds of aluminum complexes of nitrogen oxygen multidentate ligand
Preparation method and application.
Preparation method containing two kinds of aluminum complexes of nitrogen oxygen multidentate ligand of the invention is realized according to the following steps：
By asymmetrical N2O2Part (LAPart) with symmetrical NO3Part (LBPart) mol ratio be 2:1 to schlenk
Asymmetrical N is added in bottle2O2Part, symmetrical NO3Part and toluene, then add Al (OiPr)3Toluene solution, 50
DEG C~70 DEG C at a temperature of react 32~48h, reaction solution is extruded under nitrogen atmosphere, evaporation of solvent under reduced pressure is obtained
To containing two kinds of aluminum complexes of nitrogen oxygen multidentate ligand；
Wherein described asymmetrical N2O2The structural formula of part isWherein R1For H,tBu or Br；
Described symmetrical NO3The structural formula of part isWherein R2For H,tBu, Cl or Br, R3For H,
Me ortBu。
Preparation method containing two kinds of aluminum complexes of nitrogen oxygen multidentate ligand of the present invention is in standard anhydrous and oxygen-free
Under the conditions of carry out, obtain C1-C7Aluminum complex.
The method that present invention aluminum complex of the application containing two kinds of nitrogen oxygen multidentate ligands prepares polylactide is according to the following steps
Realize：
Under nitrogen protection, the toluene solution of the aluminum complex containing two kinds of nitrogen oxygen multidentate ligands and LA (lactide) is added
Enter in reaction bulb, with 70 DEG C~110 DEG C of 20~48h of thermotonus, reaction solution is then removed into solvent under vacuo, collect
The solid formation for obtaining is dissolved in dichloromethane, adds cold methanol, and polymer Precipitation, the filter cake after filtering is washed using methyl alcohol
Wash, polylactide is obtained after vacuum drying.
The present invention using it is symmetrical and asymmetric two kinds it is cheap, be easily-synthesized, the part of the easy modulation of structure, synthesis multinuclear gold
Category aluminum complex, by changing ligand substituting based structures, adjusts the property of central metal, improves its catalytic performance and three-dimensional selection
Property.The larger substitution base of structure is introduced on part, utilization space steric protection metal center reduces side reaction and occurs, improves
Product yield.The aluminum complex for containing two kinds of nitrogen oxygen multidentate ligands is applied in lactide ring-opening polymerization, can make to gather
The yield of lactide reaches more than 95%, prepares the number-average molecular weight and calculated value of polymer very close to molecular weight distribution
It is narrower.In addition, further improving catalyst catalytic performance using the structure of different substituents, electronic effect on part, it is improved
Stereoselectivity, in lactide ring-opening polymerization, realizes zinc bromide, prepares stereoregulated polymer (Pm=
0.82)。
Brief description of the drawings
Fig. 1 contains two kinds of aluminum complex C of nitrogen oxygen multidentate ligand for what embodiment 2 was obtained2Crystal structure figure；
Fig. 2 is PDLLA methine same core decouplings1H NMR spectras；
Fig. 3 is PLLA methines1H NMR spectras；
Fig. 4 is PDLLA methines1H NMR spectras；
Fig. 5 is PDLLA's1H NMR spectras.
Specific embodiment
Specific embodiment one：Present embodiment contain two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand by with
Lower step is implemented：
By asymmetrical N2O2Part (LAPart) with symmetrical NO3Part (LBPart) mol ratio be 2:1 to schlenk
Asymmetrical N is added in bottle2O2Part, symmetrical NO3Part and toluene, then add Al (OiPr)3Toluene solution, 50
DEG C~70 DEG C at a temperature of react 32~48h, reaction solution is extruded under nitrogen atmosphere, evaporation of solvent under reduced pressure is obtained
To containing two kinds of aluminum complexes of nitrogen oxygen multidentate ligand；
Wherein described asymmetrical N2O2The structural formula of part isWherein R1For H,tBu or Br；
Described symmetrical NO3The structural formula of part isWherein R2For H,tBu, Cl or Br, R3For
H, Me ortBu。
Asymmetrical N described in present embodiment2O2Part and symmetrical NO3Part be referred to " Dalton Trans.,
2010,39,4440-4446 " method recorded is synthesized.
Present embodiment is urged using two kinds of different nitrogen oxygen part synthesis of lactide ring-opening polymerisation multi-nuclear metal aluminum complexes
Agent.
