CN102786674B - Schiff base aluminum compound, preparation method thereof and preparation method of polylactic acid - Google Patents

Schiff base aluminum compound, preparation method thereof and preparation method of polylactic acid Download PDF

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CN102786674B
CN102786674B CN201210310909.8A CN201210310909A CN102786674B CN 102786674 B CN102786674 B CN 102786674B CN 201210310909 A CN201210310909 A CN 201210310909A CN 102786674 B CN102786674 B CN 102786674B
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aluminum compound
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庞烜
曲智
段然龙
张涵
陈学思
庄秀丽
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Changzhou Institute Of Energy Storage Materials & Devices
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a Schiff base aluminum compound, a preparation method thereof and a preparation method of polylactic acid. The formula (I) of the Schiff base aluminum compound is shown in the description. Compared with the metal-centered Schiff base in the prior art, tetramine compounds are used to connect four C=N functional groups, so that two metal active center binding sites are provided to form the double-metal-centered Schiff base. The double-metal-centered Schiff base has larger molecular space and larger steric hindrance, so that selectivity of lactide ring opening polymerization of the double-metal-centered Schiff base is improved, and spacially structural regularity of polymerizate is improved; reaction activity of the catalyst is improved by introducing the double metal centers, and activity of polymerization reaction is improved.

Description

The preparation method of Schiff's base aluminum compound and preparation method thereof and poly(lactic acid)
Technical field
The invention belongs to catalyst field, relate in particular to the preparation method of a kind of Schiff's base aluminum compound and preparation method thereof and poly(lactic acid).
Background technology
Poly(lactic acid) is a kind of biodegradable material of chemosynthesis, in wrapping material, biological medicine and pharmaceutical industry, has a wide range of applications.Synthetic two kinds of methods, i.e. rac-Lactide (cyclic dimer of lactic acid) ring-opening polymerization and the direct polycondensation of lactic acid of conventionally adopting of poly(lactic acid).Wherein high molecular poly(lactic acid) generally adopts the method for rac-Lactide ring-opening polymerization, and has had lot of documents and patent to carry out relevant report to rac-Lactide ring-opening polymerization, as the patent No. United States Patent (USP) that is 5235031 and the patent No. United States Patent (USP) that is 5357034.
Rac-Lactide is divided into three kinds of steric isomers: levorotatory lactide (LLA), and dextrorotation rac-Lactide (DLA) and Study of Meso-Lactide, its structure is as follows respectively:
Figure BDA00002066636700011
Levorotatory lactide dextrorotation rac-Lactide Study of Meso-Lactide
The steric configuration of rac-Lactide has conclusive effect to the machinery of polymkeric substance, processing and degraded character.The conventional catalyzer of rac-Lactide ring-opening polymerization is nontoxic tin compound, as tin chloride and stannous octoate.Under the effect of tin series catalysts, optically pure DLA, LLA respectively ring-opening polymerization obtains isotactic poly-dextrorotation rac-Lactide and poly-levorotatory lactide, and these two kinds of polymkeric substance are the crystalline polymer of 180 ℃ of fusing points.But the product of rac-lactide ring-opening polymerization is under the same conditions amorphism unregulated polymer.And compare with amorphism poly(lactic acid), use temperature a wider range of crystalline polymer, can approach melt temperature.Therefore need to develop that a kind of polymerization has stereoselective ring-opening polymerization catalyst to rac-Lactide, can obtain crystalline polylactic acid by polymerization rac-lactide.
At present, about the catalyzer of rac-Lactide stereoselectivity ring-opening polymerization, there are reports, Schiff's base-the Al catalysts of the reports such as Coates (Salbinap) AlOMe is by a part 2,2'-diaminostilbene, 1'-connects dinaphthyl and two molecule salicylic aldehyde condensations obtain Schiff's base, then by a part Schiff's base, is reacted and obtains with a part aluminum isopropylate; (cyclohexylsalen) AlOiPr catalyzer of the report such as Zhong Zhiyuan, is by a part 1,2-hexamethylene diamino and two molecules 3, and the condensation of 5-di-tert-butyl salicylaldehyde obtains Schiff's base, then by a part Schiff's base, is reacted and obtains with a part aluminum isopropylate.But the catalyzer of reporting is all the salicylic aldehydes by salicylic aldehyde or replacement reacts the monometallic center Schiff's base obtaining with diamine, selectivity and the activity of its catalyzed reaction are lower.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide the preparation method of a kind of Schiff's base aluminum compound and preparation method thereof and poly(lactic acid), and this Schiff's base aluminum compound catalysis poly(lactic acid) is synthetic has higher reactive behavior and selectivity.
The invention provides a kind of Schiff's base aluminum compound, as shown in the formula (I):
Figure BDA00002066636700021
In formula (I), R is-CH 3,-CH 2cH 3,-OCH 3,-OCH 2cH 3,-OCH (CH 3) 2or-OCH 2ph;
R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2.
The preparation method who the invention provides a kind of Schiff's base aluminum compound, comprises the following steps:
By Schiff's base and the Al(R ' of formula (II) structure) 3in solvent, react, obtain the Schiff's base aluminum compound of formula (III) structure;
Figure BDA00002066636700022
R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2;
R ' is-CH 3or-CH 2cH 3.
Preferably, also comprise:
The Schiff's base aluminum compound of described formula (III) structure is reacted in solvent with R 〞 H, obtain the Schiff's base aluminum compound of formula (IV) structure;
Figure BDA00002066636700032
R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2;
R 〞 is-OCH 3,-OCH 2cH 3,-OCH (CH 3) 2or-OCH 2ph.Preferably, Schiff's base and the Al(R ' of described formula (II) structure) 3the temperature of reaction of reaction is 60 ℃ ~ 100 ℃, and the reaction times is 9 ~ 11h.
