CN106380478A - Three-metal-center Schiff base-aluminium compound, preparation method, application and preparation method of polylactic acid - Google Patents
Three-metal-center Schiff base-aluminium compound, preparation method, application and preparation method of polylactic acid Download PDFInfo
- Publication number
- CN106380478A CN106380478A CN201610781584.XA CN201610781584A CN106380478A CN 106380478 A CN106380478 A CN 106380478A CN 201610781584 A CN201610781584 A CN 201610781584A CN 106380478 A CN106380478 A CN 106380478A
- Authority
- CN
- China
- Prior art keywords
- schiff
- present
- polylactic acid
- formula
- obtains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 159
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 158
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims description 130
- 150000001399 aluminium compounds Chemical class 0.000 claims description 97
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 59
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 27
- 229940077746 antacid containing aluminium compound Drugs 0.000 claims description 19
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 17
- YOQHLDOEJYEQRA-UHFFFAOYSA-N 1-(3,5-diacetyl-2,4,6-trihydroxyphenyl)ethanone Chemical compound CC(=O)C1=C(O)C(C(C)=O)=C(O)C(C(C)=O)=C1O YOQHLDOEJYEQRA-UHFFFAOYSA-N 0.000 claims description 16
- 229910007161 Si(CH3)3 Inorganic materials 0.000 claims description 16
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 13
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 230000004044 response Effects 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 4
- 229960001553 phloroglucinol Drugs 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 16
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 9
- 239000002262 Schiff base Substances 0.000 abstract description 2
- 150000004753 Schiff bases Chemical class 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 74
- 238000004458 analytical method Methods 0.000 description 31
- 239000002253 acid Substances 0.000 description 29
- 210000000481 breast Anatomy 0.000 description 29
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 239000004793 Polystyrene Substances 0.000 description 28
- 238000005227 gel permeation chromatography Methods 0.000 description 28
- 229920002223 polystyrene Polymers 0.000 description 28
- 239000012925 reference material Substances 0.000 description 28
- 238000005303 weighing Methods 0.000 description 28
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
- 238000001953 recrystallisation Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 238000012869 ethanol precipitation Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- -1 chloroform poly- Compound Chemical class 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XILIYVSXLSWUAI-UHFFFAOYSA-N 2-(diethylamino)ethyl n'-phenylcarbamimidothioate;dihydrobromide Chemical compound Br.Br.CCN(CC)CCSC(N)=NC1=CC=CC=C1 XILIYVSXLSWUAI-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 229960004217 benzyl alcohol Drugs 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- GHIFULCJQQCBEP-UHFFFAOYSA-N 1-(2,6-diacetyl-3,4,5-trihydroxyphenyl)ethanone Chemical compound CC(=O)C1=C(O)C(O)=C(O)C(C(C)=O)=C1C(C)=O GHIFULCJQQCBEP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229920001585 atactic polymer Polymers 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 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
- 238000005406 washing Methods 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
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide 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
-
- 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)
- Toxicology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a three-metal-center Schiff base-aluminium compound, which has a structure as shown in the formula (I). By using triacetyl-m-trihydroxybenzene as the core, a three-metal active center binding site is provided to form three-metal-center Schiff base. On one hand, there is a large molecular space to obtain large steric hindrance. Thus, selectivity to ring-opening polymerization of lactide is enhanced, and regularity of the space structure of a polymerization product is raised. On the other hand, the three-metal-center special structure obviously enhances reaction activity of a catalyst and raises speed of a polymerization reaction. Thus, the Schiff base-aluminium compound provided by the invention has high catalytic activity and structural selectivity to ring-opening polymerisation of lactide, and regularity of the space structure of polylactic acid is raised. It shows through experimental results that the three-metal-center Schiff base-aluminium compound is used for preparation of polylactic acid, reaction yield can reach 95% and stereo-regularity (Pm) of polylactic acid can reach 0.98.
Description
Technical field
The present invention relates to technical field, more particularly, to a kind of three metal center Schiff's base aluminium compounds, its preparation method, should
With and polylactic acid preparation method.
Background technology
Polylactic acid is a kind of biodegradation material of chemosynthesis, has in packaging material, biological medicine and pharmaceuticals industry
And be widely applied.The synthesis of polylactic acid generally adopts two methods, i.e. lactide (cyclic dimer of lactic acid) ring-opening polymerisation
And direct polycondensation of lactic acid.The method that wherein polyphosphazene polymer lactic acid typically adopts lactide ring-opening polymerisation, and had a large amount of literary compositions
Offer and patent has carried out relevant report to lactide ring-opening polymerisation, such as the United States Patent (USP) of Patent No. 5235031 and Patent No.
5357034 United States Patent (USP).
Lactide has three kinds of stereoisomers：Levorotatory lactide (LLA), dextrorotation lactide (DLA) and meso third are handed over
Ester, its structure is as follows respectively：
At present, the catalyst that lactide ring-opening polymerisation is commonly used is nontoxic tin compound, such as stannic chloride and stannous octoate.
Stannum series catalysts effect under, optically pure DLA, LLA respectively ring-opening polymerisation obtain isotactic poly- dextrorotation lactide and
Poly- levorotatory lactide, the product of rac-lactide ring-opening polymerisation under the same conditions is atactic polymer.
Research shows, the spatial configuration of lactide has conclusive to the machinery of polymer, processing and degraded property
Effect.For example, isotactic poly- dextrorotation lactide and poly- levorotatory lactide are the crystalline polymer of 180 DEG C of fusing point,
The atactic polymer that rac-lactide polymerization obtains is noncrystallizable polymer.Compared with amorphism polylactic acid, crystallinity
The use wider range of polylactic acid, can be more advantageous close to melt temperature.It is thus desirable to exploitation a kind of to lactide
Polymerization has stereoselective ring-opening polymerization catalyst, and rac-lactide polymerization can be made to obtain crystalline polylactic acid.And have
Higher selectivity and activity.
Content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of three metal center Schiff's base aluminium compounds,
The preparation method of its preparation method, application and polylactic acid, three prepared metal center Schiff's base aluminium compounds are used for the third friendship
Polyisocyanate polyaddition reacts, and has higher selectivity and activity.