The reaction equation that present embodiment contains two kinds of aluminum complexes of nitrogen oxygen multidentate ligand is as follows：
Specific embodiment two：Present embodiment and Al (O described unlike specific embodiment oneiPr)3Toluene
Al (O in solutioniPr)3Concentration be 0.18mol/L~0.24mol/L.Other steps and parameter and the phase of specific embodiment one
Together.
Specific embodiment three：Present embodiment and Al (O unlike specific embodiment one or twoiPr)3Toluene it is molten
Al (O in liquidiPr)3With asymmetrical N2O2The mol ratio of part is 1:1.5~1:2.Other steps and parameter and specific implementation
Mode one or two is identical.
Specific embodiment four：The aluminum complex that present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares poly- third and hands over
The method of ester is realized according to the following steps：
Under nitrogen protection, two kinds of toluene of the aluminum complex and LA (rac-LA or L-LA) of nitrogen oxygen multidentate ligand will be contained
Solution is added in reaction bulb, with 70 DEG C~110 DEG C of 20~48h of thermotonus, is then removed reaction solution under vacuo molten
Agent, the solid formation that collection is obtained is dissolved in dichloromethane, adds cold methanol, and polymer Precipitation, the filter cake after filtering makes
Washed with methyl alcohol, polylactide is obtained after vacuum drying.
Present embodiment and following examples pass through1H H NMR spectroscopies determine the conversion ratio of reaction.By gel permeation chromatography
(GPC) polymer is analyzed.δ=5.16 in Fig. 2, the peak at 5.17,5.18,5.21,5.23 is respectively rmr, rmm/
Mmr, mmr/rmm, mmm, mrm peak.Quartet in Fig. 3 at δ=5.13~5.19 is the signal peak of polylactide methine.Figure
Peak in 4 at δ=5.13~5.24 is the signal peak of polylactide methine.Peak in Fig. 5 at δ=1.54~1.59 is poly- third
The signal peak of lactide methyl.
Specific embodiment five：Present embodiment is described from unlike specific embodiment four more containing two kinds of nitrogen oxygen
The aluminum complex of tooth part and the mol ratio 1 of LA:(100~600).Other steps and parameter are identical with specific embodiment four.
Specific embodiment six：Present embodiment is described from unlike specific embodiment five more containing two kinds of nitrogen oxygen
The aluminum complex of tooth part and the mol ratio 1 of LA:(100~300).Other steps and parameter are identical with specific embodiment five.
Specific embodiment seven：The first of described LA unlike one of present embodiment and specific embodiment four to six
The concentration of LA is 1.0mol/L~1.5mol/L in benzole soln.One of other steps and parameter and specific embodiment four to six phase
Together.
Specific embodiment eight：Present embodiment from the toluene solution of LA described unlike specific embodiment seven
The concentration of LA is 1.0mol/L.Other steps and parameter are identical with specific embodiment seven.
Specific embodiment nine：Described cold methanol unlike one of present embodiment and specific embodiment four to eight
Temperature be 0 DEG C~5 DEG C.Other steps and parameter are identical with one of specific embodiment four to eight.
Embodiment 1：It is real according to the following steps that the present embodiment contains two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand
Apply：
Under standard anhydrous and oxygen-free operating condition, to adding asymmetrical N in schlenk bottles2O2Part (0.37g,
1.2mmol), symmetrical NO3Part (0.33g, 0.6mmol) and 50mL toluene (being 75 μ L, about 1.8mmol containing methyl alcohol), then
Add 10mL Al (OiPr)3The toluene solution ((O containing AliPr)3It is 0.49g, about 2.4mmol), the oil bath reaction at 70 DEG C
45h, under nitrogen atmosphere extrudes reaction solution, evaporation of solvent under reduced pressure, obtains containing two kinds of nitrogen oxygen multidentate ligands
Aluminum complex C1(yield：39%)；
Wherein described asymmetrical N2O2The structural formula of part isWherein R1=H；
Described symmetrical NO3The structural formula of part isWherein R2=tBu, R3=H.
The present embodiment elementary analysis result (%), calculated value (C77H91Al4N5O12):C,66.70；H,6.62；N, 5.05. are surveyed
Definite value:C,66.65；H,6.57；N,4.99.
