CN102260283B - Heterocycle substituted bidentate amino ligand aluminium complex as well as preparation method thereof and application thereof - Google Patents

Heterocycle substituted bidentate amino ligand aluminium complex as well as preparation method thereof and application thereof Download PDF

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CN102260283B
CN102260283B CN201110093009.8A CN201110093009A CN102260283B CN 102260283 B CN102260283 B CN 102260283B CN 201110093009 A CN201110093009 A CN 201110093009A CN 102260283 B CN102260283 B CN 102260283B
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CN102260283A (en
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马海燕
刘峻鹏
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East China University of Science and Technology
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Abstract

The invention discloses a heterocycle substituted bidentate amino ligand aluminum complex as well as a preparation method thereof and an application thereof in catalyzing lactone polymerization. The preparation method comprises the following steps of: directly reacting heterocycle substituted bidentate amino ligand and aluminum alkyl; and then obtaining a target compound from a reactant through filtering, concentrating and recrystallization steps. The heterocycle substituted bidentate amino ligand aluminum complex disclosed by the invention is a high-efficiency lactone ring-opening polymerization catalyst, which can be used for polymerization reaction of lactide, epsilon-caprolactone and the like. The novel aluminum complex disclosed by the invention has very obvious advantages of easily obtained raw material, simple synthesis route, high product yield, comparatively stable property, higher catalytic activity and narrow molecular weight distribution; polylactide with high molecular weight and polycaprolactone with high molecular weight can be obtained; and requirements of industrial departments can be satisfied. The structural formulas of the ligand and the complex are shown in the specification.

Description

Heterocyclic substituted bidentate amido ligand aluminum complex compound and its preparation method and application
Technical field
The present invention relates to heterocycle substituted bidentate amido ligand aluminum metal complex, with and application in ring-opening polymerization of lactone by catalysis.
Background technology
Annular lactone compounds, wherein outbalance has 6-caprolactone (ε-CL) and a rac-Lactide (LA) etc., can under the effect of catalyzer, ring-opening polymerization obtain polylactone compound, and this is also the important method of preparing polylactone material.With social development, people also improve day by day to the requirement of the environmental-protecting performance of material.Because polylactone class material has good biodegradability, and good bio-compatibility, plasticity-, good machining property, be regarded as having most the material of application prospect.In fields such as wrapping material, medical and health, medicine equipment and clothes, all there is very huge application potential.
Polycaprolactone and polylactide are of paramount importance two classes in polylactone material, and they all have the irreplaceable performance of other materials.Polycaprolactone is owing to having good medicine penetrance, preferably water transport property, vivo degradation are slower, is very good material implanted.The raw material of rac-Lactide, from lactic acid, so rac-Lactide can be obtained by plant resources, has great significance to solving the situation being becoming tight fossil resource day.The organometallics that research shows various metals all shown higher catalyzing lactone compound ring-opening polymerization active (Coord.Chem.Rev.2006,250,602-626).Metallic aluminium atom is acid owing to having stronger Lewis, so research is relatively many.2003, Hillmyer group reported the aluminium alkoxyl group complex compound of nitrogenous claw type part, to the ring-opening polymerization of 6-caprolactone shown higher katalysis (Daton Trans., 2003,3082-3087).2007, Dagorne group reported the aluminium methyl complex compound of substituted benzyl phenyl amines part, and the aluminum alkoxide generating with Virahol effect can the polymerization of highly active catalytic 6-caprolactone, and the narrower (Chem.Eur.J. of the molecular weight distribution of resulting polymers, 2007,13,3202-3217).2010, Mountford etc. have reported that ring-opening polymerization has shown catalytic activity to rac-Lactide for the bidentate of nitrogenous ligating atom and the aluminium ethyl complex compound of claw type structure part, the feature in catalytic process with living polymerization, but research finds that such catalyzer is not when having alcohol to cause, and catalytic activity is very low.2010, the catalytic activity of the aluminium trimethide complex compound that Fontaine etc. have studied cyclohexyl bridging three tooth nitrogen atom ligands to caprolactone and rac-Lactide, research shows that catalyzer is not adding under the condition of alcohol, catalysis caprolactone has been shown to catalytic activity, but resulting polymers molecular weight distribution wider (2.91-2.03); After adding benzylalcohol, catalytic activity is significantly improved, and the controllability of molecular weight distribution (1.87) has also been had to obvious improvement.
Research in recent years shows amido aluminium complex, aspect catalysis 6-caprolactone and rac-Lactide ring-opening polymerization, has higher catalyzed polymerization active, and the molecular weight of polymerisate and structure are had to controllability, is to have very much researchdevelopment potentiality.
Comprise now that the problem that the organic lactone ring opening polymerization catalyzer of metal of metallic aluminium catalyzer faces is, add into catalyzer the alcohol compound of equivalence ratio simultaneously, catalyzer just can show higher activity and catalysis controllability.Due to adding the tolerance range of the amount of alcohol to have higher requirement restriction, this has brought larger difficulty to industrial production.Develop and there is high catalytic activity and catalysis controllability, and synthetic easy, cost is lower, the catalyzer of being convenient to industrial operation is very necessary.
Summary of the invention
One of object of the present invention is the aluminium complex of open heterocycle substituted bidentate amido part, the defect existing to overcome prior art.
Two of object of the present invention is preparation methods of open heterocycle substituted bidentate amido ligand aluminum complex compound.
Three of object of the present invention is the effects in catalysis rac-Lactide and 6-caprolactone ring-opening polymerization as catalyzer of open heterocycle substituted bidentate amido ligand aluminum complex compound.
Technical conceive of the present invention:
By the method for metal complex to catalyze cyclic ester ring-opening polymerization, it is one of important method of production polyester compound.The subject matter facing is now the problems such as the catalyst activity causing not completely due to the initiation of catalyzer is low, molecular weight distribution is wide.For addressing this problem the method generally adopting, be in catalyst system, to add the alcohol compound that becomes integer equivalent with catalyzer, such as Virahol, benzylalcohol etc., make alcohol compound and catalyzer generate the metal alcoxyl key of easy catalysis cyclic ester open loop, thereby make the catalyzer formation of original comparatively inertia there is efficient, single active centre.But the metal complex of many nitrogen ligands also may make complex compound decompose when the alcohol compound with additional reacts generation alcoxyl key, causes dissociation of ligand, loses controllability.To become equivalent ratio to add with catalyzer fashionable for alcohol compound in addition, and in system, catalytic active center is just more single, and catalytic effect is just best.This has just proposed higher requirement to operation.Mainly for the problems referred to above, we have designed the aluminium complex of this Novel series heterocyclic substituted bidentate amido part.Wish to utilize the adjustability of imido nitrogen atom Coordinate property, obtain the catalyzer that do not need to add other initiators, can directly cause internal ester monomer controllable polymerization, to adapt to the needs of preparing the polymkeric substance that molecular weight is controlled, molecular weight distribution is narrow.
Heterocyclic substituted bidentate amido ligand compound provided by the invention (I), and aluminium complex (II), is characterized in that having following general structure:
In formula (I), (II):
R 1～R 5represent respectively hydrogen, C 1～C 12the alkyl of straight or branched structure, halogen; R 6for C 1～C 6straight chain, the alkyl of side chain; X is methylene radical or Sauerstoffatom.
