CN106380478B - A kind of preparation method of three metal centers schiff bases aluminium compound, preparation method, application and polylactic acid - Google Patents
A kind of preparation method of three metal centers schiff bases aluminium compound, preparation method, application and polylactic acid Download PDFInfo
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- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
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- 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
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- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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Abstract
The present invention provides a kind of three metal center schiff bases aluminium compounds, have structure shown in formula (I).The present invention is core using triacetyl phloroglucin; three metal active centres binding sites are provided; form three metal center schiff bases; on the one hand there is larger molecule space to obtain larger steric hindrance; it is set to improve the regularity of polymerizate space structure to the Selective long-range DEPT of lactide ring-opening polymerisation；On the other hand the special construction of such three metal center clearly enhances the reactivity of catalyst, improves the speed of polymerisation.Therefore, ring-opening polymerisation of the schiff bases aluminium compound provided by the invention to lactide has higher catalytic activity and structure selectivity, improves the regularity of polylactic acid space structure.The experimental results showed that three metal centers schiff bases aluminium compound provided by the invention, is used to prepare polylactic acid, reaction yield can reach 95%, and the three-dimensional regularity (Pm) of obtained polylactic acid is up to 0.98.
Description
Technical field
The present invention relates to technical field, more particularly to a kind of three metal center schiff bases aluminium compounds, preparation method, answer
With and polylactic acid preparation method.
Background technology
Polylactic acid is a kind of chemically synthesized biodegradation material, is had in packaging material, biological medicine and pharmaceuticals industry
It and is widely applied.The two methods of synthesis generally use of polylactic acid, 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 generally uses lactide ring-opening polymerisation, and had a large amount of texts
It offers and patent has carried out relevant report to lactide ring-opening polymerisation, such as the United States Patent (USP) and Patent No. of Patent No. 5235031
5357034 United States Patent (USP).
There are three types of stereoisomers for lactide tool：Levorotatory lactide (LLA), dextrorotation lactide (DLA) and meso third are handed over
Ester, structure difference are as follows：
Currently, the common catalyst of lactide ring-opening polymerisation is nontoxic tin compound, such as stannic chloride and stannous octoate.
Tin series catalysts effect under, optically pure DLA, LLA respectively ring-opening polymerisation obtain isotactic poly- dextrorotation lactide and
The product of poly- levorotatory lactide, rac-lactide ring-opening polymerisation under the same conditions is atactic polymer.
Studies have shown that the spatial configuration of lactide to the machinery of polymer, processing and degradation property have it is conclusive
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 polymerize is noncrystallizable polymer.Compared with amorphism polylactic acid, crystallinity
The use temperature range of polylactic acid is wider, can be more advantageous close to melting temperature.Therefore it needs to develop a kind of to lactide
Polymerization has the ring-opening polymerization catalyst of stereoselectivity, and rac-lactide can be made to polymerize to obtain crystalline polylactic acid.And have
Higher selectivity and activity.
Invention content
In view of this, the technical problem to be solved in the present invention be to provide a kind of three metal center schiff bases aluminium compounds,
The preparation method of preparation method, application and polylactic acid, three prepared metal center schiff bases aluminium compounds are handed over for third
Polyisocyanate polyaddition reacts, and has higher selectivity and activity.
The present invention provides a kind of three metal center schiff bases 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。
The present invention also provides a kind of preparation methods of three metal centers schiff bases aluminium compound, include the following steps：
By schiff bases shown in formula (II) structure and Al (R ')3Reaction, obtains schiff bases calorize shown in formula (III) structure
Close object；
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。
The present invention also provides a kind of preparation methods of three metal centers schiff bases aluminium compound, include the following steps：
A) by schiff bases shown in formula (II) structure and Al (R ')3Reaction, obtains schiff bases aluminium shown in formula (III) structure
Compound；
B schiff bases aluminium compound shown in the formula (III) structure is reacted with R 〞 H), is obtained shown in formula (IV) structure
Schiff bases 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 〞 are-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph。
Preferably, schiff bases shown in formula (II) structure and Al (R ')3Molar ratio be 1:3.
