CN100497350C - Rare earth complex catalyzing lactide stereo selective polymerization - Google Patents
Rare earth complex catalyzing lactide stereo selective polymerization Download PDFInfo
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- CN100497350C CN100497350C CNB2006100171335A CN200610017133A CN100497350C CN 100497350 C CN100497350 C CN 100497350C CN B2006100171335 A CNB2006100171335 A CN B2006100171335A CN 200610017133 A CN200610017133 A CN 200610017133A CN 100497350 C CN100497350 C CN 100497350C
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Abstract
The present invention is RE complex capable of being used in catalyzing the bulk and solution stereo selective ring-opening polymerization of racemic lactide. The bulk ring-opening polymerization of racemic lactide is performed at 70-120 deg.c, and reaction for 0.1-5 hr can reach monomer converting rate up to 100%. The solution ring-opening polymerization of racemic lactide is performed in solvent tetrahydrofuran, methane dichloride or toluene. In tetrahydrofuran solution, the ring-opening polymerization of racemic lactide is performed at 20-70 deg.c, and reaction for 0.1-5 hr can reach monomer converting rate up to 100%. In toluene solvent, the ring-opening polymerization of racemic lactide is performed at 20-100 deg.c, and reaction for 0.1-5 hr can reach monomer converting rate up to 100%. The present invention can reach polylactide heterotactic content up to 0.99.
Description
Technical field:
The present invention relates to catalytic lactide stereo selectirity poly rare earth compound.
Background technology:
Commodity polymer materials such as polyolefine develop invention and the development that has benefited from metallocene catalyst to a great extent rapidly, make that the macro property of controlled material is able to smooth implementation on the polymer chain structure level.Therefore, metallocene catalyst mainly is meant the early transition metal title complex, causes scientists research enthusiasm greatly, and has obtained great successes.A patent of the relevant metallocene of EXXON company application just reaches 500 pages.Yet the crisis that development is hidden is behind also appeared in one's mind gradually: 1. Organometallic scholar and company must seek new research point and develop outlet to avoid covering extremely wide patent.2. although polyolefine has impayable performance and price advantage, however the white pollution that environment is caused and the dependence of petroleum resources also become human survival and develop extremely white elephant.The biodegradable polymer that Here it is does not rely on petroleum resources in recent years more and more is subjected to the reason that investigator, company and government pay close attention to, and also is the reason of studying like a raging firely non-cyclopentadienyl rear transition metal and occurring.
So far, studying maximum and most widely used Biodegradable Polymers is polylactide, because monomer whose derives from farm crop tunnings such as corn, and final degraded product is carbonic acid gas and water, alleviate dependence to a certain extent, can not pollute again after the use environment to petroleum resources.Therefore, be widely used in medical equipment and replace the human body active material, can repair, repairing, replacing damaged or infected tissue or reduce react to each other with biosystem, as interim skeleton or supporting (sutures, bone fixing part), interim obstacle (preventing tissue adhesion).The material of this perishability can hydrolysis and be degraded into the product that can be absorbed by the body and very little to the influence of organ, also can reduce the number of times of operation simultaneously.In field of pharmaceutical preparations as the dressing composition in slowly-releasing, controlled release or the targeting preparation.Another important use is that replacement or part replace general-purpose plastics, and this requires polymkeric substance to have high molecular weight and degree of crystallinity.Therefore, different purposes, to the performance requriements difference of polylactide, and performance depends on the molecular chain structure of polylactide, the spy is steric configuration in addition.Therefore the development of new catalyzer just can be satisfied the demand.
Rac-Lactide ring-opening polymerization under the special catalyst effect is revolved on a left side (right side), if polymkeric substance keeps monomeric opticity, its steric configuration is full isostructure, crystallization, and fusing point is 165-180 ℃.Study of Meso-Lactide, ring-opening polymerization under the special catalyst effect, if polymkeric substance keeps monomeric opticity, its steric configuration is an isostructure, crystallization, fusing point is 152-160 ℃.Racemic rac-Lactide, ring-opening polymerization under the special catalyst effect, the steric configuration of polymkeric substance can be a block complex polymerisation thing, crystallization, fusing point is 190-230 ℃; Or assorted same, random structure, be amorphous polymer, non-crystallizable, the spy is applicable to pharmaceutical carrier in addition.The relation of the opticity of lactide monomer and the steric configuration of polylactide, as follows:
The rac-Lactide polymerizing catalyst of initial invention is rare earth metal inorganic (oxygen bunch close, a phenol oxygen) compound, the cyclopentadienyl rare-earth metal organic coordination compound, transition metal complex such as stannous octoate and zinc, calcium, characteristics are that high reactivity, polyreaction are controlled, the maintenance of monomer optically active form.This class catalyzer is had to the product of random structure during to the rac-lactide polymerization.Find chiral catalyst afterwards, can the polymerization of catalysis rac-lactide help isostructure.Schiff's base (Salen) aluminium alcoxyl title complex, β-diamines zinc alcoxyl title complex have been reported recently.This two classes title complex can the polymerization of catalysis rac-lactide obtain block polymer or assorted isostructure polymkeric substance (P
r=0.9).With the amido bis-phenol be the rare earth aminate of part be unique so far can the assorted isostructural achirality rare-earth metal catalyst of catalysis rac-lactide preparation, under the effect of alcohol, the assorted of polymkeric substance can be increased to 0.90 with content.