R 1～R 5for hydrogen, C 1～C 6the alkyl of straight or branched structure, halogen.
R 1～R 5for hydrogen, methyl, ethyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclohexyl, phenyl, methoxyl group; R 6for methyl, ethyl, isopropoxy, the structure of preferred aluminum compound is:
Preferred ligand structure is:
The complex compound (II) of heterocyclic substituted bidentate amido ligand compound of the present invention (I) and metallic aluminium thereof, preparation method's following steps:
By the heterocyclic substituted phenyl aldehyde shown in (IV) formula and substituted aniline generation condensation reaction, generate corresponding Schiff alkali cpd, add again reductive agent, in organic medium, react 15～48 hours, then from reduzate, collect corresponding ligand compound (I).
Said heterocyclic substituted phenyl aldehyde is 2-piperidyl phenyl aldehyde, 2-morpholine benzaldehyde.
In said substituted aniline, R 1～R 5represent respectively hydrogen, C 1～C 12straight chain, the alkyl of branched structure, halogen.
The mol ratio of heterocyclic substituted phenyl aldehyde and substituted aniline is 1: 1～2, preferably 1: 1～1.2.
The preferred sodium borohydride of said reductive agent.
The imines generating and the mol ratio of sodium borohydride are 1: 8～20, preferably 1: 10～15.
Above-mentioned organic medium is selected from methyl alcohol, ethanol, tetrahydrofuran (THF), one or both in toluene, preferred alcohol.
Again the heterocyclic substituted bidentate amido ligand compound shown in formula (I) is reacted in organic medium with alkylaluminium cpd, generate heterocyclic substituted bidentate amido ligand aluminum complex compound, temperature of reaction is 0～110 ℃, preferably 70～90 ℃, reaction times is 15～48 hours, at-20 ℃ of recrystallizations, obtains target product.
Said alkylaluminium cpd is AlR 3, wherein R is C 1～C 6the alkyl of straight or branched.
The mol ratio of heterocyclic substituted bidentate amido ligand compound and aluminum alkyls is 1: 0.5～3, preferably 1: 1～1.5.
Described organic medium is selected from, one or both in toluene, normal hexane, benzene, sherwood oil, preferably toluene.
Heterocyclic substituted bidentate amido ligand aluminum compound of the present invention is a kind of catalyzer of efficient ring-opening polymerization of lactone by catalysis, be used for catalyzing lactone as the controlled ring-opening polymerization of caprolactone, rac-Lactide, polymerization process can not add any alcohol compound, but still keeps the higher active and high controllability to molecular weight distribution.Polymerization methods can be mass polymerization, solution polymerization.
The heterocyclic substituted bidentate amido aluminum compound of the present invention of take is catalyzer, makes caprolactone polymerization under 25～110 ℃ of conditions.During polymerization, the mol ratio of catalyzer and 6-caprolactone is 1: 1～3000, preferably 1: 50～500.
The heterocyclic substituted bidentate amido aluminum compound of the present invention of take is catalyzer, makes rac-Lactide polymerization under 50～110 ℃ of conditions.During polymerization, the mol ratio of catalyzer and rac-Lactide is 1: 1～3000, preferably 1: 50～500.
Catalyzer raw material provided by the invention is easy to get, and prepares easyly, and catalytic activity is high, the molecular weight of polymkeric substance is had to very high controllability, and molecular weight distribution is narrow.The needs that can meet industrial production sector, have a wide range of applications.Below by example, further illustrate the present invention, but the invention is not restricted to this.
Embodiment
The preparation of heterocyclic substituted bidentate amido part is obtained through sodium borohydride reduction by corresponding Schiff alkali.Corresponding Schiff alkali prepare reference literature (J.Chem.Soc., Perkin Trans.1,1976,1725-1734).
Embodiment 1
Synthetic ligands compound L 1
In the DMF solution of 2-piperidyl phenyl aldehyde (20mL, 20mmol), add 2-chloroaniline (21mL, 20mmol) and anhydrous K 2cO 3(3g, 22mmol), backflow 4h.Add 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH4 (240mmol), refluxes, and adds in water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water, at-20 ℃ of recrystallizations, purify, obtain white solid (3.48g, productive rate: 58%), structural formula is as follows:
mp?73℃；δ H(400MHz，CDCl 3，25℃)：7.34(d，J＝7.5Hz，1H，Ar-H)，7.26-7.21(m，2H，Ar-H)，7.18-6.98(m，3H，Ar-H)，6.71(d，J＝7.2Hz，1H，Ar-H)，6.60(td，J＝7.7，1.3Hz，1H，Ar-H)，5.21(br，1H，-NH)，4.44(d，J＝3.8Hz，2H，Ar-CH 2-)，3.01-2.80(m，4H，-NCH 2-)，1.79-1.68(m，4H，-CH 2-)，1.62-1.55(m，2H，-CH 2-).δ C(101MHz，CDCl 3，25℃)：151.67(Ar-C)，143.21(Ar-C)，132.23(Ar-C)，127.98(Ar-C)，127.86(Ar-C)，127.03(Ar-C)，126.68(Ar-C)，122.59(Ar-C)，119.06(Ar-C)，118.12(Ar-C)，115.95(Ar-C)，110.45(Ar-C)，53.09(Ar-CH 2)，43.15(-NCH 2-)，25.59(-CH 2-)，23.24(-CH 2-).Anal.Calcd.for?C 18H 21ClN 2：C，71.87；H，7.04；N，9.31；Found：71.93；H，7.27；N，9.27％。