Preferably, the Schiff's base of described formula (II) structure is prepared according to following steps:
By season penta tetramine react with the substituted salicylic aldehydes of formula V structure, obtain the Schiff's base of formula (II) structure;
Figure BDA00002066636700041
In formula V, R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2.
Preferably, tetramine is prepared according to following steps described season penta:
S1) tetramethylolmethane is reacted in solvent with Methanesulfonyl chloride, obtain compound VI a;
S2) described compound VI a and sodiumazide are warming up to 100 ℃ ~ 120 ℃ in solvent, after reaction 20 ~ 30h, obtain compound VI b;
S3) described compound VI b is reacted in solvent with lithium aluminum hydride, obtain season penta tetramine;
Figure BDA00002066636700042
Preferably, described step S3 is specially:
Under the condition of shielding gas and ice bath, described compound VI b is reacted in solvent to 1.5 ~ 2.5h with lithium aluminum hydride; Reaction system is warming up to room temperature, and stirring reaction 1.5 ~ 2.5h, obtains season penta tetramine.
The preparation method who the invention provides a kind of poly(lactic acid), comprises the following steps:
Rac-Lactide is reacted in solvent with the Schiff's base aluminum compound of formula (I) structure, obtain poly(lactic acid);
In formula (I), R is-CH 3,-CH 2cH 3,-OCH 3,-OCH 2cH 3,-OCH (CH 3) 2or-OCH 2ph;
R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2.
Preferably, the Schiff's base aluminum compound of described formula (I) structure and the mol ratio of rac-Lactide are 1:70 ~ 1:400.
Preferably, the temperature of reaction of described reaction is 35 ℃ ~ 110 ℃, and the reaction times is 1.5 ~ 31h.
The preparation method who the invention provides a kind of Schiff's base aluminum compound and preparation method thereof and poly(lactic acid), the structure of this Schiff's base aluminum compound as shown in the formula (I).Compare with prior art monometallic center Schiff's base, the present invention utilizes tetramine compound to connect four C=N functional groups, thereby two metal active center binding sites are provided, and forms bimetallic center Schiff's base.Bimetallic center Schiff's base has on the one hand larger molecule space and has obtained larger sterically hinderedly, and its selectivity to rac-Lactide ring-opening polymerization is strengthened, and has improved the regularity of polymerisate space structure; The introducing of bimetallic center has also strengthened the reactive behavior of catalyzer on the other hand, improves the activity of polyreaction.
Experimental result shows, the poly(lactic acid) that Schiff's base aluminum compound catalysis rac-lactide of the present invention obtains is the crystalline polymer of 144 ℃ ~ 199 ℃ of fusing points.
Embodiment
The invention provides a kind of schiff base compounds, its structure as shown in the formula (I):
Figure BDA00002066636700051
In formula (I), R is-CH 3,-CH 2cH 3,-OCH 3,-OCH 2cH 3,-OCH (CH 3) 2or-OCH 2ph; R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2.
Compare with monometallic center Schiff's base, schiff base compounds of the present invention is bimetallic center Schiff's base, and for rac-Lactide ring-opening polymerization provides two avtive spots, reactive behavior strengthens; Meanwhile, bimetal Schiff's base also has larger sterically hindered, thereby the selectivity of rac-Lactide ring-opening polymerization is strengthened, and has improved the regularity of polymerisate space structure.
Selectively, when R is-CH 3or-CH 2cH 3time, the present invention also provides a kind of preparation method of Schiff's base aluminum compound, comprises the following steps: by Schiff's base and the Al(R ' of formula (II) structure) 3in solvent, react, obtain the Schiff's base aluminum compound of formula (III) structure.Wherein, described solvent is organic solvent well known to those skilled in the art, is preferably tetrahydrofuran (THF) or toluene.
R 1and R 2selection affect the selection of solvent, work as R 1and R 2independently selected from-H ,-F ,-Cl ,-Br or-NO 2time, reaction solvent is preferably tetrahydrofuran (THF), works as R 1and R 2independently selected from-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3time, reaction solvent is preferably toluene.
Figure BDA00002066636700061
R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2;
R ' is-CH 3or-CH 2cH 3.
Al(R ' described in the present invention) 3be preferably Al(CH 3) 3or Al(CH 2cH 3) 3.R ' in formula (III) is from Al(R ') 3.Described Al(R ') 3with the mol ratio of the Schiff's base of formula (II) structure be 2:1, schiff base compounds of the present invention is metal complexes, this ratio can guarantee a metal active center simultaneously and two C=N functional groups form coordinate bonds.
Described Schiff's base and Al(R ') 3the temperature of reaction of reaction is 60 ℃ ~ 100 ℃, and the selection of reaction solvent is depended in the selection of temperature, is preferably 65 ℃ ~ 75 ℃ or 85 ℃ ~ 95 ℃, and the reaction times is 9 ~ 11h, is preferably 9 ~ 10h.
Wherein, the Schiff's base of described formula (II) structure is preferably prepared according to following steps: by season penta tetramine react with the substituted salicylic aldehydes of formula V structure, obtain the Schiff's base of formula (II) structure;
In formula V, R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2.
Season penta tetramine and the substituted salicylic aldehydes generation condensation reaction of formula V structure, need under the condition refluxing, react 10 ~ 14h, be preferably 12 ~ 14h.