Summary of the invention
The purpose of this invention is to provide catalytic lactide stereo selectirity poly rare earth compound, have the structure of formula 1:
Wherein: R is the substituting group on the phenol ring, is hydrogen, methyl or the tertiary butyl;
R ' is the substituting group on the diamines, is methyl, ethyl or pyridyl;
R " refer to form the group of σ-key with rare earth ion, be alkyl, amido or phenol oxygen base;
Rare earth metal (Ln) is yttrium (Y), lutetium (Lu) or scandium (Sc).
The catalytic lactide stereo selectirity poly rare earth compound of preferred formula 1 has suc as formula the structure shown in the 2-3:
R=H, R '=cH
3, R "=CH
2SiMe
3, title complex 1, Fw=546.6
R=CH
3, R '=CH
3, R "=CH
2SiMe
3, title complex 2, Fw=602.7
R=
tBu, R '=CH
3, R "=CH
2SiMe
3, title complex 3, Fw=771.0
R=H, R '=CH
2CH
3, R "=CH
2SiMe
3, title complex 4, Fw=574.7
R=CH
3, R '=CH
2CH
3, R "=CH
2SiMe
3, title complex 5, Fw=630.8
R=
tBu, R '=CH
2CH
3, R "=CH
2SiMe
3, title complex 6, Fw=799.1
R=H, R '=C
5H
4N, R "=CH
2SiMe
3, title complex 7, Fw=672.7
R=CH
3, R '=C
5H
4N, R "=CH
2SiMe
3, title complex 8, Fw=728.8
R=
tBu, R '=C
5H
4N, R "=CH
2SiMe
3, title complex 9, Fw=897.1
R=H, R ' C
5H
4N, R "=NHCH
2SiMe
3, title complex 10, Fw=687.7
R=CH
3, R '=C
5H
4N, R "=NHCH
2SiMe
3, title complex 11, Fw=743.8
R=
tBu, R '=C
5H
4N, R "=NHCH
2SiMe
3, title complex 12, Fw=912.2
R=H, R '=CH
2CH
3, R "=O
iPr title complex 13, Fw=518.5
R=CH
3, R '=CH
2CH
3, R "=O
i Pr title complex 14, Fw=574.6
R=
tBu, R '=CH
2CH
3, R "=O
iPr title complex 15, Fw=742.9
The molecular structure of formula 2. title complex 1-15
Ln=Lu, R=H, R '=CH
3, R "=CH
2SiMe
3, title complex 16, Fw=632.6
Ln=Lu, R=CH
3, R '=CH
3, R "=CH
2SiMe
3, title complex 17, Fw=688.7
Ln=Lu, R=
tBu, R '=CH
3, R "=CH
2SiMe
3, title complex 18, Fw=857.0
Ln=Sc, R=H, R '=CH
2CH
3, R "=CH
2SiMe
3, title complex 19, Fw=530.7
Ln=Sc, R=CH
3, R '=CH
2CH
3, R "=CH
2SiMe
3, title complex 20, Fw=586.8
Ln=Sc, R=
tBu, R '=CH
2CH
3, R "=CH
2SiMe
3, title complex 21, Fw=755.1
The molecular structure of formula 3. title complex 16-21
Introduce the preparation method of catalytic lactide stereo selectirity poly rare earth compound of the present invention below.
The step and the condition of the catalytic lactide stereo selectirity poly rare earth compound shown in the preparation formula 1 are as follows:
(1), the part of catalytic lactide stereo selectirity poly rare earth compound shown in the preparation formula 1, this part has structure as shown in Equation 5:
Formula 5
Wherein: R is the substituting group on the phenol ring, is hydrogen, methyl or the tertiary butyl;
R ' is the substituting group on the diamines, is methyl, ethyl or pyridyl;
In reactor, add the aniline that mol ratio is 2:1:2.73:10 respectively, dimethyl-ethylenediamine, volume ratio are the aqueous solution and the methyl alcohol of 36% formaldehyde, back flow reaction 24-48h.Behind the question response mixing solutions cool to room temperature, supernatant liquid is toppled over, layer oily matter is smashed to pieces in 50-60 ℃ methanol solution, obtains the part shown in the formula 5 of white powder.Productive rate 80-90%.
(2). catalytic lactide stereo selectirity poly rare earth compound shown in the preparation formula 1
In glove box, the alkyl rare earth of mol ratio 1:1 is added drop-wise in the hexane solution of part shown in the formula 5, keep-30 ℃ conditioned response 12h.Precipitation is washed with-30 ℃ hexane solution, promptly obtain the catalytic lactide stereo selectirity poly rare earth compound shown in the white formula 1.Productive rate 60-70%.
Catalytic lactide stereo selectirity poly rare earth compound of the present invention, its step and condition that is used for catalytic method is as follows:
(1), earlier rac-lactide (rac-LA) with ethyl acetate 65 ℃～80 ℃ dissolvings down, the pure system of recrystallization makes lactic acid content be lower than 10ppm after the cooling.
(2), rac-lactide bulk polymerization:
With catalytic lactide stereo selectirity poly rare earth compound shown in the formula 1 is catalyzer, the mol ratio 100～3000 of rac-lactide monomer and this composition catalyst, the molar ratio of best monomer and this composition catalyst is 500～2500, temperature of reaction is 70～120 ℃, best polymeric reaction temperature is 120 ℃, and the reaction times is 0.1～5 hour, is cooled to room temperature, with volume ratio is the chloroformic solution termination reaction of 10% hydrochloric acid, obtains the white solid product polylactide.The assorted isostructure content P of polylactide wherein
r=0.65～0.90.The molecular weight of polylactide is measured with gel permeation chromatograph (Waters 410), polylactide assorted with content P
rProton homonuclear decoupling NMR (Nuclear Magnetic Resonance) spectrum by methylene is calculated.