Embodiment 2：It is real according to the following steps that the present embodiment contains two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand
Apply：
Under standard anhydrous and oxygen-free operating condition, to adding asymmetrical N in schlenk bottles2O2Part (0.51g,
1.2mmol), symmetrical NO3Part (0.33g, 0.6mmol) and 50mL toluene (being 75 μ L, about 1.8mmol containing methyl alcohol), then
Add 10mL Al (OiPr)3The toluene solution ((O containing AliPr)3It is 0.49g, about 2.4mmol), the oil bath reaction at 70 DEG C
48h, under nitrogen atmosphere extrudes reaction solution, evaporation of solvent under reduced pressure, obtains containing two kinds of nitrogen oxygen multidentate ligands
Aluminum complex C2(yield：37%)；
Wherein described asymmetrical N2O2R in the structural formula of part1=tBu；
Described symmetrical NO3R in the structural formula of part2=tBu, R3=H.
The present embodiment elementary analysis result (%), calculated value (C93H123Al4N5O12):C,69.34；H,7.70；N,4.35.
Measured value:C,69.29；H,7.65；N,4.32.
Embodiment 3：It is real according to the following steps that the present embodiment contains two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand
Apply：
Under standard anhydrous and oxygen-free operating condition, to adding asymmetrical N in schlenk bottles2O2Part (0.37g,
1.2mmol), symmetrical NO3Part (0.39g, 0.6mmol) and 50mL toluene (being 75 μ L, about 1.8mmol containing methyl alcohol), then
Add 10mL Al (OiPr)3The toluene solution ((O containing AliPr)3It is 0.49g, about 2.4mmol), the oil bath reaction at 70 DEG C
45h, under nitrogen atmosphere extrudes reaction solution, evaporation of solvent under reduced pressure, obtains containing two kinds of nitrogen oxygen multidentate ligands
Aluminum complex C3(yield：45%)；
Wherein described asymmetrical N2O2R in the structural formula of part1=H；
Described symmetrical NO3R in the structural formula of part2=Br, R3=H.
The present embodiment elementary analysis result (%), calculated value (C61H55Al4Br4N5O12):C,49.58；H,3.75；N,
4.74. measured value:C,49.53；H,3.72；N,4.69.
Embodiment 4：It is real according to the following steps that the present embodiment contains two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand
Apply：
Under standard anhydrous and oxygen-free operating condition, to adding asymmetrical N in schlenk bottles2O2Part (0.56g,
1.2mmol), symmetrical NO3Part (0.33g, 0.6mmol) and 50mL toluene (being 75 μ L, about 1.8mmol containing methyl alcohol), then
Add 10mL Al (OiPr)3The toluene solution ((O containing AliPr)3It is 0.49g, about 2.4mmol), the oil bath reaction at 70 DEG C
32h, under nitrogen atmosphere extrudes reaction solution, evaporation of solvent under reduced pressure, obtains containing two kinds of nitrogen oxygen multidentate ligands
Aluminum complex C4(yield：48%)；
Wherein described asymmetrical N2O2R in the structural formula of part1=Br；
Described symmetrical NO3R in the structural formula of part2=tBu, R3=H.
The present embodiment elementary analysis result (%), calculated value (C77H87Al4Br4N5O12):C,54.33；H,5.15；N,
4.11. measured value:C,54.29；H,5.11；N,4.08.
Embodiment 5：It is real according to the following steps that the present embodiment contains two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand
Apply：
Under standard anhydrous and oxygen-free operating condition, to adding asymmetrical N in schlenk bottles2O2Part (0.56g,
1.2mmol), symmetrical NO3Part (0.39g, 0.6mmol) and 50mL toluene (being 75 μ L, about 1.8mmol containing methyl alcohol), then
Add 10mL Al (OiPr)3The toluene solution ((O containing AliPr)3It is 0.37g, about 1.8mmol), in 50 DEG C of oil bath reactions
42h, under nitrogen atmosphere extrudes reaction solution, evaporation of solvent under reduced pressure, obtains containing two kinds after n-hexane washing
The aluminum complex C of nitrogen oxygen multidentate ligand5(yield：51%)；
Wherein described asymmetrical N2O2R in the structural formula of part1=Br；
Described symmetrical NO3R in the structural formula of part2=Br, R3=H.
The present embodiment elementary analysis result (%), calculated value (C61H51Al4Br8N5O12):C,40.86；H,2.87；N,
3.91. measured value:C,40.84；H,2.84；N,3.88.