Preferably, schiff bases shown in formula (II) structure and Al (R ')3The reaction temperature of reaction is 60 DEG C~90 DEG C,
Reaction time is 9~12h.
Preferably, schiff bases shown in formula (II) structure is prepared according to the following steps：
Compound shown in formula (V) is reacted with substituted salicylic aldehydes shown in formula (VI), obtains 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 the formula (V) is prepared according to the following steps：
S1) phloroglucin, acetic acid are reacted with acetic anhydride under the catalytic action of the concentrated sulfuric acid, obtained between triacetyl
Benzenetriol；
S2 compound shown in formula (V)) is obtained by the reaction in triacetyl phloroglucin and 1,2- diamino -2- methylpropanes.
It is anti-as lactide polymerization that the present invention also provides three metal center schiff bases aluminium compounds shown in formula (I) structure
The application of catalyst is answered,
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。
The present invention also provides a kind of preparation methods of polylactic acid, include the following steps：
Lactide is reacted with schiff bases 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 molar ratio of schiff bases aluminium compound and lactide shown in formula (I) structure is 1:50~1:
10000。
Compared with prior art, the present invention provides a kind of three metal center schiff bases aluminium compounds, have shown in formula (I)
Structure.The present invention is core using triacetyl phloroglucin, provides three metal active centres binding sites, forms three metals
On the one hand center schiff bases there is larger molecule space to obtain larger steric hindrance, make it to lactide ring-opening polymerisation
Selective long-range DEPT, improve the regularity of polymerizate space structure；On the other hand the special construction of such three metal center
The reactivity for clearly enhancing catalyst improves the speed of polymerisation.Therefore, schiff bases calorize provided by the invention is closed
Ring-opening polymerisation of the object to lactide has higher catalytic activity and structure selectivity, improves the rule of polylactic acid space structure
Whole property.The experimental results showed that three metal centers schiff bases aluminium compound provided by the invention, is used to prepare polylactic acid, reaction is received
Rate can reach 95%, and the three-dimensional regularity (Pm) of obtained polylactic acid is up to 0.98.
Specific implementation mode
The present invention provides a kind of three metal center schiff bases 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。
The present invention is core using triacetyl phloroglucin, provides three metal active centres binding sites, forms three
On the one hand metal center schiff bases there is larger molecule space to obtain larger steric hindrance, make it to lactide open loop
The Selective long-range DEPT of polymerization improves the regularity of polymerizate space structure；On the other hand such three metal center is special
Structure clearly enhances the reactivity of catalyst, improves the speed of polymerisation.Therefore, schiff bases aluminium provided by the invention
Ring-opening polymerisation of the compound to lactide has higher catalytic activity and structure selectivity, improves polylactic acid space structure
Regularity.The experimental results showed that three metal centers schiff bases aluminium compound provided by the invention, is used to prepare polylactic acid, instead
Yield is answered to can reach 95%, the three-dimensional regularity (Pm) of obtained polylactic acid is up to 0.98.
In structure shown in above-mentioned formula (I), methyl is indicated with singly-bound.
The present invention also provides a kind of preparation methods of three metal centers schiff bases aluminium compound, include the following steps：
By schiff bases shown in formula (II) structure and Al (R ')3Reaction, obtains schiff bases calorize shown in formula (III) structure
Close object；
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。
The reaction carries out in a solvent.The solvent can be organic solvent well known to those skilled in the art, preferably
For tetrahydrofuran or toluene.
Preferably, work as R1And R2Independently selected from-H ,-F ,-Cl ,-Br or-NO2When, the reaction dissolvent is preferably tetrahydrochysene
Furans；Work as R1And R2Independently selected from-CH3、-CH2CH3、-CH(CH3)2Or-C (CH3)3When, the reaction dissolvent is preferably first
Benzene.
In the present invention, the Al (R ')3Preferably Al (CH3)3Or Al (CH2CH3)3.R ' in formula (III) comes from Al
(R′)3。
The Al (R ')3Molar ratio with schiff bases shown in formula (II) structure is preferably 3:1, seat provided by the present invention
Husband's alkali cpd is metal complex, above-mentioned molar ratio can guarantee metal active centres simultaneously with two C=N functional groups
Form coordinate bond.