(3), the solution polymerization process of rac-lactide:
The solvent that adopts is toluene, methylene dichloride or tetrahydrofuran (THF), the rac-lactide monomer concentration is 15～50wt%, polymeric reaction temperature is 20～100 ℃, best polymeric reaction temperature is 20～70 ℃, the mol ratio of the catalyzer of catalyzer lactide stereo selectirity poly rare earth compound is 300～2500 shown in best monomer and the formula 1, and the reaction times is 0.1～5 hour, is cooled to room temperature, with volume ratio is the chloroformic solution termination reaction of 10% hydrochloric acid, obtains the white solid product polylactide.The assorted isostructure content P of polylactide wherein
r=0.64～0.99.The molecular weight of polylactide is measured with gel permeation chromatograph (Waters 410), polylactide assorted with content P
rProton homonuclear decoupling NMR (Nuclear Magnetic Resonance) spectrum by methylene is calculated.Catalytic lactide stereo selectirity poly rare earth compound of the present invention, the molecular structural formula of title complex 6 is shown in Fig. 2-1.The crystalline structure figure that the X-ray single crystal diffraction of title complex 6 characterizes is shown in Fig. 2-2.
Catalytic lactide stereo selectirity poly rare earth compound of the present invention is the initiation center with active rare earth metal carbon bond, amine key or oxygen key, has the feature of living polymerization, and polymerization rate is fast, temperature of reaction is low, gained polylactide molecular weight height.And, utilize the side group that contains the different spaces obstacle, regulate the steric effect and the electronic effect of catalyst active center, the final control that realizes the polymkeric substance steric configuration, acquisition is assorted to be up to 0.99 polylactide product with content.The polylactide of bibliographical information is assorted at present only is 0.96 with the content maximum.And this system is a catalyzer with the metallic aluminium title complex, and aluminium is poisonous to human body, is difficult to after the polyreaction remove from system, therefore limits the application of polymkeric substance in field of medicaments that is obtained by this catalyzer.
As everyone knows, because the composition principle of heterotactic polymer belongs to two kinds of monomer alternating polymerizations that opticity is different, system is very responsive to catalyzer and environment, and therefore improving assorted also is very difficult with content 0.01.Comparatively speaking, the present invention obtains to mix and is up to 0.99 polylactide product with content, truly has sizable difficulty technically.And center of the present invention rare earth ion is easy to remove from polymer product, and this is particularly important for the biodegradable material that is applied to field of medicaments, can cause accumulation in the body and intoxicating because trace metal is present in.
Catalytic lactide stereo selectirity poly rare earth compound provided by the invention can prepare assorted isostructural high molecular polylactide.The polymeric temperature of reaction is lower, and room temperature promptly can be carried out solution polymerization.Side reaction is few, and monomer almost all is converted into polymkeric substance, and transformation efficiency reaches 100%, does not therefore have waste.Polymerization rate is fast, is generally 1 hour; And the temperature of reaction of bibliographical information prior art is generally 70 ℃, and the reaction times is generally 24 hours.The molecular weight of product has the characteristics of living polymerization by the mol ratio control of monomer and initiator,
It is important: invention goes into to have carried out fruitful summary, as shown in Figure 1, can improve the molecular weight of polymkeric substance by the mol ratio that changes monomer and catalyzer.Undertaken by the 300:1 mol ratio as monomer and catalyzer, theoretical molecular is 4.32 ten thousand, owing to be living polymerization, the actual polylactide that can obtain about molecular weight 40,000.Assorted with structure, polymerization temperature and the medium control of content by catalyzer.
Description of drawings
Fig. 1 is monomer in the polymerization process (LA) and the mol ratio of catalyzer (Y) and the linear relationship of polylactide molecular weight.
Fig. 2-1 is the molecular structural formula of title complex 6.
Fig. 2-2 is the crystalline structure figure that the X-ray single crystal diffraction of title complex 6 characterizes.
Embodiment:
The preparation of preparation embodiment 1 title complex 3
(1) preparation of title complex 3 used ligand is.Its reaction process is as follows:
In reactor, add 2 respectively, 4-22 tertiary butyl aniline 3.0g, (14.52mmol), dimethyl-ethylenediamine 0.81ml, (7.38mmol), the aqueous solution 1.5ml of 36% formaldehyde, (20.16mmol), 10ml methyl alcohol.80 ℃ of back flow reaction 24h.Behind the question response mixing solutions cool to room temperature, supernatant liquid is toppled over, layer oily matter is smashed to pieces in the methanol solution of 9ml heat, gets white powder, i.e. ligand i.Its weight is 3.09g, and productive rate is 80%.With deuterochloroform (CDCl
3) for reagent with 300 megahertz nuclear magnetic resonance analyser (hydrogen spectrum,
1H NMR) characterized the structure of ligand i: δ=9.78 (br, 2H, OH), 7.19 (s, 2H, C
6H
2), 6.87 (s, 2H, C
6H
2), 3.60 (s, 4H, ArCH
2N), 2.58 (s, 4H, N (CH
2)
2N), 2.31 (s, 6H, N (CH
3)
2), 1.38 (s, 18H, C (CH
3)
3), 1.26 (s, 18H, C (CH
3)
3).