Embodiment 2
Synthetic ligands compound L 2
In the DMF solution of 2-piperidyl phenyl aldehyde (20mL, 20mmol), add cumidine (21mL, 20mmol), and anhydrous K 2cO 3(3g, 22mmol), backflow 4h, adds 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH 4(240mmol), reflux, add in water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water, at-20 ℃ of recrystallizations, purify, obtain white solid (4.13g, productive rate: 67%), structural formula is as follows:
mp?68℃；δ H(400MHz，CDCl 3，25℃)：7.36(d，J＝7.5Hz，1H，Ar-H)，7.22(t，J＝7.2Hz，1H，Ar-H)，7.10(dd，J＝7.9，0.8Hz，1H，Ar-H)，7.06-7.01(m，3H，Ar-H)，6.61(d，J＝7.5Hz，2H，Ar-H)，4.50(br，1H，-NH)，4.35(s，2H，Ar-CH 2-)，2.90-2.81(m，4H，-NCH 2-)，2.79[hept.，J＝6.9Hz，1H，-CH(CH 3) 2]，1.75-1.67(m，4H，-CH 2-)，1.60-1.55(m，2H，-CH 2-)，1.20(d，J＝6.9Hz，6H，-CH(CH 3) 2).δ C(101MHz，CDCl 3，25℃)：151.44(Ar-C)，145.59(Ar-C)，136.60(Ar-C)，132.93(Ar-C)，128.06(Ar-C)，126.74(Ar-C)，125.94(Ar-C)，122.52(Ar-C)，118.83(Ar-C)，112.03(Ar-C)，53.85(Ar-CH 2-)，53.01(-NCH 2-)，43.96(-CH 2-)，32.09[-CH(CH 3) 2]，25.68(-CH 2-)，23.04[-CH(CH 3) 2].Anal.Calcd.for?C 21H 28N 2：C，81.77；H，9.15；N，9.08；Found：C，82.01；H，9.26；N，9.32％。
Embodiment 3
Synthetic ligands compound L 3
In the DMF solution of 2-piperidyl phenyl aldehyde (20mL, 20mmol), add aniline (21mL, 20mmol), and anhydrous K 2cO 3(3g, 22mmol), backflow 4h, adds 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH 4(240mmol), reflux, be added to the water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water, at-20 ℃ of recrystallizations, purify, obtain white solid (3.40g, productive rate: 64%), structural formula is as follows:
mp?64℃；δ H(400MHz，CDCl 3，25℃)：7.35(d，J＝7.5Hz，1H，Ar-H)，7.25(d，J＝7.2Hz，1H，Ar-H)，7.18-7.14(m，2H，Ar-H)，7.11(d，J＝7.9Hz，1H，Ar-H)，7.03(t，J＝7.5Hz，1H，Ar-H)，6.70-6.63(m，3H，Ar-H)，4.60(br，1H，-NH)，4.37(s，2H，Ar-CH 2-)，3.02-2.79(m，4H，-NCH 2-)，1.81-1.66(m，4H，-CH 2-)，1.58(m，3H，-CH 2-).δ C(101MHz，CDCl 3，25℃)：151.56(Ar-C)，147.62(Ar-C)，132.71(Ar-C)，128.13(Ar-C)，128.07(Ar-C)，126.85(Ar-C)，122.53(Ar-C)，118.96(Ar-C)，116.19(Ar-C)，111.96(Ar-C)，53.01(Ar-CH 2)，43.75(-NCH 2-)，25.71(-CH 2-)，23.24(-CH 2-).Anal.Calcd.for?C 18H 22N 2：C，81.16；H，8.32；N，10.52；Found：C，81.01；H，8.43；N，10.34％。
Embodiment 4
Synthetic ligands compound L 4
In the DMF solution of 2-piperidyl phenyl aldehyde (20mL, 20mmol), add p-Chlorobenzoic acid amide (21mL, 20mmol), and anhydrous K 2cO 3(3g, 22mmol), backflow 4h, adds 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH 4(240mmol), reflux, be added to the water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water, at-20 ℃ of recrystallizations, purify, obtain white solid (3.84g, productive rate: 64%), structural formula is as follows:
mp?77℃；δ H(400MHz，CDCl 3，25℃)7.31(d，J＝7.5Hz，1H，Ar-H)，7.24(d，J＝8.5Hz，1H，Ar-H)，7.14-7.07(m，3H，Ar-H)，7.03(td，J＝7.4，1.0Hz，1H，Ar-H)，6.55(d，2H，J＝7.3Hz，Ar-H)，4.71(br，1H，-NH)，4.26(s，2H，Ar-CH 2-)，2.95-2.71(m，4H，-NCH 2-)，1.73-1.58(m，4H，-CH 2-)，1.61-1.52(m，2H，-CH 2-).δ C(101MHz，CDCl 3，25℃)：152.79(Ar-C)，148.34(Ar-C)，133.59(Ar-C)，129.47(Ar-C)，128.63(Ar-C)，127.05(Ar-C)，123.34(Ar-C)，119.06(Ar-C)，117.43(Ar-C)，112.05(Ar-C)，54.05(Ar-CH 2-)，44.38(-NCH 2-)，26.53(-CH 2-)，22.84(-CH 2-).Anal.Calcd.forC 18H 21ClN 2：C，71.87；H，7.04；N，9.31；Found：C，71.68；H，7.23；N，9.18％。
Embodiment 5
Synthetic ligands compound L 5
In the DMF solution of 2-piperidyl phenyl aldehyde (20mL, 20mmol), add m-chloro aniline (21mL, 20mmol), and anhydrous K 2cO 3(3g, 22mmol), backflow 4h, adds 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH 4(240mmol), reflux 3, add in water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water, at-20 ℃ of recrystallizations, purify, obtain white solid (4.02g, productive rate: 67%), structural formula is as follows:
mp?72℃；δ H(400MHz，CDCl 3，25℃)：7.31(d，J＝7.6Hz，1H，Ar-H)，7.27-7.22(m，1H，Ar-H)，7.12(d，J＝7.2Hz，1H，Ar-H)，7.07-7.01(m，2H，Ar-H)，6.68-6.62(m，2H，Ar-H)，6.52(d，J＝7.4Hz，1H，Ar-H)，4.82(br，1H，-NH)，4.34(s，2H，Ar-CH 2-)，2.96-2.83(m，4H，-NCH 2-)，1.81-1.64(m，4H，-CH 2-)，1.59(m，2H，-CH 2-).δ C(101MHz，CDCl 3，25℃)：152.67(Ar-C)，149.74(Ar-C)，135.01(Ar-C)，133.18(Ar-C)，130.14(Ar-C)，129.16(Ar-C)，128.18(Ar-C)，123.74(Ar-C)，120.18(Ar-C)，117.07(Ar-C)，112.53(Ar-C)，111.45(Ar-C)，54.15(Ar-CH 2-)，44.53(-NCH 2-)，26.81(-CH 2-)，24.29(-CH 2-).Anal.Calcd.for?C 18H 21ClN 2：C，71.87；H，7.04；N，9.31；Found：C，71.72；H，7.21；N，9.27％。
Embodiment 6
Synthetic ligands compound L 6
In the DMF solution of 2-piperidyl phenyl aldehyde (20mL, 20mmol), add 2,6-xylidine (21mL, 20mmol), and anhydrous K 2cO 3(3g, 22mmol), backflow 4h, adds 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH 4(240mmol), reflux, add in water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water at-20 ℃ of recrystallizations, purify (3.94g, productive rate: 67%), structural formula is as follows:
