CN101775042A - Novel polydentate monophenoxy ligand magnesium complex, and preparation method and applications thereof - Google Patents
Novel polydentate monophenoxy ligand magnesium complex, and preparation method and applications thereof Download PDFInfo
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Abstract
The invention discloses a novel polydentate monophenoxy ligand magnesium complex, and a preparation method and applications thereof. The preparation method thereof comprises the following steps of: reaction ligand L with Mg[N(SiMe3)2]2 and then collecting target product from reaction product. The magnesium complex described in the invention containing asymmetric polydentate monophenoxy ligands is an effective lactone ring-opening polumerization catalyst and can be used for the ring-opening polumerization reaction of caprolactone, lactide and the like, when catalyzed rac-lactide is subject to ring-opening polumerization reaction, polymers with certain isotacticity can be obtained, and when catalyzed L-lactide is subject to ring-opening polumerization reaction, isotactic polymers can be obtained. The polydentate monophenoxy ligand magnesium complex according to the invention has extremely obvious advantages of: good availability of raw materials, simple synthesis process, easy separation and purification, relatively stable property, high catalytic activity and converting 86% of 10000 equivalent of monomer within 5 minutes. Polylactone resulted from catalysis has high molecular weight and narrow molecular weight distribution (PDI is equal to 1.07), and can meet the demand of industrial departments. The structure thereof has the following formula: FORMULA.
Description
Technical field
The present invention relates to the MAGNESIUM METAL complex compound that a class contains multiple tooth single phenol oxygen ylidene ligands, and this class complex compound application in lactone ring opening polymerization.
Background technology
By by caprolactone (ε-CL, ε-Caprolactone) and lactic acid (LA, Lactic Acid or rac-Lactide LA, lactide) and poly-fats lactone (Aliphatic Polyester) product that obtains of other limb fat family lactone ring opening polymerization reaction have advantages such as favorable mechanical plasticity-, water-disintegrable and biocompatibility.These characteristics make them have a wide range of applications in biomedical and pharmacy field: as the material of carrier, surgical graft and the animal body tissue repair of sustained release medicine, move as artificial skin, dental operation, artery connect, contact pin and be used for the treatment of the nail of fracture and retaining plate etc.In addition, the polyester product also can significantly reduce the pollution problem of current petroleum-type Chemicals to environment because its good plasticity-and biological degradability also can be used for making agricultural mulch films, holding food processing apparatus and various packing bag.Therefore the catalysis ring-opening polymerization research to rac-Lactide and caprolactone has caused extensive concern (PolymerReviews, 2008,48,11).
ε-CL does not have chirality, has only a kind of configuration, is linear aliphatic adoption ester by the PCL of ε-CL by the ring-opening polymerization gained.It is a kind of macromolecular compound of half hitch crystal formation, has the perviousness of excellent drug, to organic nontoxicity and biological degradability.PCL at room temperature is a rubbery state, better heat stability, and decomposition temperature is more much higher than other polyester, and the product after the degraded is carbonic acid gas and water, environmentally safe.Rac-Lactide is made by acid by dehydrating lactic, and lactic acid can obtain from the fermentation of renewable resourcess such as cereal, corn, beet seed.PLA can be by lactic acid direct polymerization dehydration at high temperature or by rac-Lactide ring-opening polymerization and getting in the presence of catalyzer or initiator.Because directly condensation polymerization is a balanced reaction, the micro-moisture in the polymerization reaction late stage system is difficult to remove fully usually, be not easy to obtain high-molecular weight PLA, thereby this route has significant limitation.Mitsui east presses chemical company to announce that they are by using high boiling solvent azeotropic technology to obtain high-molecular weight PLA by the lactic acid direct esterification, U.S. Cargill Dow LLC company also announces directly to adopt low-cost operate continuously to obtain high-molecular weight PLA by lactic acid, but most of at present big research still concentrate on rac-Lactide ring-opening polymerization.
The microcosmic three-dimensional arrangement of polylactide has determined its macro physical performance, as: the fusing point (T of the isotaxy polylactide (PLLA or PDLA) that obtains by D-LA or L-LA polymerization
m) about 180 ℃, second-order transition temperature (T
g) be 60 ℃; Its fusing point of racemic mixture that the PLLA of equivalent volumes isotactic poly and PDLA form can be up to 230 ℃; By Study of Meso-Lactide (meso-LA) or rac-lactide (rac-LA) polymerization obtain between rule polylactide fusing point can reach 153 ℃, second-order transition temperature is 45 ℃.Random polylactide and assorted rule polylactide are armorphous polymkeric substance, and practical ranges is less.The microcosmic three-dimensional arrangement of polylactide can be controlled by the stereoselective polymerization of rac-Lactide under the complex catalysis of different metal, and therefore designing the synthesizing new metal complex catalyst in recent years becomes the research focus in polylactone field in order to realize the upright structure controllable polymerization of rac-Lactide open loop.Wherein, magnesium metal complex activity is very high, and of light color, and is still all significant in the application of medical field to the protection environment as hypotoxicity metal complex to catalyze lactone ring opening polymerization.