The temperature of the reaction is preferably 60 DEG C~90 DEG C, and the selection of temperature depends on the selection of reaction dissolvent, more preferably
It it is 70 DEG C or 90 DEG C, the reaction time is preferably 9~12h, more preferably 10h.
The reaction preferably uses the method for column chromatography to be purified.
The present invention also provides a kind of preparation methods of three metal centers schiff bases aluminium compound, include the following steps：
A) by schiff bases shown in formula (II) structure and Al (R ')3Middle reaction obtains schiff bases shown in formula (III) structure
Aluminium compound；
B schiff bases aluminium compound shown in the formula (III) structure is reacted with R 〞 H), is obtained shown in formula (IV) structure
Schiff bases 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 〞 are preferably-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph。
Above-mentioned steps A) solvent, reaction temperature, reaction time be same as above, details are not described herein.
The Al (R ')3Selection be same as above, details are not described herein.
Above-mentioned steps B) it carries out in a solvent.The solvent can be organic solvent well known to those skilled in the art, excellent
It is selected as tetrahydrofuran or toluene.
Preferably, work as R1And R2Independently selected from-H ,-F ,-Cl ,-Br or-NO2When, the reaction dissolvent is preferably tetrahydrochysene
Furans；Work as R1And R2Independently selected from-CH3、-CH2CH3、-CH(CH3)2Or-C (CH3)3When, the reaction dissolvent is preferably first
Benzene.
The R 〞 H are preferably CH3OH、CH3CH2OH、(CH3)2CHOH or Ph CH2OH。
The molar ratio of the R 〞 H and schiff bases aluminium compound shown in formula (III) structure are preferably 3:1.
The temperature of the reaction is preferably 60 DEG C~90 DEG C, and the selection of temperature depends on the selection of reaction dissolvent, more preferably
It it is 70 DEG C or 90 DEG C, the reaction time is preferably 9~12h, more preferably 10h.
The reaction preferably uses the method for column chromatography to be purified.
In the present invention, schiff bases is preferably prepared according to the following steps shown in formula (II) structure：
Compound shown in formula (V) is reacted with substituted salicylic aldehydes shown in formula (VI), obtains 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 carries out in a solvent.The solvent can be organic solvent well known to those skilled in the art, preferably
For ethyl alcohol.
The temperature of the reaction is preferably room temperature, and the time of reaction is preferably 10~30h.
The reaction preferably uses the method for column chromatography to be purified.
Compound is preferably prepared according to the following steps shown in the formula (V)：
S1) phloroglucin, acetic acid are reacted with acetic anhydride under the catalytic action of the concentrated sulfuric acid, obtained between triacetyl
Benzenetriol；
S2 compound shown in formula (V)) is obtained by the reaction in triacetyl phloroglucin and 1,2- diamino -2- methylpropanes.
The step S1) in, the temperature of reaction is preferably 60~80 DEG C, and the time of the reaction is preferably 10~15h.
After reaction, reaction system is poured into water, and filtering, solid preferably uses the method for column chromatography to be purified.
The step S2) in, the temperature of reaction is preferably room temperature, and the reaction time is preferably 2~4 days.
After reaction, filtering can be obtained compound shown in formula (V).
In the present invention, remaining required reagent is commercially available.
It is anti-as lactide polymerization that the present invention also provides three metal center schiff bases aluminium compounds shown in formula (I) structure
Answer the application of catalyst.
When being prepared for polylactic acid, preparation method includes the following steps：
Lactide is reacted with schiff bases aluminium compound shown in formula (I) structure, obtains polylactic acid.
The reaction carries out in a solvent, and the solvent can be organic solvent well known to those skilled in the art, preferably
For tetrahydrofuran or toluene.
The molar ratio of schiff bases aluminium compound and lactide shown in formula (I) structure is preferably 1:50~1:10000,
More preferably 1:300~1:3000.
The reaction temperature of the lactide polymerisation is preferably 25~130 DEG C, and the reaction time is preferably 1.0~72h.It should
Reaction preferably carries out under conditions of anhydrous and oxygen-free, it is possible to reduce the generation of side reaction.