(2) preparation of title complex 3.
Its preparation process is as follows:
In glove box, under-30 ℃ the condition, with (I) 0.019g, (0.037mmol) be dissolved in the 10ml normal hexane, and it is added drop-wise to Y (CH
2SiMe
3)
3(THF)
20.181g, (0.037mmol) in the hexane solution of 5ml, keep-30 ℃ condition 12h.Precipitation is washed the title complex 3 that obtains white with-30 ℃ normal hexane.Its weight is 0.19g, and its productive rate is 70%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum ((
1H NMR), 400 megahertzes) and carbon spectrum (
13C NMR), 100 megahertzes) characterized the structure of part.
1HNMR(400MHz，C
6D
6)：δ＝7.72(d，Hz，2H，C
6H
2)，7.23(d，2H，C
6H
2)，4.06(br，2H，THF)，3.87(s，1H，ArCH
2N)，3.84(s，1H，ArCH
2N)，3.01(s，1H，ArCH
2N)，2.98(s，1H，ArCH
2N)，2.39(br，2H，N(CH
2)
2N)，1.90(s，18H，C(CH
3)
3)，1.83(s，6H，N(CH
3)
2)，1.70(br，2H，N(CH
2)
2N)，1.57(s，18H，C(CH
3)
3)，1.27(br，2H，THF)，0.62(s，9H，CH
2Si(CH
3)
3)，-0.35(d，2H，CH
2SiMe
3).
13C?NMR(100MHz，C
6D
6)：162.3(2C，2，4-tBu
2-C
6H
2)，137.4(2C，2，4-tBu
2-C
6H
2)，136.9(2C，2，4-tBu
2-C
6H
2)，126.3(2C，2，4-tBu
2-C
6H
2)，125.2(2C，2，4-tBu
2-C
6H
2)125.1(2C，2，4-tBu
2-C
6H
2)，72.3(2C，THF)，65.9(2C，ArCH
2N)，60.47(1C，N(CH
2)
2N)，48.9(1C，N(CH
2)
2N)，46.8(2C，N(CH
3)
2)，36.2(2C，C(CH
3)
3)，34.7(2C，C(CH
3)
3)，32.7(6C，C(CH
3)
3)，31.1(6C，C(CH
3)
3)，26.1(1C，CH
2SiMe
3)，25.6(2C，THF)，5.4(3C，Si(CH
3)
3)。
The preparation of preparation embodiment 2 title complexs 6
(1) preparation of title complex 6 used ligand i I, its reaction process is as follows:
In reactor, add 2 respectively, the 4-di-tert-butyl aniline (3.0g, 14.52mmol); Diethyl ethylenediamine (1.06ml, 7.38mmol); The aqueous solution of 36% formaldehyde (1.5ml, 20.16mmol); 10ml methyl alcohol.Back flow reaction 24h under 80 degree.Behind the question response mixing solutions cool to room temperature, supernatant liquid is toppled over, layer oily matter is smashed to pieces in the methanol solution (9ml) of heat, white powder, i.e. ligand i I (3.46g), productive rate is 85%.With deuterochloroform (CDCl
3) for reagent with 300 megahertz nuclear magnetic resonance analyser (hydrogen spectrum,
1H NMR) characterized the structure of ligand i I:
1H NMR (300MHz, CDCl
3): δ=9.65 (br, 2H, OH), 7.20 (s, 2H, C
6H
2), 6.88 (s, 2H, C
6H
2), 3.59 (s, 4H, ArCH
2N), 2.67-2.63 (m, 8H, N (CH
2)
2N, NCH
2CH
3), 1.40 (s, 18H, C (CH
3)
3), 1.28 (s, 18H, C (CH
3)
3), 1.12 (t, J
H-H=7.11Hz, 6H, NCH
2CH
3).
(2) preparation of title complex 6, its reaction process is shown below
In glove box, under-30 ℃ the condition, (0.019g 0.037mmol) is dissolved in the 10ml normal hexane, and it is added drop-wise to Y (CH with (II)
2SiMe
3)
3(THF)
2(0.181g 0.037mmol) in the hexane solution of 5ml, keeps-30 ℃ condition 12h.Precipitation with cold normal hexane (30 ℃) washing, is obtained white title complex 6 (0.18g), and its productive rate is 64%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum ((
1H NMR), 400 megahertzes) and carbon spectrum ((
13C NMR), 100 megahertzes) characterized the structure of part.
1H?NMR(400MHz，C
6D
6)：δ＝7.71(d，2H，C
6H
2)，7.23(d，2H，C
6H
2)，4.05(m，2H，THF)，3.88(s，1H，ArCH
2N)，3.85(s，1H，ArCH
2N)，3.03(s，1H，ArCH
2N)，3.00(s，1H，ArCH
2N)，2.75(m，2H，N(CH
2CH
3)
2)，2.47(br，2H，N(CH
2)
2N)，2.22(br，2H，N(CH
2CH
3)
2)，1.99(br，2H，N(CH
2)
2N)，1.91(s，18H，C(CH
3)
3)，1.56(s，18H，C(CH
3)
3)，1.32(m，2H，THF)，0.63(s，9H，CH
2Si(CH
3)
3)，0.56(t，6H，N(CH
2CH
3)
2)，-0.29(d，2H，CH
2Si(CH
3)
3).