The invention provides a kind of three metal center Schiff's base aluminium compounds, there is structure shown in formula (I)：
Wherein, R is-CH3、-CH2CH3、-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph；
R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC(CH3)3
(CH3)2,-F ,-Cl ,-Br or-NO2.
Present invention also offers a kind of preparation method of three metal center Schiff's base aluminium compounds, comprise the following steps：
By the Schiff's base shown in formula (II) structure and Al (R ')3Reaction, obtains the Schiff's base calorize shown in formula (III) structure
Compound；
Wherein, R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC
(CH3)3(CH3)2,-F ,-Cl ,-Br or-NO2；
R ' is-CH3Or-CH2CH3.
Present invention also offers a kind of preparation method of three metal center Schiff's base aluminium compounds, comprise the following steps：
A) by the Schiff's base shown in formula (II) structure and Al (R ')3Reaction, obtains the Schiff's base aluminum shown in formula (III) structure
Compound；
B) the Schiff's base aluminium compound shown in described formula (III) structure is reacted with R H, obtain shown in formula (IV) structure
Schiff's base aluminium compound；
Wherein, R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC
(CH3)3(CH3)2,-F ,-Cl ,-Br or-NO2；
R ' is-CH3Or-CH2CH3；
R is-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph.
Preferably, the Schiff's base shown in described formula (II) structure and Al (R ')3Mol ratio be 1:3.
Preferably, the Schiff's base shown in described formula (II) structure and Al (R ')3The reaction temperature of reaction is 60 DEG C～90 DEG C,
Response time is 9～12h.
Preferably, the Schiff's base shown in described formula (II) structure is prepared according to following steps：
Compound shown in formula (V) and the substituted salicylic aldehydes shown in formula (VI) are reacted, obtains the seat shown in formula (II) structure
Husband's alkali；
In formula (VI), R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-
SiC(CH3)3(CH3)2,-F ,-Cl ,-Br or-NO2.
Preferably, compound shown in described formula (V) is prepared according to following steps：
S1) phloroglucinol, acetic acid and acetic anhydride are reacted under the catalytic action of concentrated sulphuric acid, obtained between triacetyl
Benzenetriol；
S2) triacetyl phloroglucinol is reacted with 1,2- diaminourea -2- methylpropane and obtain compound shown in formula (V).
Present invention also offers three metal center Schiff's base aluminium compounds shown in formula (I) structure are anti-as lactide polymerization
Answer the application of catalyst,
Wherein, R is-CH3、-CH2CH3、-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph；
R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC(CH3)3
(CH3)2,-F ,-Cl ,-Br or-NO2.
Present invention also offers a kind of preparation method of polylactic acid, comprise the following steps：
Lactide is reacted with the Schiff's base aluminium compound shown in formula (I) structure, obtains polylactic acid；
Wherein, R is-CH3、-CH2CH3、-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph；
R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC(CH3)3
(CH3)2,-F ,-Cl ,-Br or-NO2.
Preferably, the Schiff's base aluminium compound shown in described formula (I) structure and the mol ratio of lactide are 1:50～1:
10000.
Compared with prior art, the invention provides a kind of three metal center Schiff's base aluminium compounds, have shown in formula (I)
Structure.It is core that the present invention utilizes triacetyl phloroglucinol, provides three metal active centres binding sites, forms three metals
Center Schiff's base, on the one hand have larger molecule space obtain larger sterically hindered so as to lactide ring-opening polymerisation
Selective long-range DEPT, improve the regularity of polymerizate space structure；On the other hand the special construction of this kind of three metal centers
Clearly enhance the reactivity of catalyst, improve the speed of polyreaction.Therefore, the Schiff's base calorize that the present invention provides is closed
The ring-opening polymerisation to lactide for the thing, has higher catalysis activity and structure selectivity, improves the rule of polylactic acid space structure
Whole property.Test result indicate that, the three metal center Schiff's base aluminium compounds that the present invention provides, it is used for preparing polylactic acid, reaction is received
Rate can reach 95%, and the three-dimensional regularity (Pm) of the polylactic acid obtaining is up to 0.98.
Specific embodiment
The invention provides a kind of three metal center Schiff's base aluminium compounds, there is structure shown in formula (I)：
Wherein, R is-CH3、-CH2CH3、-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph；
R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC(CH3)3
(CH3)2,-F ,-Cl ,-Br or-NO2.
It is core that the present invention utilizes triacetyl phloroglucinol, provides three metal active centres binding sites, forms three
Metal center Schiff's base, on the one hand have larger molecule space obtain larger sterically hindered so as to lactide open loop
The Selective long-range DEPT of polymerization, improves the regularity of polymerizate space structure；On the other hand this kind of three metal centers is special
Structure clearly enhances the reactivity of catalyst, improves the speed of polyreaction.Therefore, the Schiff's base aluminum that the present invention provides
The ring-opening polymerisation to lactide for the compound, has higher catalysis activity and structure selectivity, improves polylactic acid space structure
Regularity.Test result indicate that, the three metal center Schiff's base aluminium compounds that the present invention provides, it is used for preparing polylactic acid, instead
Yield is answered to can reach 95%, the three-dimensional regularity (Pm) of the polylactic acid obtaining is up to 0.98.
In structure shown in above-mentioned formula (I), methyl is all represented with singly-bound.
Present invention also offers a kind of preparation method of three metal center Schiff's base aluminium compounds, comprise the following steps：
By the Schiff's base shown in formula (II) structure and Al (R ')3Reaction, obtains the Schiff's base calorize shown in formula (III) structure
Compound；
Wherein, R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC
(CH3)3(CH3)2,-F ,-Cl ,-Br or-NO2；
R ' is preferably-CH3Or-CH2CH3.
Described reaction is carried out in a solvent.Described solvent can be organic solvent well known to those skilled in the art, preferably
For oxolane or toluene.
Preferably, work as R1And R2Independently selected from-H ,-F ,-Cl ,-Br or-NO2When, described reaction dissolvent is preferably tetrahydrochysene
Furan；Work as R1And R2Independently selected from-CH3、-CH2CH3、-CH(CH3)2Or-C (CH3)3When, described reaction dissolvent is preferably first
Benzene.