The lactide can be levorotatory lactide, dextrorotation lactide or Study of Meso-Lactide.
It is described after reaction, it is preferred to use the method for recrystallization is purified.
The present invention is preferably dissolved obtained ring-opening polymerization product using chloroform, and it is heavy to add excessive ethyl alcohol
It is dry after shallow lake polymer, filtering, obtain polylactic acid.
The present invention does not have the dosage of the chloroform special limitation, can dissolve obtained reaction product i.e.
It can；The present invention does not have special limitation to the filtering and dry method, using filtering well known to those skilled in the art and
Dry technical solution；The drying in the present invention is preferably dried in vacuo, time of the drying be preferably 36h~
60h, more preferably 39h~57h, most preferably 45h~48h.
After obtaining polylactic acid, the present invention uses the selectivity of homonuclear decoupling hydrogen nuclear magnetic resonance spectrum analysis reaction, polymerization to obtain
Polylactide backbone sequence distribution, using " mmm " indicate segment be to be connected together by the lactide of identical configuration,
[mmr], [rmm], [mrm], [rmr] indicate that there is the lactide for differing configuration in segment connects together.According to level-one
Markovian is counted, and five kinds of sequence relative intensities of poly- rac-lactide can be indicated by a 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.The result shows that schiff bases aluminium compound provided by the invention has lactide ring-opening polymerization
There is stronger selectivity, improves the regularity of polymerizate space structure.
The schiff bases aluminium compound is three Metal Schiff _ base Al catalysts, and there are three metal active centres, reactions for tool
Activity is higher, and the dosage of catalyst is less, and reaction temperature is relatively low.Meanwhile it with larger steric hindrance, being catalyzed lactide and opening
The Selective long-range DEPT of cyclopolymerization has higher catalytic activity and structure selectivity, improves the regular of polylactic acid space structure
Property.The experimental results showed that the yield that method provided by the invention prepares polylactic acid can reach 95%, the solid of obtained polylactic acid
Regularity (Pm) is up to 0.98.
In order to further illustrate the present invention, with reference to embodiment to three metal centers schiff bases calorize provided by the invention
The preparation method for closing object, preparation method, application and polylactic acid is described in detail.
The preparation of compound shown in 1 intermediate formula (V) of embodiment
1.1 mix 3.0g phloroglucins, 15mL acetic acid with 15mL acetic anhydrides, and the 2mL concentrated sulfuric acids are added dropwise, and are heated to 75 DEG C instead
12h is answered, after reaction, pours into 200mL water and stirs 10min, is filtered, three times, each 10mL ethyl alcohol is washed for each 50mL washings
Three times, vacuum pumps solvent, and after solid column chromatography, obtained white solid is compound triacetyl phloroglucin.
1.0g triacetyl phloroglucins are slowly added to 4mL 2- methyl-1s by 1.2, in 2- propane diamine, are reacted at room temperature 3 days,
After filtering, pentane washs to obtain yellow solid, is compound shown in formula (V).
The compound obtained respectively to 1.1,1.2 using nuclear magnetic resonance is analyzed, and the hydrogen spectrum of each compound, knot are obtained
Fruit is as follows：
Compound triacetyl phloroglucin：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)2 18H)。
The synthesis of 2 schiff bases IIa of embodiment
IIa：R1=R2=-H.
Compound shown in the formula (V) obtained in 0.9g 1.2 is dissolved in 10ml ethyl alcohol, the 10ml of 1.0g salicylides is added
Ethanol solution reacts at room temperature 20h, and revolving removes most of solvent, and column chromatography purification obtains schiff bases IIa.
The schiff bases IIa obtained in embodiment 2 is analyzed using nuclear magnetic resonance, 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 ArCCH3 9H),1.42,1.29(m C(CH3)2 18H)。
The synthesis of 3 schiff bases IIb of embodiment
IIb：R1=R2=-C (CH3)3
Compound shown in the formula (V) obtained in 0.9g 1.2 is dissolved in 10ml ethyl alcohol, 1.5g 3,5- di-t-butyls is added
The 10ml ethanol solutions of salicylide react at room temperature 20h, and revolving removes most of solvent, and column chromatography purification obtains schiff bases IIb.