According to the present invention, described season penta tetramine preferably according to following steps, prepare: S1) tetramethylolmethane is reacted in solvent with Methanesulfonyl chloride, obtains compound VI a; S2) described compound VI a and sodiumazide are warming up to 100 ℃ ~ 120 ℃ in solvent, after reaction 20 ~ 30h, obtain compound VI b; S3) described compound VI b is reacted in solvent with lithium aluminum hydride, obtain season penta tetramine.
Figure BDA00002066636700072
Wherein, solvent described in step S1 is organic solvent well known to those skilled in the art, is preferably pyridine.
Solvent in described step S2 is organic solvent well known to those skilled in the art, is preferably dimethyl sulfoxide (DMSO).Temperature of reaction is 90 ℃ ~ 120 ℃, is preferably 100 ℃ ~ 115 ℃, and the reaction times is 20 ~ 30h, is preferably 22 ~ 25h.
Described step S3 is specially: under the condition of shielding gas and ice bath, described compound VI b is reacted in solvent to 1.5 ~ 2.5h with lithium aluminum hydride, be preferably 1.8 ~ 2h; Reaction system is warming up to room temperature, and stirring reaction 1.5 ~ 2.5h, is preferably 1.8 ~ 2h.Described solvent is organic solvent well known to those skilled in the art, is preferably tetrahydrofuran (THF).
Selectively, when R is-OCH 3,-OCH 2cH 3,-OCH (CH 3) 2or-OCH 2during Ph, the invention provides the preparation method of another kind of Schiff's base aluminum compound, this preparation method continues reaction on the basis of the Schiff's base aluminum compound preparation process of above-mentioned formula (III) structure, obtains the different Schiff's base aluminum compound of substituted radical.This preparation method is on the basis of above-mentioned steps, further comprising the steps of: the Schiff's base aluminum compound of described formula (III) structure is reacted in solvent with R 〞 H, obtain the Schiff's base aluminum compound of formula (IV) structure.Described solvent is organic solvent well known to those skilled in the art, is preferably tetrahydrofuran (THF) or toluene.Described R 〞 H is preferably CH 3oH, CH 3cH 2oH, (CH 3) 2cHOH or PhCH 2oH.
Figure BDA00002066636700081
In formula (IV), R 〞 is-OCH 3,-OCH 2cH 3,-OCH (CH 3) 2or-OCH 2ph.R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2.
Wherein, the mol ratio of the Schiff's base aluminum compound of described R 〞 H and formula (III) structure is 2:1.
The present invention also provides a kind of preparation method of poly(lactic acid), comprises the following steps: rac-Lactide is reacted in solvent with the Schiff's base aluminum compound of formula (I) structure, obtain poly(lactic acid).Described solvent is organic solvent well known to those skilled in the art, is preferably tetrahydrofuran (THF) or toluene.
Wherein, the Schiff's base aluminum compound of formula (I) structure is that rac-Lactide polymerization generates the catalyzer in poly(lactic acid) reaction.The mol ratio of this catalyzer and rac-Lactide is 1:70 ~ 1:400.
In the present invention, the temperature of reaction of rac-Lactide polyreaction is 35 ~ 110 ℃, and the reaction times is 1.5 ~ 31h.This reaction is preferably carried out under the condition of anhydrous and oxygen-free, can reduce the generation of side reaction.
Described Schiff's base aluminum compound is bimetal Schiff's base Al catalysts, has two metal active centers, and its reactive behavior is higher, and the consumption of catalyzer is less, and temperature of reaction is lower.Simultaneously, it has larger sterically hindered, the selectivity of catalyzing ring-opening polymerization of lactide strengthens, and not only can catalysis rac-lactide obtains fusing point and be the crystalline polylactic acid of 144 ℃ ~ 199 ℃, can also catalyzing levorotatory lactide and dextrorotation rac-Lactide mixture obtain crystalline polylactic acid.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method of Schiff's base aluminum compound provided by the invention and preparation method thereof and poly(lactic acid) is described in detail.
In following examples, reagent used is commercially available.
The preparation of embodiment 1 season penta tetramine
1.1 stir 13.6g tetramethylolmethane and 100ml pyridine under condition of ice bath, slowly add 51.5g Methanesulfonyl chloride, after reaction 3h, reaction solution is poured in the mixed solution of 200ml concentrated hydrochloric acid, 400ml water and 1000ml methyl alcohol, filter, after difference water and methanol wash three times, drain, obtain compound VI a.
1.2 are slowly heated to 100 ℃ by the compound VI a obtaining in 11.2g1.1,500mlDMSO and 10g sodiumazide under the condition stirring, after reaction 25h, reaction system is poured in 600ml water, petroleum ether extraction three times, merge organic phase, wash anhydrous magnesium sulfate drying three times, filter, revolve to steam and remove that to obtain white crystal after organic solvent be compound VI b.
1.3 under the condition of ice bath, argon shield; 1.5g lithium aluminum hydride is added in 100ml tetrahydrofuran (THF), drips the tetrahydrofuran solution 50ml that is dissolved with the compound VI b obtaining in 2.36g 1.2, after reaction 2h; be warming up to stirring at room 2h; under cooling ice bath, drip 1.5g water and stir 15min, add the sodium hydroxide solution of 1.5g15% to stir 15min, add 4.5g water to stir 30min; be warming up to after stirring at room 30min; filter, revolve and steam except desolventizing, obtaining faint yellow oily matter is season penta tetramine.