1996, Chisholm group with three purine radicals boron hydrogen hydride compounds (trispyrazolyl hydroborate) and three indazolyl boron hydrogen hydride compounds (trisindazolylhydroborate) as part, synthetic tridentate ligand magnesium metal complex (Chem.Commun.1996,853), studied with them catalyzed polymerization L-LA and meso-LA, it is linear and range of molecular weight distributions is less to have obtained polymericular weight and transformation efficiency (below 90%), is indicated as controllable polymerization.2002, Coates study group has synthesized beta-diimine class magnesium complex and has been used for catalyzed polymerization rac-LA (J.Am.Chem.Soc.2002,124,15239), make of methylene dichloride that transformation efficiency can reach 98% in following 2 minutes of the solvent room temperature, generate random PLA, then obtained the PLA of assorted rule when making solvent with tetrahydrofuran (THF).2004, it is magnesium complex (the Dalton Trans.2004 of part with three tooth beta-diimines that Gibson is combined into same for a short time, 570), just can reach transformation efficiency when being used for catalyzed polymerization rac-LA in 10 minutes greater than 80%, but controllability is relatively poor, and molecular weight distribution wide (PDI=1.53-1.78), molecular weight and the non-linear relation of monomeric transformation efficiency, explanation is non-living polymerization.2005, the magnesium complex that it is part that Lin has been combined into the big diphenol of steric hindrance for a short time is used for catalysis L-LA and ε-CL polymerization, and (Polymer 2005,46,5909), this magnesium complex is done solvent catalysis ε-CL polymerization with toluene and is obtained the polymkeric substance of molecular weight distribution narrower (PDI=1.06-1.10) under 25 ℃ of conditions.Be the PLA that solvent catalysis L-LA polymerization obtains narrow molecular weight distribution equally with ethylene dichloride.In the same year, the complex compound (DaltonTrans.2005,2047) that it is the magnesium of part that Sobota group has reported with big sterically hindered phenol amine is at CH
2Cl
2Middle catalyzed polymerization L-LA obtains the PLA of molecular weight distribution very narrow (PDI=1.10-1.12), the linear living polymerization that is indicated as of the molecular weight of polymkeric substance and reaction times.2007, it is the complex compound (Polyhedron.2007 of the magnesium of part with the amino-pyrazol that Carpentier has been combined into for a short time, 26,3817), be catalyzed polymerization rac-LA under the solvent room temperature with toluene or THF, obtain the random PLA of molecular weight distribution relative narrower (PDI=1.28-1.34), the linear controllable polymerization that is indicated as of molecular weight of [rac-LA]/[In] and PLA.The same year, Lin has been combined into the complex compound (Macromolecules that a series of ketoimines are the magnesium of part for a short time, 2007,40, all shown very high activity during 8855) with their catalysis L-LA polymerizations, and be polymerized to controlledly, substituent steric hindrance electronic effect has a significant impact polymerization result on the ketoimine.2009, Lin group has reported that again with [NNO] three tooth Schiff's base be the magnesium complex catalysis L-LA polymerization (Inorg.Chem.2009 of part, 48,728), the complex compound of these magnesium has all shown very high catalytic activity, with the introducing of part electron-donating group, reactive behavior is improved, and the introducing of introducing electron-withdrawing group has then reduced catalytic activity.In the same year, it is that the complex compound of the magnesium of part is used for catalysis L-LA polymerization (Dalton Trans.2009,9068) with diamino azoles quinoline that Chen has been combined into a series of for a short time, and under the room temperature condition, in THF, BnOH exists down, with different [LA]
0/ [Mg]
0The ratio polymerization obtains the polymkeric substance of molecular weight distribution narrower (PDI=1.06～1.46).
In sum, the complex compound great majority of at present synthetic resulting magnesium are to have the monokaryon of symmetrical structure or the metal complex of double-core, carry out polymerization by end of the chain control, in polymerization process, chain transfer or chain permutoid reaction take place easily, and obtaining is the amido in no generation.
R
1～R
4Be hydrogen, methyl, the tertiary butyl, cumyl, trityl group or halogen; R
5Be C
2～C
3Alkylidene group, cyclohexylidene, phenylene; R
6Be ethyl, isopropoxy or two (trimethyl silicane) amido; X
1Be C
1～C
3Alkoxyl group or C
1～C
3The secondary amine that alkyl replaces, fluorine; X
2Be C
1～C
2Alkoxyl group, C
1～C
3The secondary amine that alkyl replaces, preferred magnesium compound structure is:
Complex compound (I) the preparation method following steps of asymmetric multiple tooth single phenol oxygen Base Metal magnesium of the present invention:
Again asymmetric multiple tooth single phenols ligand compound and the magnesium organometallics shown in the formula (II) reacted in organic medium, generate asymmetric multiple tooth single phenol oxygen base magnesium compound, the preferred magnesium ethide of described magnesium organometallics or two { two (trimethyl silicane) amido } magnesium, temperature of reaction is-20～80 ℃, preferred 0～50 ℃, reaction times is 18～48 hours, collects target compound (I) then from reaction product.
Asymmetric multiple tooth single phenols ligand compound and the metal-organic mol ratio of magnesium are 1: 0.5～1.5, preferred 0.8～1.2.