In the present invention, described Al (R ')3It is preferably Al (CH3)3Or Al (CH2CH3)3.R ' in formula (III) is derived from Al
(R′)3.
Described Al (R ')3It is preferably 3 with the mol ratio of the Schiff's base shown in formula (II) structure:1, seat provided by the present invention
Husband's alkali cpd be metal complex, above-mentioned mol ratio can ensure metal active centres simultaneously with two C=N functional groups
Form coordinate bond.
The temperature of described reaction is preferably 60 DEG C～90 DEG C, and the selection of temperature depends on the selection of reaction dissolvent, more preferably
For 70 DEG C or 90 DEG C, the response time is preferably 9～12h, more preferably 10h.
The method that described reaction preferably employs column chromatography is purified.
Present invention also offers a kind of preparation method of three metal center Schiff's base aluminium compounds, comprise the following steps：
A) by the Schiff's base shown in formula (II) structure and Al (R ')3Middle reaction, obtains the Schiff's base shown in formula (III) structure
Aluminium compound；
B) the Schiff's base aluminium compound shown in described formula (III) structure is reacted with R H, obtain shown in formula (IV) structure
Schiff's base aluminium compound；
Wherein, R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC
(CH3)3(CH3)2,-F ,-Cl ,-Br or-NO2；
R ' is preferably-CH3Or-CH2CH3；
R is preferably-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph.
Above-mentioned steps A) solvent, reaction temperature, the response time ibid, will not be described here.
Described Al (R ')3Selection ibid, will not be described here.
Above-mentioned steps B) carry out in a solvent.Described solvent can be organic solvent well known to those skilled in the art, excellent
Elect oxolane or toluene as.
Preferably, work as R1And R2Independently selected from-H ,-F ,-Cl ,-Br or-NO2When, described reaction dissolvent is preferably tetrahydrochysene
Furan；Work as R1And R2Independently selected from-CH3、-CH2CH3、-CH(CH3)2Or-C (CH3)3When, described reaction dissolvent is preferably first
Benzene.
Described R H is preferably CH3OH、CH3CH2OH、(CH3)2CHOH or Ph CH2OH.
Described R H is preferably 3 with the mol ratio of the Schiff's base aluminium compound shown in formula (III) structure:1.
The temperature of described reaction is preferably 60 DEG C～90 DEG C, and the selection of temperature depends on the selection of reaction dissolvent, more preferably
For 70 DEG C or 90 DEG C, the response time is preferably 9～12h, more preferably 10h.
The method that described reaction preferably employs column chromatography is purified.
In the present invention, the Schiff's base shown in described formula (II) structure is preferably prepared according to following steps：
Compound shown in formula (V) and the substituted salicylic aldehydes shown in formula (VI) are reacted, obtains the seat shown in formula (II) structure
Husband's alkali；
In formula (VI), R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-
SiC(CH3)3(CH3)2,-F ,-Cl ,-Br or-NO2.
Above-mentioned reaction is carried out in a solvent.Described solvent can be organic solvent well known to those skilled in the art, preferably
For ethanol.
The temperature of described reaction is preferably room temperature, and the time of reaction is preferably 10～30h.
The method that described reaction preferably employs column chromatography is purified.
Compound shown in described formula (V) is preferably prepared according to following steps：
S1) phloroglucinol, acetic acid and acetic anhydride are reacted under the catalytic action of concentrated sulphuric acid, obtained between triacetyl
Benzenetriol；
S2) triacetyl phloroglucinol is reacted with 1,2- diaminourea -2- methylpropane and obtain compound shown in formula (V).
Described step S1) in, the temperature of reaction is preferably 60～80 DEG C, and the time of described reaction is preferably 10～15h.
After reaction terminates, reaction system is poured into water, and filters, and the method that solid preferably employs column chromatography is purified.
Described step S2) in, the temperature of reaction is preferably room temperature, and the response time is preferably 2～4 days.
After reaction terminates, filter and can get compound shown in formula (V).
In the present invention, reagent needed for remaining is commercially available.
Present invention also offers three metal center Schiff's base aluminium compounds shown in formula (I) structure are anti-as lactide polymerization
Answer the application of catalyst.
When preparing for polylactic acid, preparation method comprises the following steps：
Lactide is reacted with the Schiff's base aluminium compound shown in formula (I) structure, obtains polylactic acid.
Described reaction is carried out in a solvent, and described solvent can be organic solvent well known to those skilled in the art, preferably
For oxolane or toluene.
Schiff's base aluminium compound shown in described formula (I) structure is preferably 1 with the mol ratio of lactide:50～1:10000,
More preferably 1:300～1:3000.
The reaction temperature of described lactide polyreaction is preferably 25～130 DEG C, and the response time is preferably 1.0～72h.Should
Reaction is carried out preferably under conditions of anhydrous and oxygen-free, it is possible to reduce the generation of side reaction.
Described lactide can be levorotatory lactide, dextrorotation lactide or Study of Meso-Lactide.
After described reaction terminates, it is preferred to use the method for recrystallization is purified.
The ring-opening polymerization obtaining product is preferably adopted chloroform to dissolve by the present invention, adds excessive ethanol and sinks
It is dried after shallow lake polymer, filtration, obtain polylactic acid.
The present invention does not have special restriction to the consumption of described chloroform, by the product obtaining dissolving can be
Can；The present invention to described filter and be dried method there is no special restriction, using well known to those skilled in the art filter and
The technical scheme being dried；Described drying in the present invention is preferably and is vacuum dried, time of described drying be preferably 36h～
60h, more preferably 39h～57h, most preferably 45h～48h.
After obtaining polylactic acid, the present invention adopts the selectivity of homonuclear decoupling proton nmr spectra analytical reactions, and polymerization obtains
Polylactide backbone sequence distribution, using " mmm " represent segment be to be connected together by the lactide of identical configuration,
[mmr], [rmm], [mrm], [rmr] represent to exist in segment and differ the lactide of configuration and connect together.According to one-level
Markovian counts, and five kinds of sequence relative intensities of poly- rac-lactide can be represented by parameter Pm：Pm refers to one
After the lactide of one configuration of catalyst molecule ring-opening polymerisation, continue one probability with identical configuration lactide of polymerization,
[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.Result shows, the Schiff's base aluminium compound that the present invention provides has to lactide ring-opening polymerization
There is stronger selectivity, improve the regularity of polymerizate space structure.