mp?71℃；δ H(400MHz，CDCl 3，25℃)：7.36(dd，J＝7.5，1.4Hz，1H，Ar-H)，7.23(td，J＝7.8，1.6Hz，1H，Ar-H)，7.11(dd，J＝7.9，0.9Hz，1H，Ar-H)，7.03(td，J＝7.4，1.1Hz，1H，Ar-H)，6.98(d，J＝7.5Hz，2H，Ar-H)，6.80(t，J＝7.5Hz，1H，Ar-H)，4.16(s，2H，Ar-CH 2-)，3.79-3.57(br，1H，-NH)，2.91-2.86(m，4H，-NCH 2-)，2.28(s，6H，Ar-CH 3)，1.76-1.68(m，4H，-CH 2-)，1.60-1.55(m，2H，-CH 2-).δ C(101Hz，CDCl 3，25℃)：151.91(Ar-C)，145.54(Ar-C)，134.68(Ar-C)，128.66(Ar-C)，128.61(Ar-C)，127.70(Ar-C)，126.98(Ar-C)，122.72(Ar-C)，120.67(Ar-C)，119.18(Ar-C)，53.61(-N(CH 2) 2-)，47.75(-NCH 2-)，25.66(-CH 2-)，23.26(-CH 2-)，17.60(Ar-CH 3)Anal.Calcd.forC 20H 26N 2：C，81.59；H，8.90；N，9.51；Found：C，81.64；H，9.10；N，9.47％。
Embodiment 7
Synthetic ligands compound L 7
In the solution of the DMF of 2-morpholine benzaldehyde (20mL, 20mmol), add 2-aminotoluene (2.54g, 20mmol), and anhydrous K 2cO 3(3g, 22mmol), backflow 4h, adds 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH 4(240mmol), reflux, add in water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water, at-20 ℃ of recrystallizations, purify, obtain faint yellow solid (3.67g, productive rate: 65%), structural formula is as follows:
mp?70℃；δ H(400MHz，CDCl 3，25℃)7.39(dd，J＝7.5，1.2Hz，1H，Ar-H)，7.28(td，J＝7.8，1.5Hz，1H，Ar-H)，7.17-7.04(m，4H，Ar-H)，6.64-6.48(m，2H，Ar-H)，4.43(s，2H，Ar-CH 2-)，4.14(br，1H，-NH)，3.90-3.79(m，4H，-OCH 2-)，3.01-2.92(m，4H，-NCH 2-)，2.17(s，3H，Ar-CH 3)；δ C(101MHz，CDCl 3，25℃)150.08(Ar-C)，145.26(Ar-C)，132.97(Ar-C)，129.02(Ar-C)，128.34(Ar-C)，127.19(Ar-C)，126.13(Ar-C)，123.28(Ar-C)，120.93(Ar-C)，118.82(Ar-C)，116.02(Ar-C)，108.87(Ar-C)，66.42(Ar-CH 2)，52.00(-OCH 2-)，43.18(-NCH 2-)，16.61(Ar-CH 3).Anal.Calcd.forC 18H 22N 2O：C，76.56；H，7.85；N，9.92；Found：C，76.41；H，7.77；N，9.87％。
Embodiment 8
Synthetic ligands compound L 8
In the DMF solution of 2-morpholine benzaldehyde (20mL, 20mmo), add 2,6-xylidine (2.54g, 20mmol), and anhydrous K 2cO 3(3g, 22mmol), backflow 4h, adds 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH 4(240mmol), reflux, add in water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water, at-20 ℃ of recrystallizations, purify, obtain faint yellow solid (3.55g, productive rate: 60%), structural formula is as follows:
mp?72℃；δ H(400MHz，CDCl 3，25℃)：7.44(dd，J＝7.5，1.4Hz，1H，Ar-H)，7.28(td，J＝7.9，1.6Hz，1H，Ar-H)，7.16-7.11(m，2H，Ar-H)，6.99(d，J＝7.5Hz，2H，Ar-H)，6.82(t，J＝7.5Hz，1H，Ar-H)，4.19(s，2H，Ar-CH 2-)，3.86-3.74(m，4H，-OCH 2-)，2.93-2.86(m，4H，-NCH 2-)，2.28(s，6H，Ar-CH 3).δC(101MHz，CDCl 3，25℃)：151.37(Ar-C)，146.45(Ar-C)，135.88(Ar-C)，130.05(Ar-C)，129.71(Ar-C)，128.87(Ar-C)，128.34(Ar-C)，124.64(Ar-C)，122.01(Ar-C)，120.36(Ar-C)，67.48(Ar-CH 2-)，53.50(-NCH 2-)，48.53(-CH 2-)，18.69(Ar-CH 3).Anal.Calcd.for?C 19H 24N 2O：C，76.99；H，8.16；N，9.45；Found：C，77.18；H，8.35；N，9.37％。
Embodiment 9
Synthetic ligands compound L 9
In the DMF solution of 2-morpholine benzaldehyde (20mL, 20mmol), add 2-chloroaniline (2.54g, 20mmol), and anhydrous K 2cO 3(3g, 22mmol), backflow 4h, adds 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH 4(240mmol), reflux, add in water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water, at-20 ℃ of recrystallizations, purify, obtain faint yellow solid (3.81g, productive rate: 63%), structural formula is as follows:
mp?75℃；δ H(400MHz，CDCl 3，25℃)：7.28(dd，J＝7.6，1.1Hz，1H，Ar-H)，7.22-7.13(m，2H，Ar-H)，7.08(d，J＝7.1Hz，1H，Ar-H)，7.04-6.98(m，2H，Ar-H)，6.62(dd，J＝7.2Hz，1.3Hz，，1H，Ar-H)，6.53(td，J＝7.7，1.2Hz，1H，Ar-H)，5.00(br，1H，-NH)，4.36(s，2H，Ar-CH 2-)，3.82-3.71(m，4H，-OCH 2-)，2.95-2.83(m，4H，-NCH 2-)；δ C(101MHz，CDCl 3，25℃)：150.13(Ar-C)，143.04(Ar-C)，132.37(Ar-C)，128.27(Ar-C)，128.09(Ar-C)，127.38(Ar-C)，126.76(Ar-C)，123.45(Ar-C)，119.22(Ar-C)，118.13(Ar-C)，116.22(Ar-C)，110.39(Ar-C)，66.43(Ar-CH 2-)，52.01(-OCH 2-)，43.17(-NCH 2-).Anal.Calcd.for?C 17H 19ClN 2O：C，67.43；H，6.32；N，9.25；Found：C，67.45；H，6.21；N，9.37％。
Embodiment 10
Synthetic ligands compound L 10
In the DMF solution of 2-morpholine benzaldehyde (20mL, 20mmol), add 3-chloroaniline (2.54g, 20mmol), and anhydrous K 2cO 3(3g, 22mmol), backflow 4h, adds 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH 4(240mmol), reflux, add in water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water, at-20 ℃ of recrystallizations, purify, obtain faint yellow solid (3.74g, productive rate: 62%), structural formula is as follows:
mp?68℃；δ H(400MHz，CDCl 3，25℃)：7.34(dd，J＝7.6，1.3Hz，1H，Ar-H)，7.26(td，J＝7.9，1.6Hz，1H，Ar-H)，7.15-6.99(m，3H，Ar-H)，6.66-6.60(m，2H，Ar-H)，6.49(dd，J＝7.2，1.1Hz，1H，Ar-H)，4.52(br，1H，NH)，4.33(s，2H，Ar-CH 2-)，3.90-3.78(m，4H，-OCH 2-)，2.93-2.77(m，4H，-NCH 2-)；δC(101MHz，CDCl 3，25℃)：150.01(Ar-C)，148.40(Ar-C)，133.97(Ar-C)，132.29(Ar-C)，129.12(Ar-C)，128.26(Ar-C)，127.35(Ar-C)，123.39(Ar-C)，119.02(Ar-C)，116.17(Ar-C)，111.37(Ar-C)，110.25(Ar-C)，66.39(Ar-CH 2-)，52.03(-OCH 2-)，42.88(-NCH 2-).Anal.Calcd.forC 17H 19ClN 2O：C，67.43；H，6.32；N，9.25；Found：C，67.47；H，6.32；N，8.98％。
Embodiment 11
Synthetic ligands compound L 11