Described organic medium is selected from a kind of in tetrahydrofuran (THF), ether, toluene, benzene, normal hexane, Skellysolve A and the sherwood oil.
The application of asymmetric multiple tooth single phenol oxygen base magnesium compound is characterized in that, is used for the ring-opening polymerization of lactones such as caprolactone, rac-Lactide or beta-butyrolactone.
Asymmetric multiple tooth single phenol oxygen base magnesium compound of the present invention is a kind of catalyzer of lactone ring opening polymerization efficiently, make lactone be caprolactone, L-rac-Lactide, rac-rac-Lactide-40～110 ℃ of polymerizations, catalyzer and monomer mole ratio are 1: 1～5000 during polymerization.
Under the condition that alcohol exists, make lactone such as caprolactone, rac-Lactide-40～110 ℃ of polymerizations, catalyzer and alcohol and monomer mole ratio are 1: 1～50: 1～5000 during polymerization.
Described alcohol is selected from methyl alcohol, ethanol, Virahol, the trimethyl carbinol, benzylalcohol.
Change polymerizing condition, the polymerization activity of catalyzer has change in various degree.Optimum polymerizing condition is: polymerization temperature is-40～110 ℃, preferred-10～70 ℃ of following polymerizations; Catalyst concn is [M]
0=0.5～2.0M, [Mg]
0=0.0005～0.01M, preferred concentration are [M]
0=1.0M, [Mg]
0=0.005M; Polymerization time is 1～120min; Catalyzer and monomer mole ratio are 1: 1～5000 during polymerization, preferred 1: 200～2000, and catalyzer, Virahol and monomer mole ratio are 1: 1～50: 1～5000 when Virahol exists, preferred 1: 1～20: 200～2000.
Catalyzer raw material provided by the invention is easy to get, and is easy to prepare, and stable in properties has advantages of high catalytic activity simultaneously, easily obtains the polylactone of ultra-high molecular weight and narrow distribution.Can satisfy the needs of industrial sector, have a wide range of applications.Further specify the present invention below by example, but the invention is not restricted to this.
Embodiment
Embodiment 1
Synthetic complex compound C1
Under argon shield, in 100mL Schlenk bottle, add the 6-tertiary butyl-2-[N-(2-methoxy-benzyl)-N-(2-methoxy ethyl) methylamino]-4-methylphenol (0.408g), toluene 20mL, room temperature condition add Mg[N (SiMe down
3)
2]
2(0.380g), stirring at room 24 hours is put into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.310g, productive rate 51.0%).Code name C1.
H?NMR(400MHz，C6D6)：δ7.38(s，1H，Ar-H)，6.91(t，1H，J＝7.2Hz，ArH)，6.67-6.70(m，2H，ArH)，6.61(d，1H，J＝7.2Hz，ArH)，6.55(d，1H，J＝8.3Hz，1H，ArH)，3.96(d，1H，J＝12.8Hz，ArCH
2)，3.79(d，1H，J＝11.6Hz，Ar-CH
2)，3.69(s，3H，OCH
3)，3.12(s，3H，Ar-OCH
3)，2.85(td，1H，J＝4.4Hz，J＝11.6Hz，NCH
2CH
2O)，2.57(dt，1H，J＝6.7Hz，J＝11.9Hz，1H，NCH
2)，2.42(s，3H，Ar-CH
3)，2.30-2.50(m，3H，NCH
2CH
2O，Ar-CH
2)，1.84(s，9H，C(CH
3)
3)，1.23(dd，1H，J＝4.0Hz，J＝12.0Hz，NCH
2)，0.36(s，18H，SiCH
3)；Anal.Calcd.for?C
29H
50MgN
2O
3Si
2：C，62.74；H，9.08；N，5.05.Found：C，62.83；H，9.17；N，5.10％.
Embodiment 2
Synthetic complex compound C2
Under argon shield, in 100mL Schlenk bottle, add 4,6-dicumyl-2-[N-(2-methoxy-benzyl)-N-(2-methoxy ethyl) methylamino] phenol (0.537g), toluene 20mL, room temperature condition add Mg[N (SiMe down
3)
2]
2(0.345g), stirring at room 24 hours is put into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.360g, productive rate 50.0%).Code name C2.
1H?NMR(400MHz，C
6D
6)δ：7.56(d，2H，J＝7.6Hz，ArH)，7.52(d，1H，J＝2.0Hz，Ar-H)，7.47(d，2H，J＝7.6Hz，ArH)，7.38(dd，1H，J＝7.2Hz，J＝8.0Hz，ArH)，7.22(t，2H，J＝7.6Hz，ArH)，6.97-7.08(m，3H，ArH)，6.88(t，1H，J＝7.2Hz，ArH)，6.75(d，1H，J＝2.4Hz，ArH)，6.64(t，1H，J＝7.6Hz，ArH)，6.53(t，2H，J＝6.4Hz，ArH)，4.01(d，1H，J＝12.8Hz，Ar-CH
2)，3.70(d，1H，J＝12.0Hz，Ar-CH
2)，3.29(s，3H，OCH
3)，3.00(s，3H，Ar-OCH
3)，2.66-2.74(m，2H，Ar-CH
2)，2.31-2.43(m，4H，NCH
2CH
2O)，2.23(s，3H，cumyl-CH
3)，2.00(s，3H，cumyl-CH
3)，1.78(s，3H，cumyl-CH
3)，1.77(s，3H，cumyl-CH
3)，0.29(s，18H，SiCH
3)；Anal.calcd.for?C
29H
50MgN
2O
3Si
2：C，62.74；H，9.08；N，5.05.Found：C，62.83；H，9.17；N，5.10％.