Described Schiff's base aluminium compound is three Metal Schiff _ base Al catalysts, has three metal active centres, its reaction
Activity is higher, and the consumption of catalyst is less, and reaction temperature is relatively low.Meanwhile, it has larger sterically hindered, and catalysis lactide is opened
The Selective long-range DEPT of cyclopolymerization, has higher catalysis activity and structure selectivity, improves the regular of polylactic acid space structure
Property.Test result indicate that, the yield that the method that the present invention provides prepares polylactic acid can reach 95%, the solid of the polylactic acid obtaining
Regularity (Pm) is up to 0.98.
In order to further illustrate the present invention, the three metal center Schiff's base calorizes that the present invention provided with reference to embodiment
The preparation method of compound, its preparation method, application and polylactic acid is described in detail.
The preparation of compound shown in embodiment 1 intermediate formula (V)
3.0g phloroglucinol, 15mL acetic acid are mixed by 1.1 with 15mL acetic anhydride, Deca 2mL concentrated sulphuric acid, are heated to 75 DEG C instead
Answer 12h, after reaction terminates, pour stirring 10min in 200mL water into, filter, each 50mL washes three times, and each 10mL ethanol is washed
Three times, vacuum pumps solvent, and after solid column chromatography, the white solid obtaining is compound triacetyl phloroglucinol.
1.0g triacetyl phloroglucinol is slowly added to 4mL 2- methyl isophthalic acid by 1.2, in 2- propane diamine, room temperature reaction 3 days,
After filtration, pentane washing obtains yellow solid, is compound shown in formula (V).
Respectively 1.1,1.2 compounds obtaining are analyzed using nuclear magnetic resonance, NMR, obtain the hydrogen spectrum of each compound, knot
Fruit is as follows：
Compound triacetyl phloroglucinol：1H NMR (300.00MHz, CDCl3):δ=2.71 (s, CH39H).
Compound shown in formula (V)：1H NMR(300.00MHz,CDCl3):δ=3.28 (m, CH26H), 2.50 (s, CH3
9H), 1.21 (s, C (CH3)218H).
The synthesis of embodiment 2 Schiff's base IIa
IIa：R1=R2=-H.
Compound shown in the formula obtaining in 0.9g 1.2 (V) is dissolved in 10ml ethanol, adds the 10ml of 1.0g salicylide
Ethanol solution, room temperature reaction 20h, revolving removes most of solvent, and column chromatography purifies, and obtains Schiff's base IIa.
Using nuclear magnetic resonance, NMR, the Schiff's base IIa obtaining in embodiment 2 is analyzed, obtains its nuclear magnetic data result such as
Under：1H NMR(400MHz,CDCl3):δ=14.5-13.2 (m OH 6H), 8.38 (m NCH 3H), 7.28,6.95,6.86 (m
ArH 12H),3.49(m NCH2C 6H),2.36(m ArCCH39H),1.42,1.29(m C(CH3)218H).
The synthesis of embodiment 3 Schiff's base IIb
IIb：R1=R2=-C (CH3)3
Compound shown in the formula obtaining in 0.9g 1.2 (V) is dissolved in 10ml ethanol, adds 1.5g 3,5- di-t-butyl
The 10ml ethanol solution of salicylide, room temperature reaction 20h, revolving removes most of solvent, and column chromatography purifies, and obtains Schiff's base IIb.
Using nuclear magnetic resonance, NMR, the Schiff's base IIb obtaining in embodiment 3 is analyzed, obtains its nuclear magnetic data, result is such as
Under：1H NMR(400MHz,CDCl3):δ=14.56-13.46 (m OH 6H), 8.42 (m NCH 3H), 7.38,7.10 (m ArH
6H),3.51(m NCH2C 6H),2.46(m ArCCH39H),1.45,1.31(m C(CH3)3,C(CH3)272H).
The synthesis of embodiment 4 Schiff's base IIc
IIc：R1=-Si (CH3)2C(CH3)3, R2=-H
Compound shown in the formula obtaining in 0.9g 1.2 (V) is dissolved in 10ml ethanol, adds 1.5g3- (the tertiary fourth of dimethyl
Base) silicon salicylide 10ml ethanol solution, room temperature reaction 20h, revolving removes most of solvent, and column chromatography purifies, and obtains Schiff
Alkali IIc.
Using nuclear magnetic resonance, NMR, the Schiff's base IIc obtaining in embodiment 4 is analyzed, obtains its nuclear magnetic data, result is such as
Under：1H NMR(400MHz,CDCl3):δ=14.50-13.23 (m OH 6H), 8.39,8.25 (m NCH 3H), 7.41,7.28,
6.87(m ArH 9H),3.54(m NCH2C 6H),2.42(m ArCCH39H),1.45,1.26(m C(CH3)218H),0.94
(s SiC(CH3)327H),0.34(s Si(CH3)218H).
The synthesis of embodiment 5 Schiff's base aluminium compound Ia-1～Ia-5
Ia-1：R1=R2=-H, R=-CH2CH3；
Ia-2：R1=R2=-H, R=-OCH3；
Ia-3：R1=R2=-H, R=-OCH2CH3；
Ia-4：R1=R2=-H, R=-OCH (CH3)2；
Ia-5：R1=R2=-H, R=-OCH2Ph.
5.1 under conditions of inert gas shielding, and the IIa toluene solution that 2ml concentration is 1mol/L with 6ml concentration is
The AlEt of 1mol/L3Toluene solution mix and blend, 90 DEG C of reaction 10h, are down to room temperature, evacuation 0.1Mpa removes volatility thing
Matter, obtains Schiff's base aluminium compound Ia-1.
5.2 the Schiff's base obtaining in 4mmol 5.1 aluminium compound Ia-1 is dissolved in toluene, adds 12mmol methanol, obtains
To Schiff's base aluminium compound Ia-2.
The preparation method of Schiff's base aluminium compound Ia-3～Ia-5 is identical with Ia-2, and wherein difference is：By methanol respectively
It is changed to ethanol, isopropanol, benzylalcohol.