The Schiff's base IIa's that embodiment 2 structural formulas are II is synthetic
IIa：R 1=R 2=-H
By the season obtaining in 1.32g 1.3 penta tetramine be dissolved in 20ml ethanol, slowly drip the 50ml ethanol that is dissolved with 4.88g salicylic aldehyde, backflow 14h, revolves to steam and removes most of solvent, filters to obtain yellow powder, with the washing of chloroform alcohol mixed solvent, obtains Schiff's base IIa.
Utilize nucleus magnetic resonance to analyze the Schiff's base IIa obtaining in embodiment 2, obtain its hydrogen spectrum, result is as follows:
1H?NMR（300.00MHz，d 6-DMSO）：δ=13.24(s,OH?4H),8.61(s,NCH?4H),7.45、6.86(m,PhH?16H),3.76(s,CCH 2N?8H)。
Utilize ultimate analysis to analyze the Schiff's base IIa obtaining in embodiment 2, obtain its each atom content.
Elem.Anal.（%）：Calcd.C?72.24；H?5.88；N?10.21.Found:C?72.13；H?5.81；N?10.20。
The Schiff's base IIb's that embodiment 3 structural formulas are II is synthetic
IIb：R 1=R 2=-Cl
By the season obtaining in 1.32g 1.3 penta tetramine be dissolved in 20ml ethanol, slowly drip and be dissolved with 7.64g3,5-dichloro-salicylaldehyde's 50ml ethanol, backflow 14h, revolves to steam and removes most of solvent, filters to obtain greenish orange yellow powder, with the washing of chloroform alcohol mixed solvent, obtain Schiff's base IIb.
Utilize nucleus magnetic resonance to analyze the Schiff's base IIb obtaining in embodiment 3, obtain its hydrogen spectrum, result is as follows:
1H?NMR（300.00MHz，d 6-DMSO）：δ=14.34(s,OH?4H),8.65(s,NCH?4H)7.59、7.45(m,PhH?8H),3.89(s,CCH 2N8H)。
Utilize ultimate analysis to analyze the Schiff's base IIb obtaining in embodiment 3, obtain its each atom content.
Elem.Anal.（%）：Calcd.C?48.09；H?2.94；N?6.80。Found:C?48.27；H?3.11；N?6.67。
The Schiff's base IIc's that embodiment 4 structural formulas are II is synthetic
IIc：R 1=R 2=-CH 3
By the season obtaining in 1.32g 1.3 penta tetramine be dissolved in 20ml ethanol, slowly drip and be dissolved with 6.0g3, the 50ml ethanol of 5-dimethyl salicylic aldehyde, backflow 12h, revolves to steam and removes most of solvent, filters to obtain yellow powder, with after chloroform alcohol mixed solvent recrystallization, obtain Schiff's base IIc.
Utilize nucleus magnetic resonance to analyze the Schiff's base IIc obtaining in embodiment 4, obtain its hydrogen spectrum, result is as follows:
1HNMR（300.00MHz，CDCl 3）：13.20(s,OH?4H),8.34(s,NCH?4H),7.05、6.68(s,PhH?8H),3.78(s,CCH 2N8H)2.27(d,CH 324H)。
Utilize ultimate analysis to analyze the Schiff's base IIc obtaining in embodiment 4, obtain its each atom content.
Elem.Anal.（%）：Calcd.C?74.52；H?7.32；N?8.48。Found:C?73.33；H?7.18；N?8.44。
The Schiff's base IId's that embodiment 5 structural formulas are II is synthetic
IId：R 1=R 2=-C(CH 3) 3
By the season obtaining in 1.32g 1.3 penta tetramine be dissolved in 20ml ethanol, slowly drip and be dissolved with 9.36g3, the 50ml ethanol of 5-di-tert-butyl salicylaldehyde, backflow 12h, revolves to steam and removes most of solvent, filters to obtain yellow powder, with after chloroform alcohol mixed solvent recrystallization, obtain Schiff's base IId.
Utilize nucleus magnetic resonance to analyze the Schiff's base IId obtaining in embodiment 5, obtain its hydrogen spectrum, result is as follows:
1H?NMR（300.00MHz，CDCl 3）：δ=13.71(s,OH?4H),8.55(s,NCH?4H),7.46、7.18(s,PhH?8H),3.84(s,CCH 2N?8H),1.53(s,PhC(CH 3) 336H),1.35(s,PhC(CH 3) 336H)。
Utilize ultimate analysis to analyze the Schiff's base IId obtaining in embodiment 5, obtain its each atom content.
Elem.Anal.（%）：Calcd.C?78.27；H?9.70；N?5.62。Found:C?78.15；H?9.55；N?5.68。
Schiff's base aluminum compound Ia-1 ~ Ia-5's that embodiment 6 structural formulas are I is synthetic
Ia-1：R 1=R 2=-H，R=-CH 2CH 3；
Ia-2：R 1=R 2=-H，R=-OCH 3；
Ia-3：R 1=R 2=-H，R=-OCH 2CH 3；
Ia-4：R 1=R 2=-H，R=-OCH(CH 3) 2；
Ia-5：R 1=R 2=-H，R=-OCH 2Ph。
6.1 under the condition of protection of inert gas, is the tetrahydrofuran solution of the Schiff's base IIa that obtains in 1mol/L embodiment 2 and the AlEt that 8ml concentration is 1mol/L by 4ml concentration 3tetrahydrofuran solution mix and blend, 70 ℃ of reaction 10h, are down to room temperature, vacuumize 0.1Mpa and remove volatile matter, obtain Schiff's base aluminum compound Ia-1.
6.2 are dissolved in the Schiff's base aluminum compound Ia-1 obtaining in 2mmol (1310mg) 6.1 in tetrahydrofuran (THF), add 4mmol methyl alcohol, obtain Schiff's base aluminum compound Ia-2.