Embodiment 6：It is real according to the following steps that the present embodiment contains two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand
Apply：
Under standard anhydrous and oxygen-free operating condition, to adding asymmetrical N in schlenk bottles2O2Part (0.51g,
1.2mmol), symmetrical NO3Part (0.34g, 0.6mmol) and 50mL toluene (being 75 μ L, about 1.8mmol containing methyl alcohol), then
Add 10mL Al (OiPr)3The toluene solution ((O containing AliPr)3It is 0.49g, about 2.4mmol), the oil bath reaction at 70 DEG C
40h, under nitrogen atmosphere extrudes reaction solution, evaporation of solvent under reduced pressure, obtains containing two kinds of nitrogen oxygen multidentate ligands
Aluminum complex C6(yield：44%)；
Wherein described asymmetrical N2O2R in the structural formula of part1=tBu；
Described symmetrical NO3R in the structural formula of part2=tBu, R3=Me.
The present embodiment elementary analysis result (%), calculated value (C94H125Al4N5O12):C,69.48；H,7.75；N,4.31.
Measured value:C,69.43；H,7.72；N,4.29.
Embodiment 7：It is real according to the following steps that the present embodiment contains two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand
Apply：
Under standard anhydrous and oxygen-free operating condition, to adding asymmetrical N in schlenk bottles2O2Part (0.56g,
1.2mmol), symmetrical NO3Part (0.34g, 0.6mmol) and 50mL toluene (being 75 μ L, about 1.8mmol containing methyl alcohol), then
Add 10mL Al (OiPr)3The toluene solution ((O containing AliPr)3It is 0.49g, about 2.4mmol), the oil bath reaction at 50 DEG C
48h, under nitrogen atmosphere extrudes reaction solution, evaporation of solvent under reduced pressure, n-hexane washing, obtains containing two kinds of nitrogen oxygen
The aluminum complex C of multidentate ligand7(yield：46%)；
Wherein described asymmetrical N2O2R in the structural formula of part1=Br；
Described symmetrical NO3R in the structural formula of part2=tBu, R3=Me.
The present embodiment elementary analysis result (%), calculated value (C78H89Al4Br4N5O12):C,54.59；H,5.23；N,
4.08. measured value:C,54.55；H,5.18；N,4.05.
Application Example 8：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained1(0.069g, 0.05mmol) and 5mL
The toluene solution of rac-LA rac-lactides (0.72g, 5.00mmol) be added in reaction bulb, with 70 DEG C of thermotonus
36h, then removes solvent under vacuo by reaction solution, and the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL
Temperature is 0 DEG C of methyl alcohol, and polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, poly- third is obtained after vacuum drying and is handed over
Ester.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.47 ten thousand, PDI=1.31.
Application Example 9：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained1(0.069g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 70 DEG C of thermotonus 48h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.46 ten thousand, PDI=1.21.Isotacticity Pm=0.72.
Application Example 10：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained1(0.069g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 110 DEG C of thermotonus 25h, then will
Reaction solution removes solvent under vacuo, and the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is gathered
Compound Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.45 ten thousand, PDI=1.35.
Application Example 11：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained1(0.069g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 110 DEG C of thermotonus 33h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.43 ten thousand, PDI=1.29.
Application Example 12：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained2(0.081g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 70 DEG C of thermotonus 30h, then will be anti-
Liquid is answered to remove solvent under vacuo, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is polymerized
Thing Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.56 ten thousand, PDI=1.26.
Application Example 13：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained2(0.081g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 70 DEG C of thermotonus 39h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.51 ten thousand, PDI=1.17.
Application Example 14：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained2(0.081g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 110 DEG C of thermotonus 23h, then will
Reaction solution removes solvent under vacuo, and the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is gathered
Compound Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.52 ten thousand, PDI=1.27.
Application Example 15：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained2(0.081g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 110 DEG C of thermotonus 32h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.57 ten thousand, PDI=1.25.
Application Example 16：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained3(0.074g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 70 DEG C of thermotonus 33h, then will be anti-
Liquid is answered to remove solvent under vacuo, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is polymerized
Thing Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.49 ten thousand, PDI=1.35.
Application Example 17：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained3(0.074g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 70 DEG C of thermotonus 42h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.48 ten thousand, PDI=1.24.
Application Example 18：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained3(0.074g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 110 DEG C of thermotonus 20h, then will
Reaction solution removes solvent under vacuo, and the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is gathered
Compound Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.53 ten thousand, PDI=1.36.
Application Example 19：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained3(0.074g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 110 DEG C of thermotonus 30h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.44 ten thousand, PDI=1.32.
Application Example 20：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained4(0.085g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 70 DEG C of thermotonus 15h, then will be anti-
Liquid is answered to remove solvent under vacuo, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is polymerized
Thing Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.51 ten thousand, PDI=1.34.