Using elementary analysiss, the Schiff's base aluminium compound Ia-1～Ia-5 obtaining in embodiment 5 is analyzed, obtains it
Each atom content.
Ia-1:Elem.Anal. (%):Calc.C 65.37；H 6.78；N 8.97.Found:C 64.26；H 7.54；N
8.16.
Ia-2:Elem.Anal. (%):Calc.C 61.14；H 6.09；N 8.91.Found:C 60.28；H 6.73；N
8.06.
Ia-3:Elem.Anal. (%):Calc.C 62.19；H 6.45；N 8.53.Found:C 61.54；H 6.82；N
7.69.
Ia-4:Elem.Anal. (%):Calc.C 63.15；H 6.77；N 8.18.Found:C 62.56；H 7.13；N
7.86.
Ia-5:Elem.Anal. (%):Calc.C 67.68；H 5.94；N 7.11.Found:C 67.52；H 6.84；N
6.49.
Embodiment 6 Schiff's base aluminium compound Ib-1～Ib-5
Ib-1：R1=R2=-C (CH3)3, R=-CH2CH3；
Ib-2：R1=R2=-C (CH3)3, R=-OCH3；
Ib-3：R1=R2=-C (CH3)3, R=-OCH2CH3；
Ib-4：R1=R2=-C (CH3)3, R=-OCH (CH3)2；
Ib-5：R1=R2=-C (CH3)3, R=-OCH2Ph.
The preparation method of 6.1 Schiff's base aluminium compound Ib-1 is identical with Ia-1, and wherein difference is：By IIa toluene solution
It is changed to IIb toluene solution.
6.2 the Schiff's base obtaining in 4mmol 6.1 aluminium compound Ib-1 is dissolved in toluene, adds 12mmol methanol, obtains
To Schiff's base aluminium compound Ib-2.
The preparation method of Schiff's base aluminium compound Ib-3～Ib-5 is identical with Ib-2, and wherein difference is：By methanol respectively
It is changed to ethanol, isopropanol, benzylalcohol.
Using elementary analysiss, the Schiff's base aluminium compound Ib-1～Ib-5 obtaining in embodiment 6 is analyzed, obtains it
Each atom content.
Ib-1:Elem.Anal. (%):Calc.C 70.73；H 8.78；N 6.60.Found:C 70.34；H 9.23；N
6.18.
Ib-2:Elem.Anal. (%):Calc.C 67.58；H 8.27；N 6.57.Found:C 67.02；H 8.97；N
6.31.
Ib-3:Elem.Anal. (%):Calc.C 68.16；H 8.47；N 6.36.Found:C 67.33；H 8.91；N
6.64.
Ib-4:Elem.Anal. (%):Calc.C 68.70；H 8.65；N 6.16.Found:C 68.08；H 9.24；N
5.86.
Ib-5:Elem.Anal. (%):Calc.C 71.69；H 7.82；N 5.57.Found:C 70.58；H 8.06；N
5.37.
Embodiment 7 Schiff's base aluminium compound Ic-1～Ic-5
Ic-1：R1=-Si (CH3)2C(CH3)3,R2=-H, R=-CH2CH3；
Ic-2：R1=-Si (CH3)2C(CH3)3,R2=-H, R=-OCH3；
Ic-3：R1=-Si (CH3)2C(CH3)3,R2=-H, R=-OCH2CH3；
Ic-4：R1=-Si (CH3)2C(CH3)3,R2=-H, R=-OCH (CH3)2；
Ic-5：R1=-Si (CH3)2C(CH3)3,R2=-H, R=-OCH2Ph.
The preparation method of 7.1 Schiff's base aluminium compound Ic-1 is identical with Ia-1, and wherein difference is：By IIa toluene solution
It is changed to IIc toluene solution.
7.2 the Schiff's base obtaining in 4mmol 7.1 aluminium compound Ic-1 is dissolved in toluene, adds 12mmol methanol, obtains
To Schiff's base aluminium compound Ic-2.
The preparation method of Schiff's base aluminium compound Ic-3～Ic-5 is identical with Ic-2, and wherein difference is：By methanol respectively
It is changed to ethanol, isopropanol, benzylalcohol.
Using elementary analysiss, the Schiff's base aluminium compound Ic-1～Ic-5 obtaining in embodiment 7 is analyzed, obtains it
Each atom content.
Ic-1:Elem.Anal. (%):Calc.C 64.75；H 8.27；N 6.57.Found:C 63.94；H 8.78；N
6.03.
Ic-2:Elem.Anal. (%):Calc.C 61.65；H 7.76；N 6.54.Found:C 61.07；H 8.34；N
6.73.
Ic-3:Elem.Anal. (%):Calc.C 62.41H 7.97；N 6.33.Found:C 62.84；H 7.33；N
6.09.
Ic-4:Elem.Anal. (%):Calc.C 63.13；H 8.17；N 6.13.Found:C 62.55；H 8.62；N
5.81.
Ic-5:Elem.Anal. (%):Calc.C 66.64；H 7.39；N 5.55.Found:C 65.86；H 7.92；N
5.03.
Embodiment 8
Under conditions of anhydrous and oxygen-free, in rac-lactide that 20.0mmol recrystallization is crossed, 0.2mmol embodiment 5
The Schiff's base aluminium compound Ia-2 obtaining is mixed with 40mL toluene, 25 DEG C of stirring reactions 42h, adds the dissolving of 40mL chloroform poly-
Compound, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 2.0g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 0.7 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.76.
Embodiment 9
The present invention prepares polylactic acid using the technical scheme of embodiment 8, and except for the difference that, the present embodiment adopts embodiment
The Schiff's base aluminium compound Ia-3 that 5 obtain replaces the Schiff's base aluminium compound Ia-2 that embodiment 8 adopts.
The quality that present invention weighing obtains polylactic acid is 2.1g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 0.7 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.75.
Embodiment 10
The present invention prepares polylactic acid using the technical scheme of embodiment 8, and except for the difference that, the present embodiment adopts embodiment
The Schiff's base aluminium compound Ia-4 that 5 obtain replaces the Schiff's base aluminium compound Ia-2 that embodiment 8 adopts.
The quality that present invention weighing obtains polylactic acid is 2.2g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 0.75 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.75.