13CNMR(100Hz，C
6D
6)：162.2(2C，2，4-tBu
2C
6H
2O)，137.4(2C，2，4-tBu
2C
6H
2O)，136.9(2C，2，4-tBu
2C
6H
2O)，126.2(2C，2，4-tBu
2-C
6H
2O)，125.2(2C，2，4-tBu
2-C
6H
2O)，125.1(2C，2，4-tBu
2-C
6H
2O)，72.1(2C，THF)，66.0(2C，ArCH
2N)，52.8(1C，N(CH
2)
2N)，49.0(1C，N(CH
2)
2N)，45.9(2C，N(CH
2CH
3)
2)，36.2(2C，CH
3)
3)，34.7(2C，C(CH
3)
3)，32.7(6C，C(CH
3)
3)，31.3(6C，C(CH
3)
3)，26.3(1C，CH
2SiMe
3)，25.6(2C，THF)，9.0(2C，N(CH
2CH
3)
2)，5.5(3C，Si(CH
3)
3)。
The preparation of preparation embodiment 3 title complexs 12
(1) preparation of title complex 12 used ligand i II, its reaction process is as follows:
In reactor, add 2 respectively, the 4-di-tert-butyl aniline (5.0g, 242mmol); Dimethylamino pyridine (1.5ml, 14.6mmol); The aqueous solution of 36% formaldehyde (2.ml, 24mmol); 10ml methyl alcohol.Back flow reaction 24h under 80 degree.Behind the question response mixing solutions cool to room temperature, supernatant liquid is toppled over, layer oily matter is smashed to pieces in the methanol solution (9ml) of heat, white powder, i.e. ligand i II (3.96g), productive rate is 85%.With deuterochloroform (CDCl
3) for reagent with 300 megahertz nuclear magnetic resonance analyser (hydrogen spectrum,
1H NMR) characterized the structure of ligand i II:
1HNMR (300MHz, CDCl
3): δ=8.70 (d, 1H), 7.70 (ddd, 1H), 7.28 (1H), 7.10 (d, 1H), 7.20 (d, 2H), 6.92 (d, 2H), 3.84 (m, 6H), 1.40 (s, 18H, C (CH
3)
3), 1.28 (s, 18H, C (CH
3)
3).
(2) preparation of title complex 12, its reaction process is shown below
In glove box, under-30 ℃ the condition, (0.018g 0.037mmol) is dissolved in the 10ml normal hexane, and it is added drop-wise to Y (CH with III
2SiMe
3)
3(THF)
2(0.181g 0.037mmol) in the hexane solution of 5ml, keeps-30 ℃ condition 12h.Precipitation with cold normal hexane (30 ℃) washing, is obtained white title complex 6 (0.18g), and its productive rate is 64%.With deuterium for benzene (C
6D
6) for reagent with nuclear magnetic resonance analyser hydrogen spectrum ((
1H NMR), 400 megahertzes) and carbon spectrum ((
13C NMR), 100 megahertzes) characterized the structure of part.
1H?NMR(400MHz，C
6D
6)：)δ＝8.73(d，2H，Py-aH)，7.46(d，2H，C
6H
2)，7.09(d，2H，C
6H
2)，6.55(d，d，d，2H，Py-βH)，6.26(t，2H，Py-γHAr-H)，5.90(d，2H，Py-δH)，4.10(br，2H，THF)，4.07(s，1H，ArCH
2N)，4.04(s，1H，ArCH
2N)，3.36(s，2H，PyCH
2N)，3.07(s，1H，ArCH
2N)，3.04(s，1H，ArCH
2N)，1.82(s，18H，C(CH
3)
3)，1.52(s，18H，C(CH
3)
3)，1.36(m，2H，THF)，0.70(s，9H，CH
2Si(CH
3)
3)，0.09(d，2H，CH
2SiMe
3).
13CNMR(100Hz，C
6D
6)：162.6(2C，ipso-2，4-tBu
2C
6H
2O)，160.5(1C，ipso-C
6H
4N)，149.8(1C，C
6H
4N)，138.1(2C，ipso-2，4-tBu
2C
6H
2O)，136.8(2C，ipso-2，4-tBu
2C
6H
2O)，126.1(1C，C
6H
4N)，126.0(2C，ipso-2，4-tBu
2-C
6H
2O)，124.6(2C，2，4-tBu
2-C
6H
2O)，124.1(2C，ipso-2，4-tBu
2-C
6H
2O)，122.5(1C，C
6H
4N)，121.7(1C，C
6H
4N)，72.0(2C，THF)，64.9(2C，ArCH
2N)，57.5(1C，PyCH
2N)，36.0(2C，C(CH
3)
3)，34.6(2C，C(CH
3)
3)，32.8(6C，C(CH
3)
3)，30.8(6C，C(CH
3)
3)，26.8(1C，CH
2SiMe
3)，25.6(2C，THF)，5.4 (3C，CH
2Si(CH
3)
3).
Application Example 1
(1), earlier rac-lactide (rac-LA) with ethyl acetate 65 ℃ of dissolvings down, the pure system of recrystallization makes lactic acid content be lower than 10ppm after the cooling.