The preparation method of Schiff's base aluminum compound Ia-3 ~ Ia-5 is identical with Ia-2, and wherein difference is: methyl alcohol is changed to respectively to ethanol, Virahol or benzylalcohol.
Utilize ultimate analysis to analyze the Schiff's base aluminum compound Ia-1 ~ Ia-5 obtaining in embodiment 6, obtain its each atom content.
Ia-1:Elem.Anal.（%）：Calcd.C?69.61;H?6.00；N?6.41。Found:C?70.40;H6.03；N?6.75。
Ia-2:Elem.Anal.（%）：Calcd.C?65.55;H?5.35；N?6.37。Found:C?66.62;H6.03；N?6.02。
Ia-3:Elem.Anal.（%）：Calcd.C?66.37;H?5.72；N?6.11。Found:C?67.65;H5.31；N?6.82。
Ia-4:Elem.Anal.（%）：Calcd.C?67.12;H?6.06；N?5.87。Found:C?68.25;H6.49；N?6.04。
Ia-5:Elem.Anal.（%）：Calcd.C?71.01;H?5.34；N?5.18。Found:C?71.60;H5.91；N?5.62。
Schiff's base aluminum compound Ib-1 ~ Ib-5 that embodiment 7 structural formulas are I
Ib-1：R 1=R 2=-Cl，R=-CH 2CH 3；
Ib-2：R 1=R 2=-Cl，R=-OCH 3；
Ib-3：R 1=R 2=-Cl，R=-OCH 2CH 3；
Ib-4：R 1=R 2=-Cl，R=-OCH(CH 3) 2；
Ib-5：R 1=R 2=-Cl，R=-OCH 2Ph。
The preparation method of 7.1 Schiff's base aluminum compound Ib-1 is identical with Ia-1, and wherein difference is: the tetrahydrofuran solution that the tetrahydrofuran solution of the Schiff's base IIa obtaining in embodiment 2 is changed to the Schiff's base IIb obtaining in embodiment 3.
7.2 are dissolved in the Schiff's base aluminum compound Ib-1 obtaining in 2mmol 7.1 in tetrahydrofuran (THF), add 4mmol methyl alcohol, obtain Schiff's base aluminum compound Ib-2.
The preparation method of Schiff's base aluminum compound Ib-3 ~ Ib-5 is identical with Ib-2, and wherein difference is: methyl alcohol is changed to respectively to ethanol, Virahol or benzylalcohol.
Utilize ultimate analysis to analyze the Schiff's base aluminum compound Ib-1 ~ Ib-5 obtaining in embodiment 7, obtain its each atom content.
Ib-1:Elem.Anal.（%）：Calcd.C?49.01;H?3.36；N?4.51。Found:C?50.30;H3.83；N?4.84。
Ib-2:Elem.Anal.（%）：Calcd.C?46.23;H?2.91；N?4.49。Found:C?46.72;H3.40;N?4.34。
Ib-3:Elem.Anal.（%）：Calcd.C?47.38;H?3.24;N?4.36。Found:C?48.59;H3.42;N?4.80。
Ib-4:Elem.Anal.（%）：Calcd.C?48.46;H?3.56;N?4.24。Found:C?49.20;H3.23;N?4.39。
Ib-5:Elem.Anal.（%）：Calcd.C?53.02;H?3.24;N?3.86。Found:C?53.95;H3.82;N?4.42。
Schiff's base aluminum compound Ic-1 ~ Ic-5 that embodiment 8 structural formulas are I
Ic-1：R 1=R 2=-CH 3，R=-CH 2CH 3；
Ic-2：R 1=R 2=-CH 3，R=-OCH 3；
Ic-3：R 1=R 2=-CH 3，R=-OCH 2CH 3；
Ic-4：R 1=R 2=-CH 3，R=-OCH(CH 3) 2；
Ic-5：R 1=R 2=-CH 3，R=-OCH 2Ph。
The preparation method of 8.1 Schiff's base aluminum compound Ic-1 is identical with Ia-1, and wherein difference is: the tetrahydrofuran solution that the tetrahydrofuran solution of the Schiff's base IIa obtaining in embodiment 2 is changed to the Schiff's base IIc obtaining in embodiment 4.
8.2 are dissolved in the Schiff's base aluminum compound Ic-1 obtaining in 2mmol 8.1 in tetrahydrofuran (THF), add 4mmol methyl alcohol, obtain Schiff's base aluminum compound Ic-2.
The preparation method of Schiff's base aluminum compound Ic-3 ~ Ic-5 is identical with Ic-2, and wherein difference is: methyl alcohol is changed to respectively to ethanol, Virahol or benzylalcohol.
Utilize ultimate analysis to analyze the Schiff's base aluminum compound Ic-1 ~ Ic-5 obtaining in embodiment 8, obtain its each atom content.