In the DMF solution of 2-morpholine benzaldehyde (20mL, 20mmol), add 4-chloroaniline (2.54g, 20mmol), and anhydrous K 2cO 3(3g, 22mmol), backflow 4h, adds 50mL water, dichloromethane extraction, extraction liquid is by anhydrous MgSO 4dry, filter.Filtrate decompression steams after solvent, is dissolved in the dehydrated alcohol of 20mL, adds NaBH 4(240mmol), reflux, add in water and remaining NaBH 4, dichloromethane extraction, anhydrous MgSO 4dry, with alcohol-water, at-20 ℃ of recrystallizations, purify, obtain faint yellow solid (3.99g, productive rate: 66%), structural formula is as follows:
mp?80℃；δ H(400MHz，CDCl 3，25℃)：7.35(dd，J＝7.6，1.3Hz，1H，Ar-H)，7.26(td，J＝7.8，1.9Hz，1H，Ar-H)，7.15-7.04(m，4H，Ar-H)，6.56(d，J＝7.2Hz，2H，Ar-H)，4.48(br，1H，NH)，4.34(s，2H，Ar-CH 2-)，3.92-3.77(m，4H，-OCH 2-)，3.01-2.86(m，4H，-NCH 2-)；δ C?NMR(101MHz，CDCl 3，25℃)：151.08(Ar-C)，146.95(Ar-C)，133.45(Ar-C)，129.30(Ar-C)，129.11(Ar-C)，128.40(Ar-C)，124.43(Ar-C)，122.01(Ar-C)，120.11(Ar-C)，114.01(Ar-C)，67.50(Ar-C)，53.06(-OCH 2-)，44.50(-NCH 2-).Anal.Calcd.for?C 17H 19ClN 2O：C，67.43；H，6.32；N，9.25；Found：C，67.64；H，6.22；N，9.18％。
Embodiment 12
Synthetic complex compound C1
In the toluene solution of ligand L 1, in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.514g, productive rate: 36%), structural formula is as follows:
mp?105℃(D.C.)；δ H(400MHz，CDCl 3，25℃)：7.46(d，J＝8.1Hz，1H，Ar-H)，7.38-7.30(m，2H，Ar-H)，7.29-7.11(m，3H，Ar-H)，6.86(d，J＝8.2Hz，1H，Ar-H)，6.59(m，1H，Ar-H)，4.47(s，2H，Ar-CH 2-)，3.73-3.60(m，2H，-NCH 2-)，3.40-3.26(m，2H，-NCH 2-)，1.93-1.77(m，2H，-CH 2-)，1.73-1.64(m，2H，-CH 2-)，1.61-1.48(m，2H，-CH 2-)，-0.94(s，6H，Al-CH 3).δ C?NMR(101MHz，CDCl 3，25℃)：151.89(Ar-C)，143.08(Ar-C)，133.33(Ar-C)，132.44(Ar-C)，129.15(Ar-C)，128.04(Ar-C)，127.58(Ar-C)，126.35(Ar-C)，123.03(Ar-C)，122.32(Ar-C)，116.28(Ar-C)，115.78(Ar-C)，55.58(Ar-CH 2)，49.58(-NCH 2-)，23.68(-CH 2-)，21.68(-CH 2-)，-9.19(Al-CH 3).Anal.Calcd.forC 20H 26AlClN 2：C，67.31；H，7.34；N，7.85.Found：C，67.25；H，7.89；N，7.42％。
Embodiment 13
Synthetic complex compound C2
In the toluene solution of ligand L 2, in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.480g, productive rate: 33%), structural formula is as follows;
mp?107℃(D.C.)；δ H(400MHz，CDCl 3，25℃)：7.42(d，J＝8.2Hz，1H，Ar-H)，7.34-7.25(m，2H，Ar-H)，7.19(t，J＝8.8Hz，1H，Ar-H)，7.04(d，J＝8.1Hz，2H，Ar-H)，6.67(d，J＝8.1Hz，2H，Ar-H)，4.44(s，2H，Ar-CH 2-)，3.66-3.54(m，2H，-NCH 2-)，3.42-3.30(m，2H，-NCH 2-)，2.78-2.67[hept.，J＝6.9，1H，CH(CH 3) 2]，1.90-1.85(m，2H，-CH 2-)，1.72-1.64(m，2H，-CH 2-)，1.60-1.48(m，2H，-CH 2-)，1.56[d，J＝6.9，6H，CH(CH 3) 2]，-0.90(s，3H，Al-CH 3)；δ C(101MHz，CDCl 3，25℃)：151.05(Ar-C)，141.70(Ar-C)，133.83(Ar-C)，133.17(Ar-C)，131.31(Ar-C)，126.60(Ar-C)，125.61(Ar-C)，125.56(Ar-C)，121.01(Ar-C)，113.20(Ar-C)，53.60(Ar-CH 2)，49.25(N(CH 2))，32.04(CH 2)，30.56[CH(CH 3) 2]，22.43(CH 2)，13.11[-CH(CH 3) 2]，-10.92(Al-CH 3).Anal.Calcd.forC 23H 33AlN 2：C，75.79；H，9.13；N，7.69；Found：C，74.90；H，9.89；N，7.58％。
Embodiment 14
Synthetic complex compound C3
In the toluene solution of ligand L 3, in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.348g, productive rate: 27%), structural formula is as follows:
mp?93℃(D.C.)；δ H(400MHz，CDCl 3，25℃)7.44(d，J＝8.1Hz，1H，Ar-H)，7.36-7.29(m，2H，Ar-H)，7.25-7.12(m，3H，Ar-H)，6.71(d，J＝7.9Hz，2H，Ar-H)，6.59(t，J＝7.2Hz，1H，Ar-H)，4.45(s，2H，Ar-CH 2-)，3.65-3.62(m，2H，-NCH 2-)，3.42-3.38(m，2H，-NCH 2-)，1.88-1.69(m，2H，-CH 2-)，1.68-1.54(m，2H，-CH 2-)，1.61-1.54(m，2H，-CH 2-)，-0.89(s，6H，Al-CH 3)；δC(101MHz，CDCl 3)153.10(Ar-C)，141.65(Ar-C)，133.03(Ar-C)，131.42(Ar-C)，127.72(Ar-C)，126.72(Ar-C)，125.63(Ar-C)，121.09(Ar-C)，113.68(Ar-C)，113.57(Ar-C)，53.40(Ar-CH 2-)，49.26(-NCH 2-)，22.42(-CH 2-)，20.48(-CH 2-)，-11.01(Al-CH 3).Anal.Calcd.for?C 20H 27AlN 2：C，74.50；H，8.44；N，8.69Found：C，74.27；H，8.64；N，8.66％。
Embodiment 15
Synthetic complex compound C4
In the toluene solution of ligand L 4, in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.443g, productive rate: 31%), structural formula is as follows:
mp?112℃(D.C.)；δ H(400MHz，CDCl 3，25℃)7.45(d，J＝8.1Hz，1H，Ar-H)，7.32-7.23(m，2H，Ar-H)，7.25-7.18(d，J＝6.8Hz，1H，Ar-H)，7.09(d，J＝7.8Hz，2H，Ar-H)，6.61(d，J＝7.8Hz，2H，Ar-H)，4.39(s，2H，Ar-CH 2-)，3.64-3.56(m，2H，-NCH 2-)，3.40-3.20(m，2H，-NCH 2-)，1.75-1.65(m，2H，-CH 2-)，1.62-1.58(m，2H，CH 2-)，1.56-1.42(m，2H，-CH 2-)，-0.91(s，6H，Al-CH 3)；δ C(101MHz，CDCl 3，25℃)151.68(Ar-C)，141.54(Ar-C)，132.60(Ar-C)，131.44(Ar-C)，127.39(Ar-C)，126.92(Ar-C)，125.76(Ar-C)，121.14(Ar-C)，118.21(Ar-C)，114.56(Ar-C)，53.49(Ar-CH 2-)，49.33(-NCH 2-)，22.37(-CH 2-)，20.46(-CH 2-)，-11.09(Al-CH 3).Anal.Calcd.forC 20H 26AlClN 2：C，67.31；H，7.34；N，7.85；Found：C，66.27；H，8.11；N，7.50％。
Embodiment 16
Synthetic complex compound C5
In the toluene solution of ligand L 5, in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.443g, productive rate: 31%), structural formula is as follows:
mp?107℃(D.C.)；δ H(400MHz，CDCl 3，25℃)：7.37(d，J＝7.2Hz，1H，Ar-H)，7.28-7.21(m，2H，Ar-H)，7.16(d，J＝6.2Hz，1H，Ar-H)，7.06(d，J＝30.9，1H，Ar-H)，6.94(t，J＝6.7，1H，Ar-H)，6.64-6.42(m，2H，Ar-H)，4.31(s，2H，Ar-CH 2)，3.56-3.47(m，2H，-NCH 2-)，3.33-3.23(m，2H，-NCH 2-)，1.85-1.70(m，2H，-CH 2-)，1.67-1.68(m，2H，-CH 2-)，1.55-1.40(m，2H，-CH 2-)，-0.97(s，6H，Al-CH 3).δ C(101MHz，CDCl 3，25℃)：154.45(Ar-C)，141.54(Ar-C)，133.67(Ar-C)，132.42(Ar-C)，131.44(Ar-C)，128.21(Ar-C)，128.00(Ar-C)，127.19(Ar-C)，126.97(Ar-C)，125.80(Ar-C)，53.29(Ar-CH 2-)，49.34(-NCH 2-)，22.35(-CH 2-)，20.45(-CH 2-)，-11.07(Al-CH 3).Anal.Calcd.forC 20H 26AlClN 2：C，67.31；H，7.34；N，7.85；Found：C，67.25；H，7.89；N，7.42％。