Embodiment 3
Synthetic complex compound C3
Under argon shield; in 100mL Schlenk bottle, add the 6-tertiary butyl-2-[N-(the 3-tertiary butyl-2-methoxyl group-5-methyl-benzyl)-N-(2-methoxy ethyl) methylamino]-4-methylphenol (0.485g); toluene 20mL, room temperature condition add Mg[N (SiMe down
3)
2]
2(0.380g), stirring at room 24 hours is put into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.285g, productive rate 41.4%).Code name C3.
1H?NMR(400MHz，C
6D
6)δ：7.26(s，1H，ArH)，7.11(s，1H，ArH)，6.68(s，1H，ArH)，6.42(s，1H，ArH)，3.66-3.71(m，2H，Ar-CH
2)，3.62(d，1H，J＝12.0Hz，Ar-CH
2)，3.54(s，3H，OCH
3)，2.91(td，1H，J＝12.0Hz，J＝6.4Hz，NCH
2CH
2O)，2.86(d，1H，J＝14.4Hz，Ar-CH
2)，2.82(s，3H，Ar-OCH
3)，2.76(td，1H，J＝10.0Hz，J＝4.0Hz，NCH
2CH
2O)，2.47-2.54(m，1H，NCH
2CH
2O)，2.26(s，3H，Ar-CH
3)，2.13(s，3H，Ar-CH
3)，1.93(d，1H，J＝12.0Hz，NCH
2CH
2O)，1.74(s，9H，
tBu-CH
3)，1.38(s，9H，C(CH
3)
3)，0.49(s，18H，SiCH
3)；Anal.calcd.for?C
34H
60MgN
2O
3Si
2：C，65.30；H，9.67；N，4.48.Found：C，65.48；H，9.61；N，4.47％.
Embodiment 4
Synthetic complex compound C4
Under argon shield, in 100mL Schlenk bottle, add 4,6-two chloro-2-{N-[2-(N, N dimethylamine base)-5-methyl-benzyl]-N-(2-methoxy ethyl) methylamino } phenol (0.627g), toluene 20mL, room temperature condition add Mg[N (SiMe down
3)
2]
2(0.493g), stirring at room 24 hours is put into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.507g, productive rate 60.6%).Code name C4.
1H?NMR(400MHz，C
6D
6)δ：7.44(d，1H，J＝2.8Hz，ArH)，6.77(d，1H，J＝8.4Hz，ArH)，6.71(d，1H，J＝8.4Hz，ArH)，6.60(s，1H，ArH)，6.44(s，1H，ArH)，3.40(br?s，1H，Ar-CH
2)，3.18(br?s，1H，Ar-OCH
2)，3.16(s，3H，OCH
3)，2.82(br?s，1H，NH
2CH
2O)，2.68-2.73(br?s，1H，NH
2CH
2O)，2.55-2.64(m，2H，NH
2CH
2O)，2.52(s，6H，NCH
3)，2.31(d，1H，J＝11.6Hz，Ar-CH
2)，2.06(s，3H，Ar-CH
3)，1.24(d，1H，J＝12.4Hz，Ar-CH
2)，0.41(s，18H，SiCH
3)；Anal.calcd.forC
28H
43Cl
2MgN
2O
3Si
2：C，53.75；H，7.46；N，7.23.Found：C，53.55；H，7.54；N，7.07％
Embodiment 5
Synthetic complex compound C5
Under argon shield, in 100mL Schlenk bottle, add the 6-tertiary butyl-2-{N-(2-methoxy-benzyl)-N-[2-(N, N-dimethyl) ethylamino-] methylamino }-4-methylphenol (0.384g), toluene 20mL, room temperature condition add Mg[N (SiMe down
3)
2]
2(0.493g), stirring at room 24 hours is put into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.403g, productive rate 71.0%).Code name C5.
1H?NMR(C
6D
6，400MHz)：δ7.31(d，1H，J＝1.2Hz，ArH)，6.62(d，1H，J＝7.2ArH)，6.80(t，1H，J＝7.4Hz，ArH)，6.52(d，1H，J＝1.2Hz，ArH)，6.48(d，1H，J＝8.4Hz，ArH)，4.11(d，1H，J＝14.4Hz，Ar-CH
2-N)，3.96(d，1H，J＝12.8Hz，Ar-CH
2-N)，3.76(d，1H，J＝14.4Hz，Ar-CH
2-N)，3.37(s，3H，CH
3OAr)，3.09(d，1H，J＝12.8Hz，Ar-CH
2-N)，2.50-2.44(m，1H，CH
2CH
2)，2.29(s，3H，Ar-CH
3)，2.27-2.21(m，1H，CH
2CH
2)，1.91(s，7H，N(CH
3)
2overlapped?by?1H?of?CH
2CH
2signal)，1.78(s，9H，C(CH
3)
3)，1.58-1.53(m，1H，CH
2CH
2)，0.47(s，18H，N(Si(CH
3)
3)
2).