Ic-1:Elem.Anal.（%）：Calcd.C?71.95;H?7.22;N?5.47。Found:C?72.48;H7.96;N?6.35。
Ic-2:Elem.Anal.（%）：Calcd.C?68.47;H?6.66;N?5.44。Found:C?69.34;H7.05;N?6.06。
Ic-3:Elem.Anal.（%）：Calcd.C?69.07;H?6.93;N?5.25。Found:C?69.86;H6.56;N?5.62。
Ic-4:Elem.Anal.（%）：Calcd.C?69.63;H?7.18;N?5.08。Found:C?69.94;H7.53;N?5.47。
Ic-5:Elem.Anal.（%）：Calcd.C?72.79;H?6.44;N?4.55。Found:C?73.19;H6.83;N?4.96。
Schiff's base aluminum compound Id-1 ~ Id-5 that embodiment 9 structural formulas are I
Id-1：R 1=R 2=-C(CH 3) 3，R=-CH 2CH 3；
Id-2：R 1=R 2=-C(CH 3) 3，R=-OCH 3；
Id-3：R 1=R 2=-C(CH 3) 3，R=-OCH 2CH 3；
Id-4：R 1=R 2=-C(CH 3) 3，R=-OCH(CH 3) 2；
Id-5：R 1=R 2=-C(CH 3) 3，R=-OCH 2Ph。
The preparation method of 9.1 Schiff's base aluminum compound Id-1 is identical with Ia-1, and wherein difference is: the tetrahydrofuran solution that the tetrahydrofuran solution of the Schiff's base IIa obtaining in embodiment 2 is changed to the Schiff's base IId obtaining in embodiment 5.
9.2 are dissolved in the Schiff's base aluminum compound Id-1 obtaining in 2mmol 9.1 in tetrahydrofuran (THF), add 4mmol methyl alcohol, obtain Schiff's base aluminum compound Id-2.
The preparation method of Schiff's base aluminum compound Id-3 ~ Id-5 is identical with Id-2, and wherein difference is: methyl alcohol is changed to respectively to ethanol, Virahol or benzylalcohol.
Utilize ultimate analysis to analyze the Schiff's base aluminum compound Id-1 ~ Id-5 obtaining in embodiment 9, obtain its each atom content.
Id-1:Elem.Anal.（%）：Calcd.C?76.12;H?9.40;N?3.80。Found:C?76.83;H9.09;N?4.09。
Id-2:Elem.Anal.（%）：Calcd.C?73.68;H?9.00;N?3.79。Found:C?74.06;H9.38;N?4.35。
Id-3:Elem.Anal.（%）：Calcd.C?73.97;H?9.13;N?3.70。Found:C?74.83;H9.58;N?4.13。
Id-4:Elem.Anal.（%）：Calcd.C?74.25;H?9.26;N?3.61。Found:C?74.93;H9.86;N?4.18。
Id-5:Elem.Anal.（%）：Calcd.C?76.22;H?8.55;N?3.33。Found:C?77.25;H9.16;N?4.05。
Embodiment 10
Under the condition of anhydrous and oxygen-free, rac-lactide, 0.104mmol(68.1mg that 20.8mmol (3.0g) recrystallization is crossed) the Schiff's base aluminum compound Ia-1 that obtains in embodiment 6 mixes with 41.6ml tetrahydrofuran (THF), 40 ℃ of stirring reaction 31h, add 30ml trichloromethane dissolve polymer, excessive ethanol precipitation polymers, filters vacuum-drying 48h, obtain 2.3g poly(lactic acid), its fusing point is 151 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 10, the number-average molecular weight that obtains poly(lactic acid) is 1.1 ten thousand.
Embodiment 11
Under the condition of anhydrous and oxygen-free, the Schiff's base aluminum compound Ia-2 obtaining in the rac-lactide that 20.8mmol recrystallization is crossed, 0.104mmol embodiment 6 mixes with 41.6ml tetrahydrofuran (THF), 40 ℃ of stirring reaction 31h, add 30ml trichloromethane dissolve polymer, excessive ethanol precipitation polymers, filters vacuum-drying 48h, obtain 2.1g poly(lactic acid), its fusing point is 148 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 11, the number-average molecular weight that obtains poly(lactic acid) is 0.92 ten thousand.
Embodiment 12
Preparation method is identical with embodiment 10, and difference is that catalyzer is the Schiff's base aluminum compound Ia-3 obtaining in embodiment 6, obtains 2.2g poly(lactic acid), and its fusing point is 147 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 12, the number-average molecular weight that obtains poly(lactic acid) is 1.0 ten thousand.
Embodiment 13
Preparation method is identical with embodiment 10, and difference is that catalyzer is the Schiff's base aluminum compound Ia-4 obtaining in embodiment 6, obtains 2.1g poly(lactic acid), and its fusing point is 151 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 13, the number-average molecular weight that obtains poly(lactic acid) is 0.98 ten thousand.
Embodiment 14
Preparation method is identical with embodiment 10, and difference is that catalyzer is the Schiff's base aluminum compound Ia-5 obtaining in embodiment 6, obtains 1.9g poly(lactic acid), and its fusing point is 150 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 14, the number-average molecular weight that obtains poly(lactic acid) is 0.87 ten thousand.
Embodiment 15
Under the condition of anhydrous and oxygen-free, by 20.8mmol(3.0g) the recrystallization rac-lactide, the 0.297mmol(276.6mg that cross) the Schiff's base aluminum compound Ib-1 that obtains in embodiment 7 mixes with 41.6ml tetrahydrofuran (THF), 35 ℃ of stirring reaction 25h, add 30ml trichloromethane dissolve polymer, excessive ethanol precipitation polymers, filters vacuum-drying 48h, obtain 2.6g poly(lactic acid), its fusing point is 145 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 15, the number-average molecular weight that obtains poly(lactic acid) is 0.37 ten thousand.
Embodiment 16
Preparation method is identical with embodiment 15, and difference is that catalyzer is the Schiff's base aluminum compound Ib-2 obtaining in embodiment 7, obtains 2.5g poly(lactic acid), and its fusing point is 144 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 16, the number-average molecular weight that obtains poly(lactic acid) is 0.42 ten thousand.