Embodiment 11
The present invention prepares polylactic acid using the technical scheme of embodiment 8, and except for the difference that, the present embodiment adopts embodiment
The Schiff's base aluminium compound Ia-5 that 5 obtain replaces the Schiff's base aluminium compound Ia-2 that embodiment 8 adopts.
The quality that present invention weighing obtains polylactic acid is 2.0g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 0.7 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.74.
Embodiment 12
Under conditions of anhydrous and oxygen-free, in rac-lactide that 20.0mmol recrystallization is crossed, 0.03mmol embodiment 5
The Schiff's base aluminium compound Ia-2 obtaining is mixed with 40mL toluene, 70 DEG C of stirring reactions 6h, adds the dissolving of 40mL chloroform poly-
Compound, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 2.5g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 2.0 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.64.
Embodiment 13
The present invention prepares polylactic acid using the technical scheme of embodiment 12, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ia-3 that example 5 obtains replaces the Schiff's base aluminium compound Ia-2 that embodiment 12 adopts.
The quality that present invention weighing obtains polylactic acid is 2.4g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 1.9 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.66.
Embodiment 14
The present invention prepares polylactic acid using the technical scheme of embodiment 12, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ia-4 that example 5 obtains replaces the Schiff's base aluminium compound Ia-2 that embodiment 12 adopts.
The quality that present invention weighing obtains polylactic acid is 2.5g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 1.9 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.64.
Embodiment 15
The present invention prepares polylactic acid using the technical scheme of embodiment 12, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ia-5 that example 5 obtains replaces the Schiff's base aluminium compound Ia-2 that embodiment 12 adopts.
The quality that present invention weighing obtains polylactic acid is 2.3g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 1.8 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.64.
Embodiment 16
Under conditions of anhydrous and oxygen-free, in rac-lactide that 20.0mmol recrystallization is crossed, 0.03mmol embodiment 6
The Schiff's base aluminium compound Ib-2 obtaining is mixed with 40mL toluene, 70 DEG C of stirring reactions 12h, adds the dissolving of 30mL chloroform poly-
Compound, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 2.6g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 4.0 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.90.
Embodiment 17
The present invention prepares polylactic acid using the technical scheme of embodiment 16, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ib-3 that example 6 obtains replaces the Schiff's base aluminium compound Ib-2 that embodiment 16 adopts.
The quality that present invention weighing obtains polylactic acid is 2.7g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 3.9 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.89.
Embodiment 18
The present invention prepares polylactic acid using the technical scheme of embodiment 16, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ib-4 that example 6 obtains replaces the Schiff's base aluminium compound Ib-2 that embodiment 16 adopts.
The quality that present invention weighing obtains polylactic acid is 2.7g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 3.9 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.90.
Embodiment 19
The present invention prepares polylactic acid using the technical scheme of embodiment 16, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ib-5 that example 6 obtains replaces the Schiff's base aluminium compound Ib-2 that embodiment 16 adopts.
The quality that present invention weighing obtains polylactic acid is 2.6g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 3.8 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.90.
Embodiment 20
Under conditions of anhydrous and oxygen-free, in rac-lactide that 20.0mmol recrystallization is crossed, 0.07mmol embodiment 7
The Schiff's base aluminium compound Ic-2 obtaining is mixed with 40mL toluene, 70 DEG C of stirring reactions 15h, adds the dissolving of 35mL chloroform poly-
Compound, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 2.6g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 2.0 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.91.
Embodiment 21
The present invention prepares polylactic acid using the technical scheme of embodiment 20, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ic-3 that example 7 obtains replaces the Schiff's base aluminium compound Ic-2 that embodiment 20 adopts.
The quality that present invention weighing obtains polylactic acid is 2.4g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 1.9 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.90.
Embodiment 22
The present invention prepares polylactic acid using the technical scheme of embodiment 20, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ic-4 that example 7 obtains replaces the Schiff's base aluminium compound Ic-2 that embodiment 20 adopts.
The quality that present invention weighing obtains polylactic acid is 2.4g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 1.9 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.92.
Embodiment 23
The present invention prepares polylactic acid using the technical scheme of embodiment 20, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ic-5 that example 7 obtains replaces the Schiff's base aluminium compound Ic-2 that embodiment 20 adopts.
The quality that present invention weighing obtains polylactic acid is 2.3g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 2.0 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.90.
Embodiment 24
Under conditions of anhydrous and oxygen-free, in rac-lactide that 20.0mmol recrystallization is crossed, 0.1mmol embodiment 7
The Schiff's base aluminium compound Ic-2 obtaining is mixed with 40mL toluene, 25 DEG C of stirring reactions 72h, adds the dissolving of 30mL chloroform poly-
Compound, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 1.6g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 0.8 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.96.
Embodiment 25
The present invention prepares polylactic acid using the technical scheme of embodiment 24, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ic-3 that example 7 obtains replaces the Schiff's base aluminium compound Ic-2 that embodiment 24 adopts.
The quality that present invention weighing obtains polylactic acid is 1.7g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 0.8 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.96.
Embodiment 26
The present invention prepares polylactic acid using the technical scheme of embodiment 24, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ic-4 that example 7 obtains replaces the Schiff's base aluminium compound Ic-2 that embodiment 24 adopts.
The quality that present invention weighing obtains polylactic acid is 1.5g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 0.75 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.98.
Embodiment 27
The present invention prepares polylactic acid using the technical scheme of embodiment 24, and except for the difference that, the present embodiment is using enforcement
The Schiff's base aluminium compound Ic-5 that example 7 obtains replaces the Schiff's base aluminium compound Ic-2 that embodiment 24 adopts.
The quality that present invention weighing obtains polylactic acid is 1.6g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 0.8 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.98.
Embodiment 28
Under conditions of anhydrous and oxygen-free, rac-lactide that 20.0mmol recrystallization is crossed, 0.013mmol embodiment 6
In the Schiff's base aluminium compound Ib-4 that obtains mix with 40ml toluene, 70 DEG C of stirring reactions 60h, add the dissolving of 30ml chloroform
Polymer, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 2.0g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 2.5 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.89.