13C{
1H}(C
6D
6，100MHz)：δ163.7，157.9，138.4，133.1，130.2，130.1，128.5，122.2，121.3，121.06，120.9，112.1(all?Ar)，60.2(CH
3O-Ar)，57.3(Ar-CH
2-N)，56.3(N-CH
2-Ar)，54.7(CH
2CH
2)，47.5(CH
2CH
2)，47.0(N(CH
3)
2)，35.5(C(CH
3)
3)30.5，(C(CH
3)
3)，21.0(Ar-CH
3)，7.16(N(Si(CH
3)
3)
2).Anal.Calcd.for?C
30H
53N
3O
2Si
2Mg：C，63.41；H，9.40；N，7.39.Found：C，63.25；H，9.47；N，7.36.
Embodiment 6
Synthetic complex compound C6
Under argon shield; in 100mL Schlenk bottle, add 4,6-dicumyl-2-{N-(the 3-tertiary butyl-2-methoxyl group-4-methyl-benzyl)-N-[2-(N, N-dimethyl) ethylamino-] methylamino } phenol (0.636g); toluene 20mL, room temperature condition add Mg[N (SiMe down
3)
2]
2(0.493g), stirring at room 24 hours is put into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.559g, productive rate 69.6%).Code name C6.
1H?NMR(CDCl
3，400MHz)：7.56(d，1H，J＝2.4Hz，ArH)，7.52(d，2H，J＝7.6Hz，CMe
2Ph)，7.36(d，2H，J＝7.6Hz，CMe
2Ph)，7.18-7.15(m，4H，CMe
2Ph?overlapped?by?C
6D
6signal)，7.06(s，1H，ArH)，7.05-6.98(m，2H，CMe
2Ph)，6.95(s，1H，ArH)，6.79(d，1H，J＝2.0Hz，ArH)，4.04(d，1H，J＝8.4Hz，Ar-CH
2-N)，4.01(d，1H，J＝8.8Hz，N-CH
2-Ar)，3.92，(d，1H，J＝13.6Hz，Ar-CH
2-N)，3.27(d，1H，J＝13.2Hz，N-CH
2-Ar)，3.27(s，3H，CH
3O-Ar)，2.29-2.21(m，2H，CH
2CH
2)，2.19(s，3H，Ar-CH
3)，1.98-1.91(m，1H，CH
2CH
2)，1.72，(s，3H，CMe
2Ph)，1.69(s，6H，CMe
2Ph)，1.67，(s，3H，CMe
2Ph)，1.62-1.31(m，6H，N(CH
3)
2and?1H，CH
2CH
2)，0.44(s，18H，N(Si(CH
3)
3)
2).
13C{
1H}NMR(CDCl
3，100MHz)：163.3，158.0，152.8，152.5，143.3，137.3，134.1，133.2，132.7，129.5，127.5，127.2，127.0，125.5，125.3，124.6，121.6(all?Ar)，63.2(CH
3O-Ar)，60.5(Ar-CH
2-N)，57.6(N-CH
2-Ar)，52.7(CH
2CH
2)，46.2(R-N(CH
3)
2)，45.8(CH
2CH
2)，42.9(CMe
2Ph)，42.5(CMe
2Ph)，35.0(C(CH
3)
3)，33.7(CMe
2Ph)，31.5(2CMe
2Ph)，31.3，(C(CH
3)
3)，26.7(CMe
2Ph)，21.1(Ar-CH
3)，7.25(N(Si(CH
3)
3)
2).Anal.Calcd.for?C
48H
73N
3O
2Si
2Mg：C，71.65；H，9.15；N，5.22.Found：C，71.78；H，9.33；N，5.17.
Embodiment 7
Synthetic complex compound C7
Under argon shield; in 100mL Schlenk bottle, add the 6-tertiary butyl-2-{N-[2-(N, N-dimethyl)-5-methyl-benzyl]-N-[2-(N, N-dimethyl) ethylamino-] methylamino }-4-methylphenol (0.411g); toluene 20mL, room temperature condition add Mg[N (SiMe down
3)
2]
2(0.493g), stirring at room 24 hours is put into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.4075g, productive rate 68.0%).Code name C7.
1H?NMR(C
6D
6，400MHz)：7.32(s，1H，ArH)，7.02(s，1H，ArH?overlapped?by?PhCH
3signal)，6.97(d，1H，J＝8.8Hz，ArH)，6.92(d，1H，J＝8.0Hz，ArH)，6.54(s，1H，ArH)，4.40(d，1H，J＝13.2Hz，Ar-CH
2-N)，4.05(d，1H，J＝12.4Hz，N-CH
2-Ar)，3.99(d，1H，J＝13.6，Ar-CH
2-N)，3.40(d，1H，J＝12.8，Ar-CH
2-N)，2.51-2.41(m，1H，CH
2CH
2)，2.38-2.30(m，1H，CH
2CH
2)，2.26(s，9H，Ar-N(CH
3)
2，Ar-CH
3)，2.23-2.22(m，1H，CH
2CH
2)，2.14(s，3H，Ar-CH
3)，1.88(s，6H，N(CH
3)
2)，1.77(s，9H，C(CH
3))，1.63-1.59(m，1H，CH
2CH
2)，0.534(s，18H，N(Si(CH
3)
3)
2).