The schiff bases IIb obtained in embodiment 3 is analyzed using nuclear magnetic resonance, obtains its nuclear magnetic data, as a result 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 ArCCH3 9H),1.45,1.31(m C(CH3)3,C(CH3)2 72H)。
The synthesis of 4 schiff bases IIc of embodiment
IIc：R1=-Si (CH3)2C(CH3)3, R2=-H
Compound shown in the formula (V) obtained in 0.9g 1.2 is dissolved in 10ml ethyl alcohol, 1.5g3- (the tertiary fourths of dimethyl are added
Base) silicon salicylide 10ml ethanol solutions, react at room temperature 20h, revolving removes most of solvent, and column chromatography purification obtains Schiff
Alkali IIc.
The schiff bases IIc obtained in embodiment 4 is analyzed using nuclear magnetic resonance, obtains its nuclear magnetic data, as a result 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)2 18H),0.94
(s SiC(CH3)3 27H),0.34(s Si(CH3)2 18H)。
The synthesis of 5 schiff bases aluminium compound Ia-1~Ia-5 of embodiment
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 solutions of a concentration of 1mol/L of 2ml and 6ml is a concentration of
The AlEt of 1mol/L3Toluene solution is mixed, and 90 DEG C of reaction 10h are down to room temperature, vacuumize 0.1Mpa and remove volatility object
Matter obtains schiff bases aluminium compound Ia-1.
5.2 are dissolved in the schiff bases aluminium compound Ia-1 obtained in 4mmol 5.1 in toluene, and 12mmol methanol is added, obtains
To schiff bases aluminium compound Ia-2.
The preparation method of schiff bases aluminium compound Ia-3~Ia-5 is identical as Ia-2, wherein difference lies in：Methanol is distinguished
It is changed to ethyl alcohol, isopropanol, benzylalcohol.
The schiff bases aluminium compound Ia-1~Ia-5 obtained in embodiment 5 is analyzed using elemental analysis, 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。
6 schiff bases aluminium compound Ib-1~Ib-5 of embodiment
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 bases aluminium compound Ib-1 is identical as Ia-1, wherein difference lies in：By IIa toluene solutions
It is changed to IIb toluene solutions.
6.2 are dissolved in the schiff bases aluminium compound Ib-1 obtained in 4mmol 6.1 in toluene, and 12mmol methanol is added, obtains
To schiff bases aluminium compound Ib-2.
The preparation method of schiff bases aluminium compound Ib-3~Ib-5 is identical as Ib-2, wherein difference lies in：Methanol is distinguished
It is changed to ethyl alcohol, isopropanol, benzylalcohol.
The schiff bases aluminium compound Ib-1~Ib-5 obtained in embodiment 6 is analyzed using elemental analysis, 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。
7 schiff bases aluminium compound Ic-1~Ic-5 of embodiment
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 bases aluminium compound Ic-1 is identical as Ia-1, wherein difference lies in：By IIa toluene solutions
It is changed to IIc toluene solutions.
7.2 are dissolved in the schiff bases aluminium compound Ic-1 obtained in 4mmol 7.1 in toluene, and 12mmol methanol is added, obtains
To schiff bases aluminium compound Ic-2.
The preparation method of schiff bases aluminium compound Ic-3~Ic-5 is identical as Ic-2, wherein difference lies in：Methanol is distinguished
It is changed to ethyl alcohol, isopropanol, benzylalcohol.
The schiff bases aluminium compound Ic-1~Ic-5 obtained in embodiment 7 is analyzed using elemental analysis, 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 was recrystallized, 0.2mmol embodiments 5
Obtained schiff bases aluminium compound Ia-2 is mixed with 40mL toluene, and 25 DEG C are stirred to react 42h, and it is poly- that the dissolving of 40mL chloroforms is added
Object, excessive ethanol precipitation polymer are closed, filtering is dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 2.0g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 0.7 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.76.