Embodiment 17
Synthetic complex compound C6
In the toluene solution of ligand L 6, in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.532g, productive rate: 38%), structural formula is as follows:
mp?102℃(D.C.)；δ H(400MHz，CDCl 3，25℃)：7.32(d，J＝8.1Hz，1H，Ar-H)，7.24-7.09(m，3H，Ar-H)，6.97(d，J＝7.4Hz，2H，Ar-H)，6.82(t，J＝7.4Hz，Ar-H)，4.26(s，2H，Ar-CH 2-)，3.65-3.55(d，J＝8.9Hz，2H，-NCH 2-)，3.35-3.26(m，2H，-NCH 2-)，2.22(s，6H，Ar-CH 3)，2.03-1.96(m，2H，-CH 2-)，1.85-1.77(m，2H，-CH 2-)，1.70-1.56(m，2H，-CH 2-)，-1.17(s，6H，Al-CH 3)；δ CNMR(101MHz，CDCl 3，25℃)：150.77(Ar-C)，145.12(Ar-C)，138.15(Ar-C)，135.65(Ar-C)，131.18(Ar-C)，128.23(Ar-C)，127.26(Ar-C)，126.42(Ar-C)，123.03(Ar-C)，120.74(Ar-C)，57.48(Ar-CH 2-)，52.79(-NCH 2-)，23.27(-CH 2-)，22.60(-CH 2-)，19.08(Ar-CH 3)，-8.54(Al-CH 3).Anal.Calcd.for?C 22H 31N 2O：C，75.39；H，8.92；N，7.99；Found：C，74.90；H，8.89；N，7.67％。
Embodiment 18
Synthetic complex compound C7
In the toluene solution of ligand L 7 (10mL, 4mmol), in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.446g, productive rate: 33%), structural formula is as follows:
mp?93℃(D.C.)；δ H(400MHz，CDCl 3，25℃)：7.45-7.34(m，3H，Ar-H)，7.31(d，J＝7.3Hz，1H，Ar-H)，7.18-7.12(m，3H，Ar-H)，7.02(d，J＝6.8Hz，1H，Ar-H)，6.78(t，J＝7.4Hz，1H，Ar-H)，4.67(s，2H，Ar-CH 2-)，4.10-3.95(m，4H，-OCH 2-)，3.78-3.58(m，4H，-NCH 2-)，2.36(s，3H，Ar-CH 3)，-0.97(s，6H，Al-CH 3)；δ C(101MHz，CDCl 3?25℃)：152.97(Ar-C)，141.31(Ar-C)，133.81(Ar-C)，131.37(Ar-C)，129.81(Ar-C)，128.72(Ar-C)，126.84(Ar-C)，126.04(Ar-C)，125.41(Ar-C)，120.57(Ar-C)，118.01(Ar-C)，117.16(Ar-C)，61.72(Ar-CH 2-)，55.46(-OCH 2-)，48.66(-NCH 2-)，19.30(Ar-CH 3)，-10.77(Al-CH 3).Anal.Calc.for?C 20H 27AlN 2O：C，70.98；H，8.04；N，8.28；Found：C，70.63；H，8.22；N，8.13％。
Embodiment 19
Synthetic complex compound C8
In the toluene solution of ligand L 8 (10mL, 4mmol), in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.479g, productive rate: 34%), structural formula is as follows:
mp?98℃(D.C.)；δ H(400MHz，CDCl 3，25℃)：7.34-7.30(m，2H，Ar-H)，7.31-7.21(m，2H，Ar-H)，7.08-7.05(m，2H，Ar-H)，6.90(t，J＝7.4d，1H，Ar-H)，4.33(s，2H，Ar-CH 2)，4.23-3.96(m，4H，-OCH 2-)，3.88-3.38(m，4H，-NCH 2-)，2.28(s，2H，Ar-CH 3)，-1.08(s，6H，Al-CH 3)；δ C(100MHz，CDCl 3，25℃)：150.31(Ar-C)，144.02(Ar-C)，137.96(Ar-C)，135.52(Ar-C)，131.54(Ar-C)，128.35(Ar-C)，127.50(Ar-C)，126.93(Ar-C)，123.27(Ar-C)，120.52(Ar-C)，63.32(Ar-CH 2-)，57.17(-OCH 2-)，51.60(-NCH 2-)，19.13(Ar-CH 3)，-8.66(Al-CH 3).Anal.Calcd.for?C 21H 29N 2O：C，71.56；H，8.29；N，7.95；Found：C，71.87；H，8.61；N，7.65％。
Embodiment 20
Synthetic complex compound C9
In the toluene solution of ligand L 9 (10mL, 4mmol), in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.487g, productive rate: 34%), structural formula is as follows:
mp?96℃(D.C.)；δ H(400MHz，CDCl 3，25℃)：7.48(dd，J＝7.8，1.4Hz，1H，Ar-H)，7.39-7.32(td，J＝8.9，1.3Hz，1H，Ar-H)，7.08-6.92(m，3H，Ar-H)，6.76(d，J＝5.3Hz，1H，Ar-H)，6.69-6.58(m，2H，Ar-H)，4.32(s，2H，Ar-CH 2)，4.15-3.97(m，4H，-OCH 2-)，3.72-3.67(m，4H，-NCH 2-)，-0.94(s，6H，Al-CH 3)；δ C(100MHz，CDCl 3，25℃)：154.21(Ar-C)，140.81(Ar-C)，133.74(Ar-C)，132.59(Ar-C)，131.72(Ar-C)，128.31(Ar-C)，127.14(Ar-C)，126.29(Ar-C)，120.83(Ar-C)，113.85(Ar-C)，113.06(Ar-C)，112.53(Ar-C)，61.52(Ar-CH 2)，52.86(-O(CH 2-)，48.56(-N(CH 2-)，-11.12(Al-CH 3).Anal.Calcd.for?C 19H 24AlClN 2O：C，63.59；H，6.74；N，7.81；Found：C，63.98；H，6.71；N，7.63.％。
Embodiment 21
Synthetic complex compound C10
In the toluene solution of ligand L 10 (10mL, 4mmol), in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.430g, productive rate: 30%), structural formula is as follows:
mp?91℃(D.C.)；δ H(400MHz，CDCl 3，25℃)：7.41-7.32(m，3H，Ar-H)，7.28(d，J＝6.8Hz，1H，Ar-H)，7.04(t，J＝7.9Hz，1H，Ar-H)，6.65(s，1H，Ar-H)，6.63-6.55(m，2H，Ar-H)，4.40(s，2H，Ar-CH 2-)，4.00-3.90(m，4H，-OCH 2-)，3.65-3.50(m，4H，-NCH 2-)，-0.87(s，6H，Al-CH 3)；δ C(100Hz，CDCl 3)：155.2(Ar-C)，141.8(Ar-C)，134.7(Ar-C)，133.6(Ar-C)，132.6(Ar-C)，129.3(Ar-C)，128.1(Ar-C)，127.3(Ar-C)，121.8(Ar-C)，114.8(Ar-C)，114.1(Ar-C)，113.5(Ar-C)，62.5(Ar-CH 2-)，54.0(-OCH 2-)，49.6(-NCH 2-)，-10.1(Al-CH 3).Anal.Calcd.for?C 19H 24AlClN 2O：C，63.59；H，6.74；N，7.81；Found：C，63.96；H，7.01；N，7.80％。
Embodiment 22
Synthetic complex compound C11
In the toluene solution of ligand L 11 (10mL, 4mmol), in room temperature, slowly add trimethyl aluminium toluene solution (2mL, 4mmol), 90 ℃ are stirred 48h.Drain solvent, add methylene chloride with normal hexane mixed solvent in-20 ℃ of crystallizations, obtain clear crystal (0.501g, productive rate: 35%), structural formula is as follows:
mp?91℃(D.C.)；δ H(400MHz，CDCl 3，25℃)：7.40-7.32(m，2H，Ar-H)，7.30-7.21(m，2H，Ar-H)，7.10(d，J＝8.5Hz，2H，Ar-H)，6.61(d，J＝8.5Hz，2H，Ar-H)，4.39(s，2H，Ar-CH 2-)，3.93(br，4H，-OCH 2-)，3.58(br，4H，-NCH 2-)，-0.88(s，6H，Al-CH 3).δ C(100MHz，CDCl 3)：152.46(Ar-C)，141.85(Ar-C)，133.77(Ar-C)，132.66(Ar-C)，129.07(Ar-C)，128.48(Ar-C)，127.14?128.09(Ar-C)，127.22(Ar-C)，121.81(Ar-C)，119.58(Ar-C)，115.64(Ar-C)，62.57(Ar-CH 2-)，54.02(-OCH 2-)，49.57(-NCH 2-)，-10.11(Al-CH 3).Anal.Calcd.for?C 19H 24AlClN 2O：C，63.59；H，6.74；N，7.81；Found：C，64.41；H，6.92；N，7.82％。