Take by weighing 1.0g (7mmol) rac-lactide (rac-LA) place 40ml to have the reaction flask of rubber tubing, reaction flask placed 70 ℃ constant temperature oil bath, treat to add behind the rac-Lactide partial melting catalytic lactide stereo selectirity poly rare earth compound 1 (hereinafter to be referred as title complex 1) that is dissolved in the 0.5ml toluene (7.7mg, 0.014mmol).The mol ratio of monomer and catalyzer 1 [rac-LA]/[title complex 1]=500.0.1h is carried out in reaction, places 0 ℃ frozen water to cool off reaction flask, and the chloroformic solution of adding 1ml 10% hydrochloric acid (volume ratio) is poured sedimentation in the ethanol into after stopping, and gets the white solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 0.746g.Transformation efficiency 74.6%.Molecular weight with the gpc analysis polylactide gets M
n=6.98 ten thousand, M
w/ M
n=1.73.P
r＝0.65(
1H?NMR，600MHz，CDCl
3)。
Application Example 2
Taking by weighing 1.0g (7mmol) racemize revolves rac-Lactide (rac-LA) places 40ml to have the reaction flask of rubber tubing, and (reaction flask is in advance through finding time, fire is roasting, cooling, argon filling is handled, this process triplicate), reaction flask placed 120 ℃ constant temperature oil bath, treat to add catalytic lactide stereo selectirity poly rare earth compound 2 (hereinafter to be referred as the title complex 2) (4.22mg that is dissolved in the 0.5ml toluene after the rac-Lactide fusion, 0.007mmol), the mol ratio of monomer and catalyzer 2 [rac-LA]/[title complex 2]=1000, reaction is carried out placing 0 ℃ frozen water to cool off reaction flask behind the 1h, adds the chloroformic solution termination reaction of 1ml 10% (volume ratio) hydrochloric acid.Pour reaction solution in ethanol sedimentation, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.0g, transformation efficiency 100%.Molecular weight with the gpc analysis polylactide gets M
n=14.11 ten thousand, M
w/ M
n=1.53, P
r=0.819 (
1H NMR, 600MHz, CDCl
3).
Application Example 3
(rac-LA) (14mmol) places 40ml to have the reaction flask of rubber tubing, and (reaction flask is in advance through finding time to take by weighing the 2.0g rac-lactide, fire is roasting, cooling, the argon filling process is handled three times), reaction flask placed 90 ℃ constant temperature oil bath, treat to add catalytic lactide stereo selectirity poly rare earth compound 3 (hereinafter to be referred as the title complex 3) (7.2mg that is dissolved in the 0.5ml toluene behind the rac-Lactide partial melting, 0.009mmol), the mol ratio of monomer and catalyzer 3 [rac-LA]/[title complex 3]=1500, reaction 3h, place 0 ℃ frozen water to cool off reaction flask, after adding the chloroformic solution termination of 2ml 10% hydrochloric acid (weight ratio), pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 2.0g, transformation efficiency 100%.The molecular weight of analyzing polylactide with 6PC gets M
n=19.32 ten thousand, M
w/ M
n=2.11.P
r＝0.90(
1HNMR，600MHz，CDCl
3)。
Application Example 4
Take by weighing 2.0g (14mmol) rac-lactide (rac-LA) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), reaction flask is placed 120 ℃ constant temperature oil bath, treat to add after the rac-Lactide fusion being dissolved in the 0.2ml toluene
4 (hereinafter to be referred as title complex 4) (4.0mg, 0.007mmol), the mol ratio of monomer and catalyzer 4 [rac-LA]/[title complex 4]=2000, reaction 5h, place 0 ℃ frozen water to cool off reaction flask, after adding the chloroformic solution termination of 3ml 10% (weight ratio) hydrochloric acid, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.7g, transformation efficiency 85%.Molecular weight with the gpc analysis polylactide gets M
n=20.44 ten thousand, M
w/ M
n=2.45.P
r＝0.845(
1H?NMR，600MHz，CDCl
3)。
Application Example 5
Take by weighing 2.0g (14mmol) racemization rac-Lactide (rac-LA) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), reaction flask is placed 120 ℃ constant temperature oil bath, treat to add after the rac-Lactide fusion being dissolved in the 0.2ml toluene
5 (hereinafter to be referred as title complex 5) (8.83mg, 0.014mmol), the mol ratio of monomer and catalyzer 5 [rac-LA]/[title complex 5]=1000, reaction 3h, place 0 ℃ frozen water to cool off reaction flask, after adding the chloroformic solution termination of 2ml 10% (volume ratio) hydrochloric acid, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.85g, transformation efficiency 92.5%.Molecular weight with the gpc analysis polylactide gets M
n=11.54 ten thousand, M
w/ M
n=2.07.P
r＝0.830(
1H?NMR，600MHz，CDCl
3)。
Application Example 6
Take by weighing 2.0g (14mmol) rac-lactide (rac-LA) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), reaction flask is placed 100 ℃ constant temperature oil bath, treat to add behind the rac-Lactide partial melting being dissolved in the 0.3ml toluene
6 (hereinafter to be referred as title complex 6) (22.4mg, 0.028mmol), the mol ratio of monomer and catalyzer 6 [rac-LA]/[title complex 6]=500, reaction 0.1h, place 0 ℃ frozen water to cool off reaction flask, after adding the chloroformic solution termination of 1ml 10% (weight ratio) hydrochloric acid, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 2.0g, transformation efficiency 100%.Molecular weight with the gpc analysis polylactide gets M
n=6.44 ten thousand, M
w/ M
n=1.97.P
r＝0.890(
1HNMR，600MHz，CDCl
3)。
Application Example 7
Take by weighing 1.0g (7mmol) rac-lactide (rac-LA) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), reaction flask is placed 120 ℃ constant temperature oil bath, treat to add after the rac-Lactide fusion being dissolved in the 0.3ml toluene