Embodiment 9
Polylactic acid is prepared using the technical solution of embodiment 8 in the present invention, unlike, the present embodiment uses embodiment
5 obtained schiff bases aluminium compound Ia-3 replace the schiff bases aluminium compound Ia-2 that embodiment 8 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.1g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 0.7 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.75.
Embodiment 10
Polylactic acid is prepared using the technical solution of embodiment 8 in the present invention, unlike, the present embodiment uses embodiment
5 obtained schiff bases aluminium compound Ia-4 replace the schiff bases aluminium compound Ia-2 that embodiment 8 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.2g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 0.75 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.75.
Embodiment 11
Polylactic acid is prepared using the technical solution of embodiment 8 in the present invention, unlike, the present embodiment uses embodiment
5 obtained schiff bases aluminium compound Ia-5 replace the schiff bases aluminium compound Ia-2 that embodiment 8 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.0g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 0.7 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, 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 was recrystallized, 0.03mmol embodiments 5
Obtained schiff bases aluminium compound Ia-2 is mixed with 40mL toluene, and 70 DEG C are stirred to react 6h, and it is poly- that the dissolving of 40mL chloroforms is added
Object, excessive ethanol precipitation polymer are closed, filtering is dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 2.5g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 2.0 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.64.
Embodiment 13
Polylactic acid is prepared using the technical solution of embodiment 12 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ia-3 that example 5 obtains replaces the schiff bases aluminium compound Ia-2 that embodiment 12 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.4g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 1.9 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.66.
Embodiment 14
Polylactic acid is prepared using the technical solution of embodiment 12 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ia-4 that example 5 obtains replaces the schiff bases aluminium compound Ia-2 that embodiment 12 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.5g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 1.9 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.64.
Embodiment 15
Polylactic acid is prepared using the technical solution of embodiment 12 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ia-5 that example 5 obtains replaces the schiff bases aluminium compound Ia-2 that embodiment 12 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.3g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 1.8 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, 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 was recrystallized, 0.03mmol embodiments 6
Obtained schiff bases aluminium compound Ib-2 is mixed with 40mL toluene, and 70 DEG C are stirred to react 12h, and it is poly- that the dissolving of 30mL chloroforms is added
Object, excessive ethanol precipitation polymer are closed, filtering is dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 2.6g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 4.0 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.90.
Embodiment 17
Polylactic acid is prepared using the technical solution of embodiment 16 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ib-3 that example 6 obtains replaces the schiff bases aluminium compound Ib-2 that embodiment 16 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.7g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 3.9 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.89.
Embodiment 18
Polylactic acid is prepared using the technical solution of embodiment 16 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ib-4 that example 6 obtains replaces the schiff bases aluminium compound Ib-2 that embodiment 16 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.7g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 3.9 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.90.
Embodiment 19
Polylactic acid is prepared using the technical solution of embodiment 16 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ib-5 that example 6 obtains replaces the schiff bases aluminium compound Ib-2 that embodiment 16 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.6g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 3.8 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, 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 was recrystallized, 0.07mmol embodiments 7
Obtained schiff bases aluminium compound Ic-2 is mixed with 40mL toluene, and 70 DEG C are stirred to react 15h, and it is poly- that the dissolving of 35mL chloroforms is added
Object, excessive ethanol precipitation polymer are closed, filtering is dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 2.6g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 2.0 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.91.
Embodiment 21
Polylactic acid is prepared using the technical solution of embodiment 20 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ic-3 that example 7 obtains replaces the schiff bases aluminium compound Ic-2 that embodiment 20 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.4g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 1.9 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.90.
Embodiment 22
Polylactic acid is prepared using the technical solution of embodiment 20 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ic-4 that example 7 obtains replaces the schiff bases aluminium compound Ic-2 that embodiment 20 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.4g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 1.9 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.92.
Embodiment 23
Polylactic acid is prepared using the technical solution of embodiment 20 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ic-5 that example 7 obtains replaces the schiff bases aluminium compound Ic-2 that embodiment 20 uses.
The quality that the present invention weighs to obtain polylactic acid is 2.3g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 2.0 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, 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 was recrystallized, 0.1mmol embodiments 7
Obtained schiff bases aluminium compound Ic-2 is mixed with 40mL toluene, and 25 DEG C are stirred to react 72h, and it is poly- that the dissolving of 30mL chloroforms is added
Object, excessive ethanol precipitation polymer are closed, filtering is dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 1.6g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 0.8 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.96.