Embodiment 23
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C1 is injected to polymerization bottle.Control temperature 70 ℃ of reactions 20 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 92%, M n=15745, PDI=1.14.
Embodiment 24
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C2 is injected to polymerization bottle.Control temperature 70 ℃ of reactions 18 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 91%, Mn=15072.PDI=1.13.
Embodiment 25
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C3 is injected to polymerization bottle.Control temperature 70 ℃ of reactions 18 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 94%, Mn=11208.PDI=1.11.
Embodiment 26
In polymerization bottle, add rac-lactide (2.88g, 10mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C3 is injected to polymerization bottle.Control temperature 90 ℃ of reactions 120 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 84%.
Embodiment 27
In polymerization bottle, add rac-lactide (2.88g, 10mmol).The toluene solution (1mL, 0.010mmol) of catalyzer C3 is injected to polymerization bottle.Control temperature 110 ℃ of reactions 8 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 58%.
Embodiment 28
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol).The toluene solution (1mL, 0.010mmol) of catalyzer C4 is injected to polymerization bottle.Control temperature 65 ℃ of reactions 15 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 88%, Mn=14919.PDI=1.08.
Embodiment 29
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol).The toluene solution (1mL, 0.010mmol) of catalyzer C4 is injected to polymerization bottle.Control temperature 110 ℃ of reactions 4.5 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 86%.
Embodiment 30
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol).The toluene solution (1mL, 0.010mmol) of catalyzer C5 is injected to polymerization bottle.Control temperature 65 ℃ of reactions 15 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 92%, M n=12342, PDI=1.08.
Embodiment 31
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol).The toluene solution (1mL, 0.010mmol) of catalyzer C6 is injected to polymerization bottle.Control temperature 25 ℃ of reactions 4 days, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 70%.
Embodiment 32
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol).The toluene solution (1mL, 0.010mmol) of catalyzer C6 is injected to polymerization bottle.Control temperature 65 ℃ of reactions 15 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 64%, M n=8377, PDI=1.06.
Embodiment 33
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C6 is injected to polymerization bottle.Control temperature 25 ℃ of reactions 75 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 74%.
Embodiment 34
In polymerization bottle, add rac-lactide (4.32g, 30.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C6 is injected to polymerization bottle.Control temperature 65 ℃ of reactions 15 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 67%.
Embodiment 35
In polymerization bottle, add rac-lactide (0.288g, 2.0mmol).The toluene solution (1mL, 0.010mmol) of catalyzer C6 is injected to polymerization bottle.Control temperature 65 ℃ of reactions 32 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 72%.
Embodiment 36
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol).The toluene solution (1mL, 0.040mmol) of catalyzer C1 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 90 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 91%.
Embodiment 37
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol).The toluene solution (1mL, 0.040mmol) of catalyzer C2 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 60 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 93%, M n=12948, PDI=1.06.
Embodiment 38
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol).The toluene solution (1mL, 0.040mmol) of catalyzer C3 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 60 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 94%.
Embodiment 39
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol).The toluene solution (1mL, 0.040mmol) of catalyzer C4 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 60 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 92%.
Embodiment 40
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol).The toluene solution (1mL, 0.040mmol) of catalyzer C5 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 60 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 97%.
Embodiment 41
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol).The toluene solution (1mL, 0.040mmol) of catalyzer C6 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 90 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 84%.