13C{
1H}(C
6D
6，100MHz)：163.7，152.8，138.4，134.8，134.2，130.8，130.3，128.8，127.4，122.0，121.4，120.9(allAr)，59.4(Ar-CH
2-N)，57.7(N-CH
2-Ar)，51.6(CH
2CH
2)，46.9(N(CH
3)
2)，45.8(Ar-N(CH
3)
2)，44.9(CH
2CH
2)，35.4(C(CH
3)
3)，30.4(C(CH
3)
3)，21.0(Ar-CH
3)，20.9(Ar-CH
3)，7.26(N(Si(CH
3)
3)
2).Anal.Calcd.for?C
32H
58N
4OSi
2Mg(3/2C
7H
8)：C，69.60；H，9.55；N，7.64.Found：C，69.25；H，9.67；N，7.77.
Embodiment 8
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 2min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 34.2%.
Embodiment 9
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 4min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 59.0%, viscosity-average molecular weight M
η=1.01 * 10
4, assorted normality P
r=0.67.
Embodiment 10
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 2min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 77.3%.
Embodiment 11
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 3min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 83.8%, assorted normality P
r=0.56.
Embodiment 12
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 13min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 46.8%.
Embodiment 13
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 20min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 73.2%.
Embodiment 14
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 27min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 76.7%, number-average molecular weight M
n=2.83 * 10
4, assorted normality P
r=0.55, PDI=1.89.
Embodiment 15
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the toluene solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 2min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 65.3%, viscosity-average molecular weight M
η=0.86 * 10
4
Embodiment 16
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the toluene solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 5min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 98.4%, number-average molecular weight M
n=2.02 * 10
4, P
m=0.63, PDI=1.67.
Embodiment 17
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL L-rac-Lactide, the THF solution 0.5mL of the described catalyzer C1 that reinjects, [L-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [L-LA]
0=1: 200, stirring at room reaction 3min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 73.7%, viscosity-average molecular weight M
η=5.33 * 10
4
Embodiment 18
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL L-rac-Lactide, the THF solution 0.5mL of the described catalyzer C1 that reinjects, [L-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [L-LA]
0=1: 200, stirring at room reaction 8min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 85.9%.
Embodiment 19
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL L-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C1 that reinjects, [L-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 2min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 100.0%, viscosity-average molecular weight M
η=4.42 * 10
4
Embodiment 20
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 5min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 18.0%.
Embodiment 21
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 10min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 37.5%, viscosity-average molecular weight M
η=1.15 * 10
4
Embodiment 22
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 14min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 43.2%.
Embodiment 23
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 5min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 38.3%.
Embodiment 24
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 10min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 54.8%, viscosity-average molecular weight M
η=1.10 * 10
4
Embodiment 25
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 60min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 54.3%.
Embodiment 26
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mLrac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 95min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 78.2%.
Embodiment 27
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 110min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 88.2%, viscosity-average molecular weight M
η=2.18 * 10
4, number-average molecular weight M
n=2.46 * 10
4, PDI=1.75, assorted normality P
r=0.59.
Embodiment 28
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 26min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 84.2%, viscosity-average molecular weight M
η=0.76 * 10
4, number-average molecular weight M
n=2.46 * 10
4, PDI=1.75, assorted normality P
r=0.52.
Embodiment 29
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 30min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 89.4%.
Embodiment 30
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL L-rac-Lactide, the THF solution 0.5mL of the described catalyzer C2 that reinjects, [L-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [L-LA]
0=1: 200, stirring at room reaction 3min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 48.7%.
Embodiment 31
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL L-rac-Lactide, the THF solution 0.5mL of the described catalyzer C2 that reinjects, [L-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [L-LA]
0=1: 200, stirring at room reaction 5min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 56.9%, viscosity-average molecular weight M
η=5.19 * 10
4
Embodiment 32
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL L-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C2 that reinjects, [L-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 1.5min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 89.2%.
Embodiment 33
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL L-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C2 that reinjects, [L-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 3min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 97.7%.
Embodiment 34
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C3 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 10min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 85.0%.
Embodiment 35
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C3 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 10min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 85.0%, viscosity-average molecular weight M
η=0.71 * 10
4, number-average molecular weight M
n=1.24 * 10
4, PDI=1.39, assorted normality P
r=0.71.
Embodiment 36
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C3 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 20min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 92.8%.
Embodiment 37
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C3 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 4min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 98.1%, assorted normality P
r=0.63.
Embodiment 38
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C3 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 7min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 41.2%.
Embodiment 39
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C3 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 11min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 67.7%, viscosity-average molecular weight M
η=2.15 * 10
4, assorted normality P
m=0.62.