Embodiment 25
Polylactic acid is prepared using the technical solution of embodiment 24 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ic-3 that example 7 obtains replaces the schiff bases aluminium compound Ic-2 that embodiment 24 uses.
The quality that the present invention weighs to obtain polylactic acid is 1.7g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 0.8 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.96.
Embodiment 26
Polylactic acid is prepared using the technical solution of embodiment 24 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ic-4 that example 7 obtains replaces the schiff bases aluminium compound Ic-2 that embodiment 24 uses.
The quality that the present invention weighs to obtain polylactic acid is 1.5g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 0.75 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.98.
Embodiment 27
Polylactic acid is prepared using the technical solution of embodiment 24 in the present invention, unlike, the present embodiment is using implementation
The schiff bases aluminium compound Ic-5 that example 7 obtains replaces the schiff bases aluminium compound Ic-2 that embodiment 24 uses.
The quality that the present invention weighs to obtain polylactic acid is 1.6g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 0.8 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.98.
Embodiment 28
Under conditions of anhydrous and oxygen-free, rac-lactide that 20.0mmol was recrystallized, 0.013mmol embodiments 6
In obtained schiff bases aluminium compound Ib-4 mixed with 40ml toluene, 70 DEG C are stirred to react 60h, and the dissolving of 30ml chloroforms is added
Polymer, excessive ethanol precipitation polymer, filtering are dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 2.0g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 2.5 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.89.
Embodiment 29
Under conditions of anhydrous and oxygen-free, rac-lactide that 20.0mmol was recrystallized, 0.007mmol embodiments 6
In obtained schiff bases aluminium compound Ib-4 mixed with 40ml toluene, 90 DEG C are stirred to react 48h, and the dissolving of 30ml chloroforms is added
Polymer, excessive ethanol precipitation polymer, filtering are dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 1.5g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 7.9 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.84.
Embodiment 30
Under conditions of anhydrous and oxygen-free, rac-lactide that 20.0mmol was recrystallized, 0.003mmol embodiments 6
In obtained schiff bases aluminium compound Ib-4 mixed with 40ml toluene, 110 DEG C are stirred to react 48h, and it is molten that 30ml chloroforms are added
Depolymerize object, excessive ethanol precipitation polymer, and filtering is dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 1.8g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 2.6 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.55.
Embodiment 31
Under conditions of anhydrous and oxygen-free, rac-lactide that 20.0mmol was recrystallized, 0.002mmol embodiments 6
In obtained schiff bases aluminium compound Ib-4 mixed with 40ml toluene, 110 DEG C are stirred to react 48h, and it is molten that 30ml chloroforms are added
Depolymerize object, excessive ethanol precipitation polymer, and filtering is dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 1.6g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 9.7 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, 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 was recrystallized, 0.10mmol embodiments 5
Obtained schiff bases aluminium compound Ia-4 is mixed with 40ml toluene, and 130 DEG C are stirred to react 1h, and it is poly- that the dissolving of 30ml chloroforms is added
Object, excessive ethanol precipitation polymer are closed, filtering is dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 2.4g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 1.2 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, 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 was recrystallized, 0.05mmol embodiments 6
The schiff bases aluminium compound Ib-3 arrived is mixed with 40ml toluene, and 60 DEG C are stirred to react 29h, and the dissolving polymerization of 30ml chloroforms is added
Object, excessive ethanol precipitation polymer, filtering are dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 2.3g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 3.5 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, 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 was recrystallized, 0.10mmol embodiments 6
The schiff bases aluminium compound Ib-4 arrived is mixed with 40ml toluene, and 70 DEG C are stirred to react 10h, and the dissolving polymerization of 30ml chloroforms is added
Object, excessive ethanol precipitation polymer, filtering are dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 2.1g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 1.7 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.99.