7 (hereinafter to be referred as title complex 7) (9.42mg, 0.014mmol), the mol ratio of monomer and catalyzer 7 [rac-LA]/[title complex 7]=500, reaction 1h, place 0 ℃ frozen water to cool off reaction flask, after adding the chloroformic solution termination of 2ml 10% (volume ratio) hydrochloric acid, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 0.96g, transformation efficiency 96.0%.Molecular weight with the gpc analysis polylactide gets M
n=6.88 ten thousand, M
w/ M
n=1.74.P
r＝0.755(
1H?NMR，600MHz，CDCl
3)。
Application Example 8
Take by weighing 1.0g (7mmol) rac-lactide (rac-LA) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 3ml tetrahydrofuran (THF) with syringe again, reaction flask is placed 20 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
8 (hereinafter to be referred as title complexs 8) (10.2mg, 0.014mmol), the mol ratio [rac-LA] of monomer and catalyzer 8/[title complex 8]=500, reaction 0.1h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 0.5ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 0.94g, transformation efficiency 94%.Molecular weight with the gpc analysis polylactide gets M
n=5.37 ten thousand, M
w/ M
n=1.55.P
r＝0.967(
1H?NMR，600MHz，CDCl
3)。
Application Example 9
Take by weighing 1.0g (7mmol) rac-lactide (rac-LA) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 3ml tetrahydrofuran (THF) with syringe again, reaction flask is placed 20 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
9 (hereinafter to be referred as title complexs 9) (12.6mg, 0.014mmol), the mol ratio [rac-LA] of monomer and catalyzer 9/[title complex 9]=600, reaction 0.3min.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 0.5ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 0.98g, transformation efficiency 98%.Molecular weight with the gpc analysis polylactide gets M
n=5.90 ten thousand, M
w/ M
n=1.48.P
r＝0.971(
1HNMR，600MHz，CDCl
3)。
Application Example 10
Take by weighing the 1.5g rac-lactide (rac-LA) (10.4mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 4ml tetrahydrofuran (THF) with syringe again, reaction flask is placed 40 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
10 (hereinafter to be referred as title complexs 10) (14.3mg, 0.021mmol), the mol ratio [rac-LA] of monomer and catalyzer 10/[title complex 10]=500, reaction 0.1h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 0.5ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.50g, transformation efficiency 100%.Molecular weight with the gpc analysis polylactide gets M
n=6.93 ten thousand, M
w/ M
n=1.52.P
r＝0.981(
1HNMR，600MHz，CDCl
3)。
Application Example 11
Take by weighing the 2.0g rac-lactide (rac-LA) (13.9mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 5ml tetrahydrofuran (THF) with syringe again, reaction flask is placed 60 ℃ constant temperature oil bath, treat that rac-Lactide dissolving back adds
11 (hereinafter to be referred as title complexs 11) (14.7mg, 0.0198mmol), the mol ratio [rac-LA] of monomer and catalyzer 11/[title complex 11]=700, reaction 2h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 1.5ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 2.0g, transformation efficiency 100%.Molecular weight with the gpc analysis polylactide gets M
n=11.56 ten thousand, M
w/ M
n=1.48.P
r＝0.947(
1H?NMR，600MHz，CDCl
3)。
Application Example 12
Take by weighing the 1.5g rac-lactide (rac-LA) (10.4mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 4ml tetrahydrofuran (THF) with syringe again, reaction flask is placed 70 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
12 (hereinafter to be referred as title complexs 12) (11.9mg, 0.013mmol), the mol ratio [rac-LA] of monomer and catalyzer 12/[title complex 12]=800, reaction 3h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 1.5ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.46g, transformation efficiency 97.3%.The molecular weight of analyzing polylactide with 6PC gets M
n=13.0l ten thousand, M
w/ M
n=1.98.P
r＝0.938(
1H?NMR，600MHz，CDCl
3)。
Application Example 13
Take by weighing the 1.5g rac-lactide (rac-LA) (10.4mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add 3ml toluene with syringe again, reaction flask is placed 80 ℃ constant temperature oil bath, treat that rac-Lactide dissolving back adds
13 (hereinafter to be referred as title complexs 13) (5.39mg, 0.0104mmol), the mol ratio [rac-LA] of monomer and catalyzer 13/[title complex 13]=1000, reaction 4h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 1.5ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.48g, transformation efficiency 98.7%.Molecular weight with the gpc analysis polylactide gets M
n=13.24 ten thousand, M
w/ M
n=2.02.P
r＝0.790(
1H?NMR，600MHz，CDCl
3)。
Application Example 14
Take by weighing the 1.5g rac-lactide (rac-LA) (10.4mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 3ml tetrahydrofuran (THF) with syringe again, reaction flask is placed 50 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
14 (hereinafter to be referred as title complexs 14) (4.02mg, 0.007mmol), the mol ratio [rac-LA] of monomer and catalyzer 14/[title complex 14]=1500, reaction 3h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 1.5ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.35g, transformation efficiency 90.0%.Molecular weight with the gpc analysis polylactide gets M
n=17.9 ten thousand, M
w/ M
n=2.38.P
r＝0.922(
1H?NMR，600MHz，CDCl
3)。
Application Example 15
Take by weighing the 2.0g rac-lactide (rac-LA) (13.9mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 4ml tetrahydrofuran (THF) with syringe again, reaction flask is placed 30 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