Embodiment 40
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol toluene solution, the toluene solution 0.5mL of the described catalyzer C3 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 4min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 77.6%.
Embodiment 41
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol toluene solution, the toluene solution 0.5mL of the described catalyzer C3 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 13min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 94.5%, P
r=0.41.
Embodiment 42
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C4 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 25min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 13.8%.
Embodiment 43
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C4 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 3.5 hours.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 61.1%, viscosity-average molecular weight M
η=2.23 * 10
4
Embodiment 44
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C4 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 4.5 hours.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 76.0%, number-average molecular weight M
n=1.02 * 10
4, PDI=1.48, assorted normality P
r=0.66.
Embodiment 45
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C4 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 30min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 63.0%, viscosity-average molecular weight M
η=1.25 * 10
4
Embodiment 46
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C5 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 3min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 95.6%, M
n=3.08 * 10
4, PDI=2.11, P
r=0.54.
Embodiment 47
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C5 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 1min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 98.0%, M
n=1.79 * 10
4, PDI=1.4, P
r=0.52.
Embodiment 48
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C5 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 5min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 89.5%, P
r=0.52.
Embodiment 49
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol toluene solution, the toluene solution 0.5mL of the described catalyzer C5 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 2min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 90.0%, M
n=1.21 * 10
4, PDI=1.46, P
m=0.56.
Embodiment 50
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C6 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 3min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 90.8%, P
r=0.53.
Embodiment 51
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C6 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 1min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 97.6%, M
n=2.08 * 10
4, PDI=1.29, P
r=0.51.
Embodiment 52
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C6 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 5min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 81.4%, M
n=2.25 * 10
4, PDI=1.85, P
m=0.55.
Embodiment 53
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C6 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200 ,-39 ℃ of stirring reaction 24min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 8.2%, P
m=0.59.
Embodiment 54
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol toluene solution, the toluene solution 0.5mL of the described catalyzer C6 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 2min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 89.5%, M
n=2.32 * 10
4, PDI=1.65, P
m=0.60.
Embodiment 55
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol toluene solution, the toluene solution 0.5mL of the described catalyzer C6 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200 ,-39 ℃ of stirring reaction 60min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 50.7%, P
m=0.65.
Embodiment 56
Under the argon shield, in the 10mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C7 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 3min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 97.2%, P
r=0.53.
Embodiment 57
Under the argon shield, in the 10mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol THF solution, the THF solution 0.5mL of the described catalyzer C7 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 1min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 97.4%, P
r=0.52.
Embodiment 58
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C7 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [rac-LA]
0=1: 200, stirring at room reaction 3min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 87.0%, M
n=1.77 * 10
4, PDI=2.0, Pr=0.51.
Embodiment 59
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C7 that reinjects, [rac-LA]
0=0.5M, [Mg]
0=0.0001M, [Mg]
0: [rac-LA]
0=1: 5000, stirring at room reaction 10min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 93.6%, P
m=0.57.
Embodiment 60
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C7 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.0001M, [Mg]
0: [rac-LA]
0=1: 10000, stirring at room reaction 15min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 91.4%.
Embodiment 61
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C7 that reinjects, [CL]
0=1.0M, [Mg]
0=0.001M, [Mg]
0: [CL]
0=1: 1000, stirring at room reaction 0.5min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 100.0%.
Embodiment 62
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol toluene solution, the toluene solution 0.5mL of the described catalyzer C7 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.005M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 200, stirring at room reaction 1min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 91.0%, M
n=2.32 * 10
4, PDI=1.56, P
m=0.58.
Embodiment 63
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol toluene solution, the toluene solution 0.5mL of the described catalyzer C7 that reinjects, [rac-LA]
0=0.5M, [Mg]
0=0.0001M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 5000, stirring at room reaction 2min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 90.5%.
Embodiment 64
Under the argon shield, in the 10mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, 0.1mL Virahol toluene solution, the toluene solution 0.5mL of the described catalyzer C7 that reinjects, [rac-LA]
0=1.0M, [Mg]
0=0.0001M, [Mg]
0: [
iPrOH]
0: [rac-LA]
0=1: 1: 10000, stirring at room reaction 5min.With wet oil ether termination reaction, after the filtration with polymkeric substance 60 ℃ of vacuum-dryings 12 hours.Monomer conversion: 84.2%, M
n=53.08 * 10
4, PDI=1.23.
Claims (10)
1. novel complex compound (I) that contains asymmetric multiple tooth single phenols ligand metal magnesium is characterized in that having following general formula:
In the formula (I):
R
1～R
4Represent hydrogen respectively, C
1～C
20The alkyl of straight chain, side chain or ring texture,-oxyl, halogen; R
5Be ethylidene; R
6Be butyl, two (trimethyl silicane) amido; X
1～X
2Represent C
1～C
12The alkoxyl group of straight chain, side chain or ring texture, dimethylin.