Embodiment 35
Under conditions of anhydrous and oxygen-free, dextrorotation third that levorotatory lactide that 8mmol was recrystallized, 12mmol were recrystallized
The schiff bases aluminium compound Ib-3 obtained in lactide, 0.10mmol embodiments 6 is mixed with 40ml toluene, and 70 DEG C are stirred to react 8h,
30ml chloroforms are added and dissolve polymer, excessive ethanol precipitation polymer, filtering is dried in vacuo 48h.
The quality that the present invention weighs to obtain polylactic acid is 2.0g；
The present invention divides the polylactic acid that the present embodiment obtains using polystyrene as reference substance, using gel permeation chromatography
Analysis, the number-average molecular weight for obtaining polylactic acid are 1.9 ten thousand；
The present invention analyzes the polylactic acid that the present embodiment obtains using homonuclear decoupling nuclear magnetic resonance spectroscopy, obtains poly- breast
The Pm of acid is 0.93.
As seen from the above embodiment, three metal centers schiff bases aluminium compound catalyst provided by the invention, there are three tools
Metal active centres, reactivity is higher, and the dosage of catalyst is less, and reaction temperature is relatively low.Meanwhile with larger sky
Between steric hindrance, the Selective long-range DEPT of catalyzing ring-opening polymerization of lactide, have higher catalytic activity and structure selectivity, improve poly-
The regularity of lactic acid space structure.The experimental results showed that the yield that method provided by the invention prepares polylactic acid can reach 95%,
The three-dimensional regularity (Pm) of obtained polylactic acid is up to 0.98.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (10)
1. a kind of three metal center schiff bases 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 centers schiff bases aluminium compound, which is characterized in that include the following steps：
By schiff bases shown in formula (II) structure and Al (R ')3Reaction, obtains schiff bases 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 centers schiff bases aluminium compound, which is characterized in that include the following steps：
A) by schiff bases shown in formula (II) structure and Al (R ')3Reaction obtains schiff bases calorize shown in formula (III) structure and closes
Object；
B schiff bases aluminium compound shown in the formula (III) structure is reacted with R 〞 H), obtains 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 〞 are-OCH3、-OCH2CH3、-OCH(CH3)2Or-OCH2Ph。
4. preparation method according to claim 2 or 3, which is characterized in that schiff bases shown in formula (II) structure with
Al(R′)3Molar ratio be 1:3.
5. preparation method according to claim 2 or 3, which is characterized in that schiff bases shown in formula (II) structure with
Al(R′)3The reaction temperature of reaction is 60 DEG C~90 DEG C, and the reaction time is 9~12h.
6. preparation method according to claim 2 or 3, which is characterized in that schiff bases is pressed shown in formula (II) structure
It is prepared according to following steps：
Compound shown in formula (V) is reacted with substituted salicylic aldehydes shown in formula (VI), obtains schiff bases 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, which is characterized in that compound shown in the formula (V) is according to the following steps
It prepares：
S1) phloroglucin, acetic acid are reacted with acetic anhydride under the catalytic action of the concentrated sulfuric acid, obtain triacetyl isophthalic three
Phenol；
S2 compound shown in formula (V)) is obtained by the reaction in triacetyl phloroglucin and 1,2- diamino -2- methylpropanes.
Application of the three metal center schiff bases aluminium compounds as lactide polymerisation catalysts shown in formula 8. (I) structure,
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, which is characterized in that include the following steps：
Lactide is reacted with schiff bases 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, which is characterized in that schiff bases calorize shown in formula (I) structure is closed
The molar ratio of object and lactide is 1:50~1:10000.
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| "Polymerization of rac-Lactide Using Schiff Base Aluminum Catalysts: Structure, Activity,and Stereoselectivity";Hongzhi Du等;《Macromolecules》;20070216;第40卷(第6期);第1905页图1-2、左栏文字部分第1-4行，第1906页方案2，第1910页表1、第1911页图12 * |
| "Trinuclear Nickel Complexes with Triplesalen Ligands: Simultaneous Occurrence of Mixed Valence and Valence Tautomerism in the Oxidized Species";Thorsten Glaser等;《Inorganic chemistry》;20050630;第44卷(第15期);第5467页右栏第1-3行，第5468页左栏第14-21行，第5472页方案3 * |
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