Application Example 21：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained4(0.085g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 70 DEG C of thermotonus 27h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.56 ten thousand, PDI=1.22.
Application Example 22：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained4(0.085g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 110 DEG C of thermotonus 10h, then will
Reaction solution removes solvent under vacuo, and the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is gathered
Compound Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.55 ten thousand, PDI=1.37.
Application Example 23：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained4(0.085g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 110 DEG C of thermotonus 14h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.53 ten thousand, PDI=1.27.
Application Example 24：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained5(0.089g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 70 DEG C of thermotonus 33h, then will be anti-
Liquid is answered to remove solvent under vacuo, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is polymerized
Thing Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.42 ten thousand, PDI=1.35.
Application Example 25：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained5(0.089g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 70 DEG C of thermotonus 43h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.45 ten thousand, PDI=1.29.
Application Example 26：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained5(0.089g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 110 DEG C of thermotonus 26h, then will
Reaction solution removes solvent under vacuo, and the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is gathered
Compound Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.48 ten thousand, PDI=1.38.
Application Example 27：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained5(0.089g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 110 DEG C of thermotonus 34h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.47 ten thousand, PDI=1.32.
Application Example 28：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained6(0.082g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 70 DEG C of thermotonus 35h, then will be anti-
Liquid is answered to remove solvent under vacuo, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is polymerized
Thing Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.44 ten thousand, PDI=1.14.
Application Example 29：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained6(0.082g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 5.00mmol) of 15mL is added in reaction bulb, with 70 DEG C of thermotonus 43h, then
Reaction solution is removed into solvent under vacuo, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols,
Polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.41 ten thousand, PDI=1.07, isotacticity Pm=0.82.
Application Example 30：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained6(0.082g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 110 DEG C of thermotonus 23h, then will
Reaction solution removes solvent under vacuo, and the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is gathered
Compound Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.46 ten thousand, PDI=1.16.
Application Example 31：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained6(0.082g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 110 DEG C of thermotonus 32h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight of polylactide is obtained for 1.52 ten thousand (theoretical values 1.41 ten thousand), PDI=1.09.
Application Example 32：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained7(0.086g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 70 DEG C of thermotonus 31h, then will be anti-
Liquid is answered to remove solvent under vacuo, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is polymerized
Thing Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.43 ten thousand, PDI=1.25.
Application Example 33：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained7(0.086g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 15mL is added in reaction bulb, with 70 DEG C of thermotonus 38h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight of polylactide is obtained for 1.42 ten thousand (theoretical values 1.37 ten thousand), PDI=1.15.
Application Example 34：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained7(0.086g, 0.05mmol) and 5mL
The toluene solution of rac-LA (0.72g, 5.00mmol) be added in reaction bulb, with 110 DEG C of thermotonus 25h, then will
Reaction solution removes solvent under vacuo, and the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, is gathered
Compound Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.54 ten thousand, PDI=1.29.
Application Example 35：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained7(0.086g, 0.05mmol) and
The toluene solution of the rac-LA (2.16g, 15.00mmol) of 10mL is added in reaction bulb, with 110 DEG C of thermotonus 33h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 1.54 ten thousand, PDI=1.26.
Application Example 36：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained1(0.069g, 0.05mmol) and
The toluene solution of the rac-LA (4.32g, 30.00mmol) of 30mL is added in reaction bulb, with 110 DEG C of thermotonus 39h, so
Reaction solution is removed into solvent under vacuo afterwards, the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds the cold first of 10mL
Alcohol, polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 2.51 ten thousand, PDI=1.22.
Application Example 37：The aluminum complex that the present embodiment application contains two kinds of nitrogen oxygen multidentate ligands prepares polylactide
Method is realized according to the following steps：
Under nitrogen protection, two kinds of aluminum complex C of nitrogen oxygen multidentate ligand will be contained1(0.069g, 0.05mmol) and 5mL
The toluene solution of L-LA (0.72g, 5.00mmol) be added in reaction bulb, with 70 DEG C of thermotonus 24h, then will reaction
Liquid removes solvent under vacuo, and the solid formation that collection is obtained is dissolved in 2mL dichloromethane, adds 10mL cold methanols, polymer
Precipitation, the filter cake after filtering is washed using methyl alcohol, and polylactide is obtained after vacuum drying.
The present embodiment passes through1H H NMR spectroscopies determine the conversion ratio of reaction.Polymer is entered by gel permeation chromatography (GPC)
Row analysis.The number-average molecular weight for obtaining polylactide is 0.44 ten thousand, PDI=1.23.