Embodiment 42
In polymerization bottle, add 6-caprolactone (4.560g, 40.0mmol).The toluene solution (1mL, 0.040mmol) of catalyzer C6 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 3 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 78%.
Embodiment 43
In polymerization bottle, add 6-caprolactone (0.228g, 2.0mmol) and rac-lactide (0.288g, 2.0mmol).The toluene solution (1mL, 0.040mmol) of catalyzer C6 is injected to polymerization bottle.Control temperature 75 ℃ of reactions 20 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.6-caprolactone transformation efficiency 9%, rac-lactide transformation efficiency 78%.
Embodiment 44
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C7 is injected to polymerization bottle.Control temperature 70 ℃ of reactions 22 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 95%, M n=14966, PDI=1.09.
Embodiment 45
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C7 is injected to polymerization bottle.Control temperature 110 ℃ of reactions 6 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 92%.
Embodiment 46
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C7 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 90 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 89%.
Embodiment 47
In polymerization bottle, add 6-caprolactone (0.456g, 40.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C7 is injected to polymerization bottle.Control temperature 65 ℃ of reactions 120 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 92%.
Embodiment 48
In polymerization bottle, add 6-caprolactone (4.560g, 40.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C7 is injected to polymerization bottle.Control temperature 65 ℃ of reactions 150 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 92%.
Embodiment 49
In polymerization bottle, add 6-caprolactone (4.560g, 40.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C7 is injected to polymerization bottle.Control temperature 110 ℃ of reactions 2 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 96%.
Embodiment 50
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C8 is injected to polymerization bottle.Control temperature 70 ℃ of reactions 24 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 94%, M n=13502, PDI=1.11.
Embodiment 51
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C8 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 60 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 86%.
Embodiment 52
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C8 is injected to polymerization bottle.Control temperature 25 ℃ of reactions 420 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 78%.
Embodiment 53
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol).The toluene solution (1mL, 0.040mmol) of catalyzer C8 is injected to polymerization bottle.Control temperature 65 ℃ of reactions 30 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 77%.
Embodiment 54
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol).The toluene solution (1mL, 0.040mmol) of catalyzer C8 is injected to polymerization bottle.Control temperature 35 ℃ of reactions 240 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 83%.
Embodiment 55
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C9 is injected to polymerization bottle.Control temperature 70 ℃ of reactions 22 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 97%, M n=16793, PDI=1.06.
Embodiment 56
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C9 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 90 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 93%.
Embodiment 57
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C10 is injected to polymerization bottle.Control temperature 70 ℃ of reactions 15 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 88%, M n=14790, PDI=1.08.
Embodiment 58
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C10 is injected to polymerization bottle.Control temperature 35 ℃ of reactions 5 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 75%.
Embodiment 59
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C10 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 60 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 94%.
Embodiment 60
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C10 is injected to polymerization bottle.Control temperature 65 ℃ of reactions 40 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 98%.
Embodiment 61
In polymerization bottle, add rac-lactide (0.144g, 1.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C11 is injected to polymerization bottle.Control temperature 70 ℃ of reactions 15 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 86%.
Embodiment 62
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol), the toluene solution (1mL, 0.040mmol) of catalyzer C11 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 60 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 92%.
Embodiment 63
In polymerization bottle, add 6-caprolactone (0.456g, 4.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C11 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 150 minutes, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 85%.
Embodiment 64
In polymerization bottle, add 6-caprolactone (0.912g, 8.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C11 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 7 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 77%.
Embodiment 65
In polymerization bottle, add 6-caprolactone (3.420g, 30.0mmol), the toluene solution (1mL, 0.010mmol) of catalyzer C11 is injected to polymerization bottle.Control temperature 45 ℃ of reactions 24 hours, add sherwood oil termination reaction.Extract solvent, resistates dissolves with methylene dichloride, adds methyl alcohol to make polymkeric substance Precipitation.Vacuum-drying 24 hours.Transformation efficiency 83%.

Claims (10)

  1. A heterocyclic substituted bidentate amido ligand compound (I) and with the complex compound (II) of metallic aluminium, it is characterized in that thering is following general formula:
    In formula (I), (II):
    R 1～R 5represent respectively hydrogen, C 1～C 12straight chain, the alkyl of branched structure, halogen; R 6for C 1～C 6the alkyl of straight or branched structure; X represents methylene radical or Sauerstoffatom.
  2. Heterocyclic substituted bidentate amido ligand compound according to claim 1 (I) and with the complex compound (II) of metallic aluminium, it is characterized in that R 1～R 5for hydrogen, C 1～C 6the alkyl of straight chain, branched structure, halogen; R 6for C 1～C 4straight chain, the alkyl of branched structure.
  3. Heterocyclic substituted bidentate amido ligand compound according to claim 1 (I) and with the complex compound (II) of metallic aluminium, it is characterized in that R 1～R 5be preferably hydrogen, methyl, sec.-propyl, chlorine; R 6be preferably methyl.
  4. Heterocyclic substituted bidentate amido ligand compound (I) described in claim 1～3 any one and with the preparation method of the complex compound (II) of metallic aluminium, comprise the steps:
    By the heterocyclic substituted phenyl aldehyde shown in (IV) formula and substituted aniline generation condensation reaction, generate corresponding Schiff alkali cpd, add again reductive agent, in organic medium, react, then from reduzate, collect corresponding heterocyclic substituted bidentate amido ligand compound (I); Described heterocyclic substituted phenyl aldehyde is 2-piperidyl phenyl aldehyde, 2-morpholine benzaldehyde; In described substituted aniline, R 1～R 5represent respectively hydrogen, C 1～C 12straight chain, the alkyl of branched structure, halogen;
    Again the heterocyclic substituted bidentate amido ligand compound shown in formula (I) is reacted in organic medium with alkylaluminium cpd, generate heterocyclic substituted bidentate amido ligand aluminum complex compound; Described alkylaluminium cpd is AlR 3, wherein R is C 1～C 6the alkyl of straight or branched.
  5. 5. method according to claim 4, is characterized in that, the mol ratio of heterocyclic substituted bidentate amido ligand compound and alkylaluminium cpd is 1: 0.5～5.
  6. 6. method according to claim 4, is characterized in that, the preferred sodium borohydride of described reductive agent; Described organic medium is selected from one or both in tetrahydrofuran (THF), ether, toluene, benzene, chloroform, methylene dichloride, sherwood oil and normal hexane.
  7. 7. the application of the heterocyclic substituted bidentate amido ligand aluminum complex compound described in claim 1～3 any one, is characterized in that, for the polymerization of lactone.
  8. 8. application according to claim 7, is characterized in that, lactone is selected from L-rac-Lactide, D-rac-Lactide, rac-rac-Lactide, 6-caprolactone.
  9. 9. application according to claim 7, is characterized in that, the heterocyclic substituted bidentate amido ligand aluminum complex compound of take described in claim 1～3 any one is catalyzer, makes the polymerization at 25～110 ℃ of rac-Lactide or 6-caprolactone.
  10. 10. application according to claim 7, is characterized in that, the heterocyclic substituted bidentate amido ligand aluminum complex compound of take described in claim 1～3 any one is catalyzer, makes rac-Lactide, 6-caprolactone copolymerization at 25～110 ℃.
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