15 (hereinafter to be referred as title complexs 15) (5.16mg, 0.007mmol), the mol ratio [rac-LA] of monomer and catalyzer 15/[title complex 15]=2000, reaction 5h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 3.0ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.87g, transformation efficiency 93.5%.Molecular weight with the gpc analysis polylactide gets M
n=23.7 ten thousand, M
w/ M
n=2.25.P
r＝0.983(
1H?NMR，600MHz，CDCl
3)。
Application Example 16
Take by weighing the 2.0g rac-lactide (rac-LA) (13.9mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 4ml tetrahydrofuran (THF) with syringe again, reaction flask is placed 20 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
16 (hereinafter to be referred as title complexs 16) (3.52mg, 0.0057mmol), the mol ratio [rac-LA] of monomer and catalyzer 16/[title complex 16]=2500, reaction 5h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 3.0ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.94g, transformation efficiency 99.0%.Molecular weight with the gpc analysis polylactide gets M
n=20.9 ten thousand, M
w/ M
n=2.65.P
r＝0.979(
1HNMR，600MHz，CDCl
3)。
Application Example 17
Take by weighing the 2.0g rac-lactide (rac-LA) (13.9mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 4ml tetrahydrofuran (THF) with syringe again, reaction flask is placed 60 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
17 (hereinafter to be referred as title complexs 17) (19.2mg, 0.028mmol), the mol ratio [rac-LA] of monomer and catalyzer 17/[title complex 17]=500, reaction 0.5h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 3.0ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.95g, transformation efficiency 97.5%.Molecular weight with the gpc analysis polylactide gets M
n=6.98 ten thousand, M
w/ M
n=1.67.P
r＝0.952(
1H?NMR，600MHz，CDCl
3)。
Application Example 18
Take by weighing the 2.0g rac-lactide (rac-LA) (13.9mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 3ml tetrahydrofuran (THF), reaction flask is placed 20 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
18 (hereinafter to be referred as title complexs 18) (29.8mg, 0.035mmol), the mol ratio [rac-LA] of monomer and catalyzer 18/[title complex 18]=400, reaction 0.3h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution that adds 2.0 ml10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 2.0g, transformation efficiency 100%.Molecular weight with the gpc analysis polylactide gets M
n=5.03 ten thousand, M
w/ M
n=1.45.P
r＝0.987(
1H?NMR，600MHz，CDCl
3)。
Application Example 19
Take by weighing the 1.5g rac-lactide (rac-LA) (10.4mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 3ml methylene dichloride, reaction flask is placed 20 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
19 (hereinafter to be referred as title complexs 19) (13.8mg, 0.026mmol), the mol ratio [rac-LA] of monomer and catalyzer 19/[title complex 19]=400, reaction 0.1h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 2.0ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.95g, transformation efficiency 97.5%.The molecular weight of analyzing polylactide with GpC gets M
n=5.88 ten thousand, M
w/ M
n=1.42.P
r＝0.773(
1H?NMR，600MHz，CDCl
3)。
Application Example 20
Take by weighing the 1.5g rac-lactide (rac-LA) (10.4mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 3ml methylene dichloride, reaction flask is placed 25 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
20 (hereinafter to be referred as title complexs 20) (6.10mg, 0.01mmol), the mol ratio [rac-LA] of monomer and catalyzer 20/[title complex 20]=1000, reaction 2h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 2.0ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 1.46g, transformation efficiency 97.3%.Molecular weight with the gpc analysis polylactide gets M
n=12.3 ten thousand, M
w/ M
n=1.75.P
r＝0.712(
1HNMR，600MHz，CDCl
3)。
Application Example 21
Take by weighing the 2.5g rac-lactide (rac-LA) (17.3mmol) place 40ml have rubber tubing reaction flask (reaction flask in advance through find time, fire is roasting, cooling, argon filling process handle three times), add the 4ml methylene dichloride, reaction flask is placed 20 ℃ water bath with thermostatic control, treat that rac-Lactide dissolving back adds
21 (hereinafter to be referred as title complexs 21) (6.53mg, 0.009mmol), the mol ratio [rac-LA] of monomer and catalyzer 21/[title complex 21]=2000, reaction 5h.Place 0 ℃ frozen water to cool off reaction flask, after the chloroformic solution of adding 2.0ml 10% (volume ratio) hydrochloric acid stops, pour sedimentation in the ethanol into, get white spongy solid product polylactide.This product is placed vacuum drying oven, and under 40 ℃, dry 48h gets product polylactide net weight 2.30g, transformation efficiency 92.0%.Molecular weight with the gpc analysis polylactide gets M
n=20.1 ten thousand, M
w/ M
n=1.99.P
r＝0.742(
1HNMR，600MHz，CDCl
3)。
Claims (2)
1, a kind of catalytic lactide stereo selectirity poly rare earth compound is characterized in that, has structure as follows:
R=CH
3, R '=CH
2CH
3, R ＂=O
iPr title complex 14,
R=
tBu, R '=CH
2CH
3, R ＂=O
iPr title complex 15.
2, a kind of catalytic lactide stereo selectirity poly rare earth compound is characterized in that, has structure as follows:
Ln=Lu, R=H, R '=CH
3, R ＂=CH
2SiMe
3, title complex 16,
Ln=Lu, R=CH
3, R '=CH
3, R ＂=CH
2SiMe
3, title complex 17,
Ln=Lu, R=
tBu, R '=CH
3, R ＂=CH
2SiMe
3, title complex 18.
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