Embodiment 17
Preparation method is identical with embodiment 15, and difference is that catalyzer is the Schiff's base aluminum compound Ib-3 obtaining in embodiment 7, obtains 2.3g poly(lactic acid), and its fusing point is 143 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 17, the number-average molecular weight that obtains poly(lactic acid) is 0.43 ten thousand.
Embodiment 18
Preparation method is identical with embodiment 15, and difference is that catalyzer is the Schiff's base aluminum compound Ib-4 obtaining in embodiment 7, obtains 2.2g poly(lactic acid), and its fusing point is 146 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 18, the number-average molecular weight that obtains poly(lactic acid) is 0.38 ten thousand.
Embodiment 19
Preparation method is identical with embodiment 15, and difference is that catalyzer is the Schiff's base aluminum compound Ib-5 obtaining in embodiment 7, obtains 2.3g poly(lactic acid), and its fusing point is 144 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 19, the number-average molecular weight that obtains poly(lactic acid) is 0.39 ten thousand.
Embodiment 20
Under the condition of anhydrous and oxygen-free, by 20.8mmol(3.0g) the recrystallization rac-lactide, the 0.13mmol(100.1mg that cross) the Schiff's base aluminum compound Ic-1 that obtains in embodiment 8 mixes with 41.6ml toluene, 70 ℃ of stirring reaction 12h, add 35ml trichloromethane dissolve polymer, excessive ethanol precipitation polymers, filters vacuum-drying 48h, obtain 2.7g poly(lactic acid), its fusing point is 158 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 20, the number-average molecular weight that obtains poly(lactic acid) is 1.1 ten thousand.
Embodiment 21
Preparation method is identical with embodiment 20, and difference is that catalyzer is the Schiff's base aluminum compound Ic-2 obtaining in embodiment 8, obtains 2.8g poly(lactic acid), and its fusing point is 159 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 21, the number-average molecular weight that obtains poly(lactic acid) is 1.0 ten thousand.
Embodiment 22
Preparation method is identical with embodiment 20, and difference is that catalyzer is the Schiff's base aluminum compound Ic-3 obtaining in embodiment 8, obtains 2.6g poly(lactic acid), and its fusing point is 157 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 22, the number-average molecular weight that obtains poly(lactic acid) is 0.98 ten thousand.
Embodiment 23
Preparation method is identical with embodiment 20, and difference is that catalyzer is the Schiff's base aluminum compound Ic-4 obtaining in embodiment 8, obtains 2.7g poly(lactic acid), and its fusing point is 158 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 23, the number-average molecular weight that obtains poly(lactic acid) is 1.0 ten thousand.
Embodiment 24
Preparation method is identical with embodiment 20, and difference is that catalyzer is the Schiff's base aluminum compound Ic-5 obtaining in embodiment 8, obtains 2.8g poly(lactic acid), and its fusing point is 159 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 24, the number-average molecular weight that obtains poly(lactic acid) is 1.0 ten thousand.
Embodiment 25
Under the condition of anhydrous and oxygen-free, by 20.8mmol(3.0g) the recrystallization rac-lactide, the 0.091mmol(100.5mg that cross) the Schiff's base aluminum compound Id-1 that obtains in embodiment 9 mixes with 41.6ml toluene, 70 ℃ of stirring reaction 9h, add 30ml trichloromethane dissolve polymer, excessive ethanol precipitation polymers, filters vacuum-drying 48h, obtain 2.4g poly(lactic acid), its fusing point is 195 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 25, the number-average molecular weight that obtains poly(lactic acid) is 1.2 ten thousand.
Embodiment 26
Preparation method is identical with embodiment 25, and difference is that catalyzer is the Schiff's base aluminum compound Id-2 obtaining in embodiment 9, obtains 2.5g poly(lactic acid), and its fusing point is 197 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 26, the number-average molecular weight that obtains poly(lactic acid) is 1.1 ten thousand.
Embodiment 27
Preparation method is identical with embodiment 25, and difference is that catalyzer is the Schiff's base aluminum compound Id-3 obtaining in embodiment 9, obtains 2.3g poly(lactic acid), and its fusing point is 198 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 27, the number-average molecular weight that obtains poly(lactic acid) is 1.0 ten thousand.
Embodiment 28
Preparation method is identical with embodiment 25, and difference is that catalyzer is the Schiff's base aluminum compound Id-4 obtaining in embodiment 9, obtains 2.4g poly(lactic acid), and its fusing point is 199 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 28, the number-average molecular weight that obtains poly(lactic acid) is 1.1 ten thousand.
Embodiment 29
Preparation method is identical with embodiment 25, and difference is that catalyzer is the Schiff's base aluminum compound Id-5 obtaining in embodiment 9, obtains 2.5g poly(lactic acid), and its fusing point is 198 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 29, the number-average molecular weight that obtains poly(lactic acid) is 1.2 ten thousand.
Embodiment 30
Under the condition of anhydrous and oxygen-free, by 20.8mmol(3.0g) the recrystallization rac-lactide, the 0.091mmol(100.5mg that cross) the Schiff's base aluminum compound Id-1 that obtains in embodiment 9 mixes with 41.6ml toluene, 90 ℃ of stirring reaction 4h, add 30ml trichloromethane dissolve polymer, excessive ethanol precipitation polymers, filters vacuum-drying 48h, obtain 2.2g poly(lactic acid), its fusing point is 184 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 30, the number-average molecular weight that obtains poly(lactic acid) is 0.9 ten thousand.