Claims (9)
1. two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand are contained, it is characterised in that be to follow these steps to realize：
By asymmetrical N2O2Part and symmetrical NO3The mol ratio of part is 2:1 in schlenk bottles to adding asymmetrical N2O2
Part, symmetrical NO3Part and toluene, then add Al (OiPr)3Toluene solution, it is anti-at a temperature of 50 DEG C~70 DEG C
32~48h is answered, under nitrogen atmosphere reaction solution is extruded, evaporation of solvent under reduced pressure obtains multiple tooth containing two kinds of nitrogen oxygen
The aluminum complex of part；
Wherein described asymmetrical N2O2The structural formula of part isWherein R1For H,tBu or Br；
Described symmetrical NO3The structural formula of part isWherein R2For H,tBu, Cl or Br, R3It is H, Me
OrtBu。
It is 2. according to claim 1 to contain two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand, it is characterised in that
Described Al (OiPr)3Toluene solution in Al (OiPr)3Concentration be 0.18mol/L~0.24mol/L.
It is 3. according to claim 1 to contain two kinds of preparation methods of the aluminum complex of nitrogen oxygen multidentate ligand, it is characterised in that
Al(OiPr)3Toluene solution in Al (OiPr)3With asymmetrical N2O2The mol ratio of part is 1:1.5~1:2.
4. the method that the application aluminum complex containing two kinds of nitrogen oxygen multidentate ligands as claimed in claim 1 prepares polylactide,
It is characterized in that following these steps to realize：
Under nitrogen protection, the toluene solution of the aluminum complex containing two kinds of nitrogen oxygen multidentate ligands and lactide is added to reaction
In bottle, with 70 DEG C~110 DEG C of 20~48h of thermotonus, reaction solution is then removed into solvent under vacuo, what collection was obtained consolidates
Phase thing is dissolved in dichloromethane, adds cold methanol, and polymer Precipitation, the filter cake after filtering is washed using methyl alcohol, vacuum
Polylactide is obtained after drying.
5. the aluminum complex that application according to claim 4 contains two kinds of nitrogen oxygen multidentate ligands prepares the side of polylactide
Method, it is characterised in that the mol ratio 1 of the described aluminum complex containing two kinds of nitrogen oxygen multidentate ligands and lactide:(100~
600)。
6. the aluminum complex that application according to claim 5 contains two kinds of nitrogen oxygen multidentate ligands prepares the side of polylactide
Method, it is characterised in that the mol ratio 1 of the described aluminum complex containing two kinds of nitrogen oxygen multidentate ligands and lactide:(100~
300)。
7. the aluminum complex that application according to claim 4 contains two kinds of nitrogen oxygen multidentate ligands prepares the side of polylactide
Method, it is characterised in that the concentration of lactide is 1.0mol/L~1.5mol/L in the toluene solution of described lactide.
8. the aluminum complex that application according to claim 7 contains two kinds of nitrogen oxygen multidentate ligands prepares the side of polylactide
Method, it is characterised in that the concentration of lactide is 1.0mol/L in the toluene solution of described lactide.
9. the aluminum complex that application according to claim 4 contains two kinds of nitrogen oxygen multidentate ligands prepares the side of polylactide
Method, it is characterised in that the temperature of described cold methanol is 0 DEG C~5 DEG C.
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Non-Patent Citations (5)
| Title |
|---|
| Group 4 initiators for the stereoselective ROP ofrac-b-butyrolactone and its copolymerization withrac-lactide;Matthew D. Jones et al.;《Chem. Commun.》;20111020;第47卷;第12328-12330页 * |
| Novel Ti(IV) and Zr(IV) complexes and their application in the ring-opening polymerisation of cyclic esters;Matthew D. Jones et al.;《Dalton Transactions》;20090811;第9020-9025页 * |
| Synthesis, structures and catalytic properties of iron(III) complexes with asymmetricN-capped tripodal NO3ligands and a pentadentate N2O3 ligand;Lok H. Tong et al.;《Dalton Transactions》;20080615;第4784–4791页 * |
| 含非对称 N2O2配体异丙氧基铝配合物催化丙交酯开环聚合研究;曹清彬等;《高师理科学刊》;20151031;第35卷(第10期);第48-50页 * |
| 对称氮氧配体钛配合物合成及催化丙交酯开环聚合研究;胡明刚等;《齐齐哈尔大学学报》;20151130;第31卷(第6期);第57-60页 * |
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