2. asymmetric multiple tooth single phenol oxygen base magnesium compound according to claim 1 is characterized in that R
1～R
4Be hydrogen or C
1～C
10The alkyl of straight chain, side chain or ring texture, alkoxyl group, C
7～C
20The alkyl that list or polyaryl replace, C
6～C
18Aryl, halogen; X
1～X
2Be C
1～C
6Alkoxyl group, dimethylin.
3. asymmetric multiple tooth single phenol oxygen base magnesium compound according to claim 2 is characterized in that R
1～R
4Be hydrogen, methyl, the tertiary butyl, cumyl, trityl group or halogen; X
1～X
2Be methoxyl group, dimethylin.
4. complex compound (I) preparation method of each described asymmetric multiple tooth single phenol oxygen base magnesium of claim 1～3 comprises the steps:
Asymmetric multiple tooth single phenols ligand compound and magnesium organometallics shown in the formula (II) are reacted in organic medium, generate asymmetric multiple tooth single phenol oxygen base magnesium compound, temperature of reaction is-20～80 ℃, preferred 0～50 ℃, reaction times is 18～48 hours, collects target compound (I) then from reaction product.
5. method according to claim 4 is characterized in that, the magnesium organometallics is dibutyl magnesium or two { two (trimethyl silicane) amido } magnesium more preferably.
6. method according to claim 4 is characterized in that, asymmetric multiple tooth single phenols ligand compound and the metal-organic mol ratio of magnesium are 1: 0.5～1.5, preferred 0.8～1.2.
7. method according to claim 4 is characterized in that, said solvent is selected from a kind of in tetrahydrofuran (THF), ether, toluene, benzene, normal hexane and the sherwood oil.
8. the application of each described asymmetric multiple tooth single phenol oxygen base magnesium complex of claim 1～3 is characterized in that, is used for the ring-opening polymerization of lactone such as caprolactone, rac-Lactide or beta-butyrolactone.
9. application according to claim 8, it is characterized in that, with 1～3 each described asymmetric multiple tooth single phenol oxygen base magnesium complex is catalyzer, make lactone such as caprolactone, rac-Lactide at-40～110 ℃, preferably-10～70 ℃ following polymerization, catalyzer and monomer mole ratio are 1: 1～5000 during polymerization, preferred 1: 200～2000, and the solvent that polymerization is adopted is methylene dichloride, tetrahydrofuran (THF), sherwood oil, toluene, ether, benzene and normal hexane.
10. application according to claim 9, it is characterized in that, with 1～3 each described asymmetric multiple tooth single phenol oxygen base magnesium complex is catalyzer, under the condition that alcohol exists, make lactone such as caprolactone, rac-Lactide at-40～110 ℃, preferably-10～70 ℃ following polymerization, catalyzer and alcohol and monomer mole ratio are 1: 1～50: 1～5000 during polymerization, preferred 1: 1～20: 200～2000.Described alcohol is selected from methyl alcohol, ethanol, Virahol, the trimethyl carbinol, benzylalcohol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060718A (en) * | 2010-11-30 | 2011-05-18 | 华东理工大学 | Polydentate amino monophenoloxy zinc complex compound as well as preparation method and application thereof |
| CN102153597A (en) * | 2011-02-23 | 2011-08-17 | 华东理工大学 | Asymmetric multi-hock type monophenoloxo magnesium complex as well as preparation method and application thereof |
| CN102838637A (en) * | 2012-09-18 | 2012-12-26 | 华东理工大学 | Imine phenol oxymagnesium compound, and preparation method and application thereof |
| CN105237552A (en) * | 2015-10-10 | 2016-01-13 | 华东理工大学 | Oxazoline ring-containing amino tocopheroxyl zinc/magnesium complexes and preparation method and application thereof |
| CN111253556A (en) * | 2020-03-20 | 2020-06-09 | 南京工业大学 | Functionalized recyclable high-molecular homopolymer and preparation method and application thereof |
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2010
- 2010-01-11 CN CN201010022624A patent/CN101775042A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060718A (en) * | 2010-11-30 | 2011-05-18 | 华东理工大学 | Polydentate amino monophenoloxy zinc complex compound as well as preparation method and application thereof |
| CN102153597A (en) * | 2011-02-23 | 2011-08-17 | 华东理工大学 | Asymmetric multi-hock type monophenoloxo magnesium complex as well as preparation method and application thereof |
| CN102838637A (en) * | 2012-09-18 | 2012-12-26 | 华东理工大学 | Imine phenol oxymagnesium compound, and preparation method and application thereof |
| CN102838637B (en) * | 2012-09-18 | 2015-08-19 | 华东理工大学 | Imine phenol oxygen base magnesium compound and its preparation method and application |
| CN105237552A (en) * | 2015-10-10 | 2016-01-13 | 华东理工大学 | Oxazoline ring-containing amino tocopheroxyl zinc/magnesium complexes and preparation method and application thereof |
| CN105237552B (en) * | 2015-10-10 | 2017-04-19 | 华东理工大学 | Oxazoline ring-containing amino tocopheroxyl zinc/magnesium complexes and preparation method and application thereof |
| CN111253556A (en) * | 2020-03-20 | 2020-06-09 | 南京工业大学 | Functionalized recyclable high-molecular homopolymer and preparation method and application thereof |
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