Embodiment 31
Under the condition of anhydrous and oxygen-free, by 20.8mmol(3.0g) the recrystallization rac-lactide, the 0.091mmol(100.5mg that cross) the Schiff's base aluminum compound Id-1 that obtains in embodiment 9 mixes with 41.6ml toluene, 110 ℃ of stirring reaction 1.5h, add 30ml trichloromethane dissolve polymer, excessive ethanol precipitation polymers, filters vacuum-drying 48h, obtain 2.1g poly(lactic acid), its fusing point is 173 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 31, the number-average molecular weight that obtains poly(lactic acid) is 1.1 ten thousand.
Embodiment 32
Under the condition of anhydrous and oxygen-free, by 20.8mmol(3.0g) the recrystallization levorotatory lactide, the 0.104mmol(81.2mg that cross) the Schiff's base aluminum compound Ic-1 that obtains in embodiment 8 mixes with 41.6ml toluene, 70 ℃ of stirring reaction 29h, add 30ml trichloromethane dissolve polymer, excessive ethanol precipitation polymers, filters vacuum-drying 48h, obtain 1.7g poly(lactic acid), its fusing point is 155 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 32, the number-average molecular weight that obtains poly(lactic acid) is 1.2 ten thousand.
Embodiment 33
Under the condition of anhydrous and oxygen-free, by 20.8mmol(3.0g) recrystallization the dextrorotation rac-Lactide, the 0.15mmol(148.5mg that cross) the Schiff's base aluminum compound Ib-4 that obtains in embodiment 7 mixes with 41.6ml tetrahydrofuran (THF), 70 ℃ of stirring reaction 31h, add 30ml trichloromethane dissolve polymer, excessive ethanol precipitation polymers, filters vacuum-drying 48h, obtain 2.3g poly(lactic acid), its fusing point is 145 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 33, the number-average molecular weight that obtains poly(lactic acid) is 0.9 ten thousand.
Embodiment 34
Under the condition of anhydrous and oxygen-free, dextrorotation rac-Lactide, 0.10mmol(111.7mg that the levorotatory lactide that 2.76mmol recrystallization is crossed, 11.04mmol recrystallization are crossed) the Schiff's base aluminum compound Id-3 that obtains in embodiment 9 mixes with 27.6ml toluene, 70 ℃ of stirring reaction 8h, add 30ml trichloromethane dissolve polymer, excessive ethanol precipitation polymers, filters vacuum-drying 48h, obtain 1.2g poly(lactic acid), its fusing point is 163 ℃.
Take polystyrene as standard substance, utilize gel permeation chromatography to analyze the poly(lactic acid) obtaining in embodiment 34, the number-average molecular weight that obtains poly(lactic acid) is 0.9 ten thousand.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (8)

1. a Schiff's base aluminum compound, as shown in the formula (I):
In formula (I), R is-CH 3,-CH 2cH 3,-OCH 3,-OCH 2cH 3,-OCH (CH 3) 2or-OCH 2ph;
R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2.
2. a preparation method for Schiff's base aluminum compound, is characterized in that, comprises the following steps:
By Schiff's base and the Al(R ' of formula (II) structure) 3in solvent, react, obtain the Schiff's base aluminum compound of formula (III) structure, described temperature of reaction is 60 ℃～100 ℃, and the reaction times is 9～11h;
Figure FDA0000466485310000012
Figure FDA0000466485310000021
R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2;
R ' is-CH 3or-CH 2cH 3;
The Schiff's base of described formula (II) structure is prepared according to following steps:
By season penta tetramine react with the substituted salicylic aldehydes of formula V structure, obtain the Schiff's base of formula (II) structure;
Figure FDA0000466485310000022
In formula V, R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2.
3. preparation method according to claim 2, is characterized in that, also comprises:
The Schiff's base aluminum compound of described formula (III) structure is reacted in solvent with R 〞 H, obtain the Schiff's base aluminum compound of formula (IV) structure;
Figure FDA0000466485310000031
R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2;
R 〞 is-OCH 3,-OCH 2cH 3,-OCH (CH 3) 2or-OCH 2ph.
4. preparation method according to claim 2, is characterized in that, described season penta tetramine according to following steps, prepare:
S1) tetramethylolmethane is reacted in solvent with Methanesulfonyl chloride, obtain compound VI a;
S2) described compound VI a and sodiumazide are warming up to 100 ℃～120 ℃ in solvent, after reaction 20～30h, obtain compound VI b;
S3) described compound VI b is reacted in solvent with lithium aluminum hydride, obtain season penta tetramine;
5. preparation method according to claim 4, is characterized in that, described step S3 is specially:
Under the condition of shielding gas and ice bath, described compound VI b is reacted in solvent to 1.5～2.5h with lithium aluminum hydride; Reaction system is warming up to room temperature, and stirring reaction 1.5～2.5h, obtains season penta tetramine.
6. a preparation method for poly(lactic acid), is characterized in that, comprises the following steps:
Rac-Lactide is reacted in solvent with the Schiff's base aluminum compound of formula (I) structure, obtain poly(lactic acid);
Figure FDA0000466485310000041
In formula (I), R is-CH 3,-CH 2cH 3,-OCH 3,-OCH 2cH 3,-OCH (CH 3) 2or-OCH 2ph;
R 1and R 2independently selected from-H ,-CH 3,-CH 2cH 3,-CH (CH 3) 2,-C (CH 3) 3,-F ,-Cl ,-Br or-NO 2.
7. preparation method according to claim 6, is characterized in that, the Schiff's base aluminum compound of described formula (I) structure and the mol ratio of rac-Lactide are 1:70～1:400.
8. preparation method according to claim 6, is characterized in that, the temperature of reaction of described reaction is 35 ℃～110 ℃, and the reaction times is 1.5～31h.
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