Embodiment 29
Under conditions of anhydrous and oxygen-free, rac-lactide that 20.0mmol recrystallization is crossed, 0.007mmol embodiment 6
In the Schiff's base aluminium compound Ib-4 that obtains mix with 40ml toluene, 90 DEG C of stirring reactions 48h, add the dissolving of 30ml chloroform
Polymer, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 1.5g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 7.9 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.84.
Embodiment 30
Under conditions of anhydrous and oxygen-free, rac-lactide that 20.0mmol recrystallization is crossed, 0.003mmol embodiment 6
In the Schiff's base aluminium compound Ib-4 that obtains mix with 40ml toluene, 110 DEG C of stirring reactions 48h, add 30ml chloroform molten
Depolymerization compound, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 1.8g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 2.6 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.55.
Embodiment 31
Under conditions of anhydrous and oxygen-free, rac-lactide that 20.0mmol recrystallization is crossed, 0.002mmol embodiment 6
In the Schiff's base aluminium compound Ib-4 that obtains mix with 40ml toluene, 110 DEG C of stirring reactions 48h, add 30ml chloroform molten
Depolymerization compound, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 1.6g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 9.7 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.57.
Embodiment 32
Under conditions of anhydrous and oxygen-free, in rac-lactide that 20.0mmol recrystallization is crossed, 0.10mmol embodiment 5
The Schiff's base aluminium compound Ia-4 obtaining is mixed with 40ml toluene, 130 DEG C of stirring reactions 1h, adds the dissolving of 30ml chloroform poly-
Compound, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 2.4g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 1.2 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.50.
Embodiment 33
Under conditions of anhydrous and oxygen-free, in levorotatory lactide that 20.0mmol recrystallization is crossed, 0.05mmol embodiment 6
The Schiff's base aluminium compound Ib-3 arriving is mixed with 40ml toluene, 60 DEG C of stirring reactions 29h, adds the dissolving polymerization of 30ml chloroform
Thing, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 2.3g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 3.5 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.99.
Embodiment 34
Under conditions of anhydrous and oxygen-free, in dextrorotation lactide that 20.0mmol recrystallization is crossed, 0.10mmol embodiment 6
The Schiff's base aluminium compound Ib-4 arriving is mixed with 40ml toluene, 70 DEG C of stirring reactions 10h, adds the dissolving polymerization of 30ml chloroform
Thing, the ethanol precipitation polymer of excess, filters, is vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 2.1g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 1.7 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.99.
Embodiment 35
Under conditions of anhydrous and oxygen-free, the dextrorotation third that levorotatory lactide that 8mmol recrystallization is crossed, 12mmol recrystallization are crossed
The Schiff's base aluminium compound Ib-3 obtaining in lactide, 0.10mmol embodiment 6 is mixed with 40ml toluene, 70 DEG C of stirring reactions 8h,
Add 30ml chloroform dissolving polymer, the ethanol precipitation polymer of excess, filter, be vacuum dried 48h.
The quality that present invention weighing obtains polylactic acid is 2.0g；
The present invention, with polystyrene as reference material, is carried out point using the polylactic acid that gel permeation chromatography obtains to the present embodiment
Analysis, the number-average molecular weight obtaining polylactic acid is 1.9 ten thousand；
The present invention is analyzed to the polylactic acid that the present embodiment obtains using homonuclear decoupling proton nmr spectra, obtains poly- breast
The Pm of acid is 0.93.
As seen from the above embodiment, the three metal center Schiff's base aluminium compound catalyst that the present invention provides, have three
Metal active centres, its reactivity is higher, and the consumption of catalyst is less, and reaction temperature is relatively low.Meanwhile, it has larger sky
Between steric hindrance, the Selective long-range DEPT of catalyzing ring-opening polymerization of lactide, there is higher catalysis activity and structure selectivity, improve poly-
The regularity of lactic acid space structure.Test result indicate that, the yield that the method that the present invention provides prepares polylactic acid can reach 95%,
The three-dimensional regularity (Pm) of the polylactic acid obtaining is up to 0.98.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that it is right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a kind of three metal center Schiff's base aluminium compounds, have structure shown in formula (I)：
Wherein, R is-CH3、-CH2CH3、-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph；
R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC(CH3)3
(CH3)2,-F ,-Cl ,-Br or-NO2.
2. a kind of preparation method of three metal center Schiff's base aluminium compounds is it is characterised in that comprise the following steps：
By the Schiff's base shown in formula (II) structure and Al (R ')3Reaction, obtains the Schiff's base aluminium compound shown in formula (III) structure；
Wherein, R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC(CH3)3
(CH3)2,-F ,-Cl ,-Br or-NO2；
R ' is-CH3Or-CH2CH3.
3. a kind of preparation method of three metal center Schiff's base aluminium compounds is it is characterised in that comprise the following steps：
A) by the Schiff's base shown in formula (II) structure and Al (R ')3Reaction, obtains the Schiff's base calorize shown in formula (III) structure and closes
Thing；
B) the Schiff's base aluminium compound shown in described formula (III) structure is reacted with R H, obtain the Schiff shown in formula (IV) structure
Alkali aluminium compound；
Wherein, R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC(CH3)3
(CH3)2,-F ,-Cl ,-Br or-NO2；
R ' is-CH3Or-CH2CH3；
R is-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph.
4. the preparation method according to Claims 2 or 3 it is characterised in that the Schiff's base shown in described formula (II) structure with
Al(R′)3Mol ratio be 1:3.
5. the preparation method according to Claims 2 or 3 it is characterised in that the Schiff's base shown in described formula (II) structure with
Al(R′)3The reaction temperature of reaction is 60 DEG C～90 DEG C, and the response time is 9～12h.
6. the preparation method according to Claims 2 or 3 is it is characterised in that the Schiff's base shown in described formula (II) structure is pressed
According to following steps preparation：
Compound shown in formula (V) and the substituted salicylic aldehydes shown in formula (VI) are reacted, obtains the Schiff's base shown in formula (II) structure；
In formula (VI), R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC
(CH3)3(CH3)2,-F ,-Cl ,-Br or-NO2.
7. preparation method according to claim 6 is it is characterised in that compound is according to following steps shown in described formula (V)
Preparation：
S1) phloroglucinol, acetic acid and acetic anhydride are reacted under the catalytic action of concentrated sulphuric acid, obtained triacetyl isophthalic three
Phenol；
S2) triacetyl phloroglucinol is reacted with 1,2- diaminourea -2- methylpropane and obtain compound shown in formula (V).
8. three metal center Schiff's base aluminium compounds shown in formula (I) structure are as the application of lactide polymerisation catalysts,
Wherein, R is-CH3、-CH2CH3、-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph；R1And R2Independently selected from-H ,-
CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC(CH3)3(CH3)2,-F ,-Cl ,-Br or-NO2.
9. a kind of preparation method of polylactic acid is it is characterised in that comprise the following steps：
Lactide is reacted with the Schiff's base aluminium compound shown in formula (I) structure, obtains polylactic acid；
Wherein, R is-CH3、-CH2CH3、-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph；
R1And R2Independently selected from-H ,-CH3、-CH2CH3、-CH(CH3)2、-C(CH3)3、-Si(CH3)3、-SiC(CH3)3
(CH3)2,-F ,-Cl ,-Br or-NO2.
10. preparation method according to claim 9 is it is characterised in that the Schiff's base calorize shown in described formula (I) structure is closed
Thing is 1 with the mol ratio of lactide:50～1:10000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610781584.XA CN106380478B (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of three metal centers schiff bases aluminium compound, preparation method, application and polylactic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610781584.XA CN106380478B (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of three metal centers schiff bases aluminium compound, preparation method, application and polylactic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106380478A true CN106380478A (en) | 2017-02-08 |
| CN106380478B CN106380478B (en) | 2018-08-28 |
Family
ID=57938616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610781584.XA Active CN106380478B (en) | 2016-08-30 | 2016-08-30 | A kind of preparation method of three metal centers schiff bases aluminium compound, preparation method, application and polylactic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106380478B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054011A (en) * | 2018-07-16 | 2018-12-21 | 中国科学院长春应用化学研究所 | A kind of preparation method of schiff bases cobalt compound, preparation method and polycarbonate |
| CN113248698A (en) * | 2021-05-31 | 2021-08-13 | 福州大学 | Bimetal Schiff base coordination metal compound and preparation method thereof |
-
2016
- 2016-08-30 CN CN201610781584.XA patent/CN106380478B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| HONGZHI DU等: ""Polymerization of rac-Lactide Using Schiff Base Aluminum Catalysts: Structure, Activity,and Stereoselectivity"", 《MACROMOLECULES》 * |
| SIDDHESHWAR K.CHAUTHE等: ""One pot synthesis and anticancer activity of dimeric phloroglucinols"", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
| THORSTEN GLASER等: ""Trinuclear Nickel Complexes with Triplesalen Ligands: Simultaneous Occurrence of Mixed Valence and Valence Tautomerism in the Oxidized Species"", 《INORGANIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054011A (en) * | 2018-07-16 | 2018-12-21 | 中国科学院长春应用化学研究所 | A kind of preparation method of schiff bases cobalt compound, preparation method and polycarbonate |
| CN113248698A (en) * | 2021-05-31 | 2021-08-13 | 福州大学 | Bimetal Schiff base coordination metal compound and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106380478B (en) | 2018-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103421034B (en) | The preparation method of Chiral aluminum compound and preparation method thereof and poly(lactic acid) | |
| CN100393771C (en) | Schiff-base aluminium catalyst for lactide open-ring polymerization, and it spreparing method and use | |
| Quan et al. | Copolymerization of CO2 and propylene oxide under rare earth ternary catalyst: design of ligand in yttrium complex | |
| CN101665565B (en) | Method for preparing polylactic acid through catalysis of carbine derivatives | |
| Huang et al. | Ring‐opening polymerization of lactides initiated by magnesium and zinc complexes based on NNO‐tridentate ketiminate ligands: Activity and stereoselectivity studies | |
| CN111574548B (en) | Preparation method of macrocyclic carrier multi-center metalloporphyrin complex and polycarbonate | |
| CN110483748B (en) | Bipyridyl bisphenol-aluminum catalyst for preparing unsaturated polyester and preparation method thereof | |
| CN100406491C (en) | Enol form lactide open-ring polymerization catalyst and its preparing method and use | |
| CN104710447B (en) | A kind of preparation method of chiral aluminum complex containing pyrrole group and preparation method thereof and PLA | |
| KR101217954B1 (en) | Group ３ post-metallocene complexes based on bis(naphthoxy)pyridine and bis(naphthoxy)thiophene ligands for the ring-opening polymerisation of polar cyclic monomers | |
| CN106380478B (en) | A kind of preparation method of three metal centers schiff bases aluminium compound, preparation method, application and polylactic acid | |
| CN105566623A (en) | Polycarbonate material and preparation method thereof | |
| CN107417739B (en) | A kind of schiff bases iron compound, preparation method and its application as catalyst | |
| CN102757457B (en) | Schiff base aluminum compound and preparation method thereof, and preparation method of polylactic acid | |
| CN104311582A (en) | Schiff base zinc compound, preparation method of schiff base zinc compound, and preparation method of polylactic acid | |
| CN102786674B (en) | Schiff base aluminum compound, preparation method thereof and preparation method of polylactic acid | |
| CN107033193A (en) | A kind of schiff bases iron compound, its preparation method and its application as catalyst | |
| Schmitz et al. | Synthesis and structures of aluminum ion-pair complexes that act as L-and racemic-lactide ring opening polymerization initiators | |
| CN103254220B (en) | The preparation method of Chiral zinc compound, its preparation method and poly(lactic acid) | |
| CN113321676B (en) | Tetrahydropyrrole diamine bridged bisphenol rare earth metal complex and preparation and application thereof | |
| CN108912010A (en) | A kind of schiff bases manganese compound, preparation method and its application | |
| CN102786544A (en) | Schiff base aluminum compound, preparation process of Schiff base aluminum compound and preparation process of polylactic acid | |
| CN103467503B (en) | With the Chiral aluminum compound and preparation method thereof of dinaphthalene derivatives and the preparation method of poly(lactic acid) | |
| CN105085560A (en) | Aluminum compound based on pyrrole derivatives, preparation method of aluminum compound and polylactic acid preparation method | |
| CN103408574B (en) | Schiff base aluminum compound and preparation method thereof, and polylactic acid preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |