CN102617369B - Similar salan monophenol ligand metal complexes as well as preparation method and application thereof - Google Patents

Similar salan monophenol ligand metal complexes as well as preparation method and application thereof Download PDF

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CN102617369B
CN102617369B CN201210036780.6A CN201210036780A CN102617369B CN 102617369 B CN102617369 B CN 102617369B CN 201210036780 A CN201210036780 A CN 201210036780A CN 102617369 B CN102617369 B CN 102617369B
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magnesium
salan
zinc
calcium
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CN102617369A (en
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马海燕
宋绍迪
杨漾
张星宇
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East China University of Science and Technology
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Abstract

The invention discloses zinc, magnesium and calcium complexes of monophenol ligands with similar salan-structures as well as a preparation method thereof and the application in lactone ring-opening polymerization. The preparation method comprises the steps as follows: the similar salan-monophenol ligands react with zinc, magnesium and calcium metallo-organic compounds, and then target products are collected from reaction coarse products. The zinc, magnesium and calcium complexes comprise asymmetrical multidentate amino monophenol oxygroup ligands with the similar salan-structures, are effective lactone ring-opening polymerization catalysts, and can be used for ring-opening polymerization of lactide, caprolactone and the like. The multidentate monophenol oxygroup zinc, magnesium and calcium complexes have the very obvious advantages as follows: raw materials are easy to get, the synthetic route is simple, separation and purification are easy, and the performance is stable relatively; meanwhile, high catalytic activity is achieved; in addition, polylactone that is obtained through catalysis has higher molecular weight, and the requirements of industrial sectors can be satisfied. The structure of the zinc, magnesium and calcium complexes has the following general formula.

Description

Mono-phenols ligand metal complex of class salan and preparation method thereof and application
Technical field
The present invention relates to metallic zinc, magnesium, calcium complex and synthetic that a class contains class salan structure list phenols part, and this class complex compound application in lactone ring opening polymerization.
Background technology
It is found that from eighties of last century the seventies polyester material has advantages of that many and polyolefin product compares favourably, and after the unexistent biocompatibility of polyolefin product and degradability, polyester material synthetic, produce and processing degradable polyester aspect obtained significant progress, and in medicine, agricultural and daily living article, be applied gradually.In current polyester research field, polylactide, polycaprolactone and their multipolymer be study much more relatively several, there is biodegradability, good biocompatibility, plasticity-, the easy advantage such as machine-shaping, be regarded as the most promising Biodegradable material.
The ring-opening polymerization of metal catalyst catalyzing lactone monomer, can obtain the multipolymer of polylactide, polycaprolactone and these two kinds of monomers of high molecular easily.The controllability that the microtexture of polymkeric substance and performance are shown when the polymerization by catalyzer is determined (Chem.Soc.Rev., 2010,39,486-494; Chem.Soc.Rev., 2010,39,165-173), therefore, design synthesizing new metal complex catalyst, realizes the vertical structure controllable polymerization of lactone open loop, to obtain the polylactone of various special constructions and performance, becomes current study hotspot.Zinc, magnesium, calcium metal complex ring-opening polymerization of lactone by catalysis effectively, and its metal ion look shallow, low toxicity, exploitation zinc, magnesium, calcium metal complex catalyst are all significant to Environmental Protection Cause or medical field.
About zinc complex, 1999, beta-diimine class zinc complex catalysis rac-LA ring-opening polymerization (J.Am.Chem.Soc.1999 for Coates, 121,11583), polymerization 20min at 20 DEG C, monomer conversion can reach 95-97%, and obtaining molecular weight is that 37900g/mol, assorted rule structure are main (P r=0.90) polymkeric substance.2000, three pyrazolyl borane compounds for Chisholm group (trispyrazolyl hydroborate) have synthesized tridentate ligand monometallic center zinc complex catalyzed polymerization L-rac-Lactide (J.Am.Chem.Soc.2000,122,11845), monomer conversion below 90% time, is aggregated in controlled.2003, Hillmyer and Tolman etc. synthesized oxyethyl group double-core zinc complex (J.Am.Chem.Soc.2003,125,11350), under room temperature at CH 2cl 2middle catalysis rac-LA ring-opening polymerization obtains polydispersity polymer (130000g/mol, [LA] 0/ [Zn] 0=1500), be random structure, and molecular weight become good linear relationship with monomer conversion.2007, the report double-core zinc complexes such as Hillmyer (Inorg.Chem.2007,46,6565), effectively catalysis ε-CL carries out ring-opening polymerization, and resulting polymers molecular weight distribution narrower (PDI=1.08～1.24).2009, [NNO] three tooth imine ligand zinc complex (J.Polym.Sci.:Part A:Polym.Chem., 2009,47,2318) catalysis rac-rac-Lactides for Lin etc., at-30 DEG C, monomer conversion has reached 85%, and assorted rule selectivity reaches 81%.
About magnesium complex, 1996, Chisholm group synthesized magnesium complex (Chem.Commun., 1996,853), catalysis L-rac-Lactide controllable polymerization with three pyrazolyl borane compounds and three indazolyl borane compounds as part.2002, Coates group found the magnesium complex (J.Am.Chem.Soc., 2002,124,15239) containing beta-diimine part, had higher catalytic activity than the zinc complex containing same structure part.In the same year, the magnesium complex (Inorg.Chem., 2002,41,2785) of Chisholm group report beta-diimine part can effectively cause rac-LA polymerization.2010, Otero group reports the magnesium complex (Inorg.Chem. of the tong-like cyclopentadienyl ligands that contains alkyl and alkoxyl group, 2010,49,2859), catalysis caprolactone ring-opening polymerization in wider temperature, only several minutes just can obtain the polymkeric substance (M of high molecular, moderate molecular weight distribution n> 10 5, M w/ M n=1.45); The polymkeric substance that can obtain moderate molecular weight when catalysis rac-LA polymerization, its molecular weight distribution may diminish to M w/ M n=1.02.
About calcium complex, 2003, the people such as Feijen found that the benzyloxy calcium binuclear complex of beta-diimine part is than calcium silicon amido binuclear complex (Polym.Bull., 2003,51,175) higher to the catalytic activity of ε-CL or L-LA polymerization, and the PDI of resulting polymers is narrower.The same year, Chisholm group found the monometallic center calcium complex (Chem.Commun., 2003,48) of three pyrazolyl boron hydrogen alkane tridentate ligands, very high to the catalytic activity of rac-LA ring-opening polymerization, and assorted rule selectivity reaches 90%.Next year, Chisholm etc. report again in beta-diimine class calcium complex (Inorg.Chem., 2004,43,6717) room temperature THF higher to rac-LA ring-opening polymerization activity, but obtain random PLA.2006, with dianion double-core calcium complex (Daltons.2006,340), to caprolactone, ring-opening polymerization had good controllability to Bochmann report, but active on the low side.2007, Lin found that Schiff's base double-core calcium complex (Polymer, 2007,48,2257), can catalysis L-LA ring-opening polymerization under benzylalcohol exists, but active not high enough.2008, Darenshbourg report Schiff's base monokaryon calcium complex (Macromolecules 2008,41,3493), catalysis rac-LA ring-opening polymerization under melting condition, activity is higher, and polymerization is controlled.And reduce assorted rule selectivity with temperature and improve, in THF ,-33 DEG C obtain P rvalue is 0.73 PLA.2009, Huang report pyridyl ligands double-core calcium complex and ketoimine complex compound three core calcium complex (Inorg.Chem., 2009,48,8004) to L-LA, ring-opening polymerization has very high catalytic activity, and in room temperature DMC, polymerization 20min monomer conversion can reach 95%.
In sum, zinc, magnesium, the calcium complex reported at present, rac-Lactide and caprolactone ring-opening polymerization are all had to higher catalytic activity, but part can not form stable chirality coordination environment effectively around metal center, monomer coordination and insertion are not had to selectivity, thereby obtain the polymkeric substance of random or assorted rule.People wish to develop that activity and selectivity is higher, cost is lower, can produce the change non-toxic catalyst with special purpose isotactic polymer, the demand of producing to meet interior polyisocyanate polyaddition.
Summary of the invention
One of the object of the invention is open a kind of asymmetric class salan-part and the complex compound with zinc, magnesium, calcium thereof, the defect existing to overcome prior art.
Two of the object of the invention is open asymmetric class salan-part and the preparation method with the complex compound of zinc, magnesium, calcium thereof.
Three of the object of the invention is open asymmetric salan-part and the complex compound application in lactone ring opening polymerization as catalyzer with zinc, magnesium, calcium thereof.
Technical conceive of the present invention:
The complex compound of zinc, magnesium, calcium easily forms dimer, and therefore its activity and selectivity can be restricted relatively.Use asymmetrical polyamines base list phenols part and introducing to there is the initiating group of larger steric hindrance, be expected to synthetic monokaryon phenol oxygen base zinc, magnesium, the calcium complex with chiral metal center.Part is that the salan-Al complex catalysis rac-lactide ring-opening polymerization of dianion often can provide the PLA (J.Am.Chem.Soc., 2004,126,2688-2689) compared with highly-solid selectively.Be divalent metal according to zinc, magnesium, calcium metal, therefore we have designed and synthesized zinc, magnesium, the calcium metal complex of the mono-phenols part of asymmetrical class salan-.Regulate the stability of part and metal center coordination by introduce different substituting groups on aromatic ring, metal chirality still can effectively be retained under polymerizing condition, in the time of polymerization, can identify better chiral monomer, thereby improve stereoselectivity, obtain the higher polylactone of degree of isotacticity.Experimental result shows, by changing ligand structure and polymerizing condition, this class zinc, magnesium, calcium cpd can produce the polylactone that molecular weight is higher, molecular weight distribution is narrower, and according to different metal complexs can partially be mixed rule or the PLA of isotactic partially.
The mono-phenols part of asymmetric class salan-provided by the invention (I) and zinc complex (II) thereof, magnesium, calcium cpd (III) is characterized in that having following general formula:
In formula (I), (II), (III):
R 1～R 2represent respectively hydrogen, C 1～C 20the alkyl of straight chain, side chain or ring texture, C 1～C 20the alkoxyl group of straight chain, side chain or ring texture, C 7～C 30the alkyl that list or polyaryl replace, halogen; R 3～R 4represent hydrogen, C 1～C 4the alkyl of straight chain, side chain; X is C 1～C 12the alkoxyl group of straight chain, side chain or ring texture; R 5for ethylidene or propylidene; R 6represent C 1～C 4alkyl, two (trimethyl silicon based) amido, two (dimethyl is silica-based) amido, isopropoxy.
R 1～R 2for hydrogen, C 1～C 10the alkyl of straight chain, side chain or ring texture, C 1～C 10the alkoxyl group of straight chain, side chain or ring texture, C 7～C 20the alkyl that list or polyaryl replace, halogen; X is C 1～C 6the alkoxyl group of straight chain, side chain or ring texture.
R 1～R 2be preferably hydrogen, methyl, the tertiary butyl, cumyl, chlorine; R 3～R 4, be preferably methyl; X is preferably methoxyl group.
Preferably ligand structure is:
Preferably selecting zinc, magnesium, calcium complex structure is:
The mono-phenols part of asymmetric class salan-of the present invention (I) and zinc complex (II) thereof, magnesium, calcium complex (III) preparation method following steps:
Be there is to western Buddhist alkali reaction in the diamines shown in the aromatic aldehyde shown in formula (IV) and formula (V), add again reductive agent reduction to obtain after new single secondary amine (VI), add and replace brooethyl phenol (VII), temperature of reaction is 60～75 DEG C, react 8～48 hours, then from reaction product, collect compound (I);
The mol ratio of aromatic aldehyde and diamines is 1: 0.8～2.
The preferred sodium borohydride of described reductive agent.
The intermediate product generating and the mol ratio of sodium borohydride are 1: 1～3.
Above-mentioned solvent is selected from one or both in tetrahydrofuran (THF), ether, ethanol, glycol dimethyl ether, toluene, normal hexane and sherwood oil.
The mono-phenols ligand compound of class salan shown in formula (I) is reacted in organic medium with zinc, magnesium, calcium organometallics, generate the mono-phenol oxygen of class salan base zinc, magnesium, calcium cpd, temperature of reaction is-10～80 DEG C, react 24～48 hours, then from reaction product, collect target compound (II) or (III).
The preferred zinc ethyl of described zinc organometallics or two [two (trimethyl silicon based) amido] zinc, the preferred dibutylmagnesium of magnesium organometallics, two [two (trimethyl silicon based) amido] magnesium and two [two (dimethyl is silica-based) amido], the preferred calcium iodide of calcium organometallics and two (tetrahydrofuran (THF)s) close { two [two (trimethyl silicon based) amido] } calcium.
The mono-phenols ligand compound of asymmetric class salan-and zinc, magnesium, the metal-organic mol ratio of calcium are 1: 0.5～1.5, preferably 1: 0.8～1.2.
Described organic medium is selected from one or both in tetrahydrofuran (THF), ether, glycol dimethyl ether, toluene, normal hexane, Skellysolve A and sherwood oil.
The mono-phenol oxygen of asymmetric class salan-of the present invention base zinc, magnesium, calcium cpd are a kind of lactone ring opening polymerization catalyzer efficiently, make lactone if 6-caprolactone, rac-Lactide are at-39～130 DEG C, preferably polymerization at 20～130 DEG C, when polymerization, catalyzer and monomer mole ratio are 1: 1～10000.Polymerization solvent used is toluene, sherwood oil, normal hexane, tetrahydrofuran (THF), ether, glycol dimethyl ether, methylene dichloride, chloroform or does not use any solvent.
Under the condition existing at alcohol, make lactone if 6-caprolactone, rac-Lactide are at-39～130 DEG C, preferably polymerization under 20～130 DEG C of conditions, when polymerization, the mol ratio of catalyzer and alcohol and monomer is 1: 1～10: 1～10000, and polymerization solvent used is toluene, sherwood oil, normal hexane, tetrahydrofuran (THF), ether, glycol dimethyl ether, methylene dichloride, chloroform or does not use any solvent.
Described alcohol is 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 20～130 DEG C of polymerizations, catalyst concn [M] 0=0.0005～0.01M, preferably [M] 0=0.005M; Polymerization time is 5min～72h; When polymerization, catalyzer and monomer mole ratio are 1: 1～10000, preferably 1: 200～2000, and in the time that alcohol exists, catalyzer, alcohol and monomer mole ratio are 1: 1～50: 50～10000, preferably 1: 1～20: 100～5000.
Catalyzer raw material provided by the invention is easy to get, easy to prepare, and stable in properties has higher catalytic activity simultaneously, easily obtains the narrower polylactone of high molecular and molecular weight distribution.The needs that can meet industrial sector, have a wide range of applications.Further illustrate the present invention below by embodiment, but the invention is not restricted to this.
Embodiment
Embodiment 1
Synthetic ligands L1
In 100mL there-necked flask, add 2.72g Benzaldehyde,2-methoxy, 20mL anhydrous methanol, 1.94g N, N '-dimethyl-ethylenediamine, reflux 24h.Add 1.52g sodium borohydride, be heated to 50 DEG C, add wherein water, with dichloromethane extraction, merge organic phase, and with anhydrous magnesium sulfate drying, pump solvent and obtain light yellow viscous liquid, add wherein the KOH that 20mL dry toluene and 1.34g are dry, drip 5.12g 3, the toluene solution of the chloro-2-benzyl of 5-bis-bromo phenol, 70 DEG C of backflows, remove by filter KOH, thick product carries out column chromatography for separation with silica gel and obtains ligand L 1 (2.49g, 22.07%).
1H?NMR(CDCl 3，400MHz)：δ7.32(dd，1H，J 1＝7.2Hz，J 2＝1.6Hz，ArH)，7.26-7.21(m，2H，ArH)，6.90(td，1H，J 1＝7.2Hz，J 2＝0.8Hz，ArH)，6.87-6.83(m，2H，ArH)，3.78(s，3H，OCH 3)，3.62(s，2H，Ar-CH 2N)，3.57(s，2H，NCH 2-Ar)，2.69-2.64(m，2H，CH 2CH 2)，2.63-2.59(m，2H，CH 2-CH 2)，2.26(s，3H，CH 3)，2.24(s，3H，CH 3)；Anal.Calcd.for?C 19H 24C 12N 2O 2：C，59.53；H，6.31；N，7.31.Found：C，59.26；H，6.13；N，7.08％.
Embodiment 2
Synthetic ligands L2
In 100mL there-necked flask, add 2.72g Benzaldehyde,2-methoxy, 20mL anhydrous methanol, 1.94g N, N '-dimethyl-ethylenediamine, reflux 24h.Add 1.52g sodium borohydride, be heated to 50 DEG C, add wherein water, with dichloromethane extraction, merge organic phase, and with anhydrous magnesium sulfate drying, pump solvent and obtain light yellow viscous liquid, add wherein the KOH that 20mL dry toluene and 1.34g are dry, drip 6.05g 3, the toluene solution of the chloro-2-benzyl of 5-bis-bromo phenol, 70 DEG C of backflows, remove by filter KOH, thick product carries out column chromatography for separation with silica gel and obtains ligand L 2 (1.94g, 22.07%).
1H?NMR(CDCl 3，400MHz)：δ7.36(d，1H，J＝7.6Hz，ArH)，7.21(t，1H，J＝7.6Hz，ArH)，7.19(s，1H，ArH)，6.91(t，1H，J＝8.0Hz，ArH)，6.84(d，1H，J＝8.0Hz，ArH)，6.80(s，1H，ArH)，3.78(s，3H，OCH 3)，3.68(s，2H，Ar-CH 2-N)，3.53(s，2H，N-CH 2-Ar)，2.61-2.65(m，4H，CH 2-CH 2)，2.28(s，3H，CH 3)，2.21(s，3H，CH 3)，1.41(s，9H，C(CH 3) 3)，1.27(s，9H，C(CH 3) 3)；Anal.Calcd.for?C 27H 42N 2O 2：C，76.01；H，9.92；N，6.57.Found：C，76.04；H，9.93；N，6.53％.
Embodiment 3
Synthetic ligands L3
In 100mL there-necked flask, add 2.72g Benzaldehyde,2-methoxy, 20mL anhydrous methanol, 1.94g N, N '-dimethyl-ethylenediamine, reflux 24h.Add 1.52g sodium borohydride, be heated to 50 DEG C, add wherein water, with dichloromethane extraction, merge organic phase, and with anhydrous magnesium sulfate drying, pump solvent and obtain light yellow viscous liquid, add wherein the KOH that 20mL dry toluene and 1.34g are dry, drip 8.81g 3, the toluene solution of 5-dicumyl-2-benzyl bromo phenol, 70 DEG C of backflows, remove by filter KOH, thick product carries out column chromatography for separation with silica gel and obtains ligand L 3 (4.96g, 45.07%).
1H?NMR(CDCl 3，400MHz)：δ7.28-7.29(m，5H，ArH)，7.17-7.25(m，7H，ArH)，7.12(t，1H，J＝6.4Hz，ArH)，6.92(t，1H，J＝7.4Hz，ArH)，6.86(d，1H，J＝8.0Hz，ArH)，6.73(s，1H，ArH)，3.78(s，3H，OCH 3)，3.57(s，2H，Ar-CH 2-N)，3.45(s，2H，N-CH 2-Ar)，2.52(t，2H，J＝6.4Hz，CH 2-CH 2)，2.45(t，2H，J＝6.4Hz，CH 2-CH 2)，2.18(s，3H，CH 3)，2.12(s，3H，CH 3)，1.70(s，6H，C(CH 3) 2C 6H 5)，1.67(s，6H，C(CH 3) 2C 6H 5)；Anal.Calc.for?C 37H 46N 2O 2：C，80.69；H，8.42；N，5.09.Found：C，80.65；H，8.22；N，4.87.
Embodiment 4
Synthetic ligands L4
In 100mL there-necked flask, add 2.72g Benzaldehyde,2-methoxy, 20mL anhydrous methanol, 2.25g N, N '-dimethylated propyl diethylenetriamine, reflux 24h.Add 1.52g sodium borohydride, be heated to 50 DEG C, add wherein water, with dichloromethane extraction, merge organic phase, and with anhydrous magnesium sulfate drying, pump solvent and obtain light yellow viscous liquid, add wherein the KOH that 20mL dry toluene and 1.34g are dry, drip 6.05g 3, the toluene solution of 5-di-t-butyl-2-benzyl bromo phenol, 70 DEG C of backflows, remove by filter KOH, thick product carries out column chromatography for separation with silica gel and obtains ligand L 4 (3.23g, 36.60%).
1H?NMR(CDCl 3，400MHz)：δ7.22-7.28(m，2H，ArH)，7.20(d，1H，J＝2.2Hz，ArH)6.84-6.92(m，2H，ArH)，6.81(d，1H，J＝2.2Hz，ArH)，3.80(s，3H，OCH 3)，3.66(s，2H，Ar-CH 2-N)，3.49(s，2H，N-CH 2-Ar)，2.48(t，2H，J＝6.0Hz，CH 2-CH 2-CH 2)，2.43(t，2H，J＝7.4Hz，CH 2-CH 2-CH 2)，2.27(s，3H，CH 3)，2.19(s，3H，CH 3)，1.78-1.83(m，2H，CH 3-CH 2-CH 3)，1.41(s，9H，C(CH 3) 3)，1.28(s，9H，C(CH 3) 3)；Anal.Calc.for?C 28H 44N 2O 2：C，76.32；H，10.06；N，6.36.Found：C，76.41；H，10.17；N，6.39.
Embodiment 5
Synthetic complex compound C1
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(the chloro-2-hydroxybenzyl of 3,5-bis-)-N, N '-dimethyl-ethylenediamine (L1) (0.383g); toluene 20mL, adds Zn[Si (NMe under room temperature 3) 2] 2(0.385g), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and obtains flesh pink transparent crystals and separates out, and drains to obtain incarnadine solid 432mg, and productive rate is 69.2%
1H?NMR(toluene-d 8，400MHz，348K)：δ7.34(d，1H，J＝2.8Hz，ArH)，7.12-6.99(m，2H，overlapped?with?the?signals?of?solvent，ArH)，6.74(t，1H，J＝7.2Hz，ArH)，6.59(d，1H，J＝2.4Hz，ArH)，6.47(d，1H，J＝8.8Hz，ArH)，3.89-3.83(m，1H，NCH 2-Ar)，3.77(d，1H，J＝12.8Hz，Ar-NCH 2)，3.22(s，3H，OCH 3)，2.52(d，1H，J＝12.8Hz，Ar-CH 2N)，2.17(s，3H，NCH 3)，2.11(s，3H，NCH 3)，1.97-1.91(m，3H，NCH 2CH 2N)，1.49-1.45(m，1H，NCH 2CH 2N)，0.36(s，18H，(N(Si(CH 3) 2))； 13C?NMR(C 6D 6，100MHz)：161.6，159.2，137.9(tol.)，134.2，133.5，130.4，130.3，129.3(tol.)，128.6(tol.)，125.7，125.7，123.9，120.9，120.6，116.8，111.2，(All，Ar-C)，56.5(OCH 3)，55.0(Ar-NCH 2)，52.9(NCH 2-Ar)，51.2(NCH 3)，48.0(NCH 3)，47.1(NCH 2CH 2N，)39.9(NCH 2CH 2N)，21.4(tol-CH 3)，6.9(N(Si(CH 3) 2).Anal.Calcd.for?C 25H 41C 12N 3O 2Si 2Zn·0.5tol：C，52.09；H，6.64；N，6.51；Found：C，52.65；H，7.07；N，7.17％.
Embodiment 6
Synthetic complex compound C2
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(3; 5-dicumyl-2-hydroxybenzyl)-N; N '-dimethyl-ethylenediamine (L3) (0.551g); toluene 20mL, adds Zn[Si (NMe under room temperature 3) 2] 2(0.385g), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and after a couple of days, obtains white easy precipitated solid 498mg, and productive rate is 62.9%.
1H?NMR(C 6D 6，400MHz)：δ7.60(d，1H，J＝1.0Hz，ArH)，7.45(d，4H，J＝7.6Hz，ArH)，7.22(t，2H，J＝8.0Hz，ArH)，7.15(s，1H，ArH)，7.10-7.05(m，2H，ArH)，6.98(s br，2H，ArH)，6.81(t，2H，J＝6.8Hz，ArH)，6.70(d，1H，ArH))，6.44(d，1H，J＝8.0Hz，ArH)，3.98(d，1H，J＝12.4Hz，Ar-NCH 2)，3.78-3.62(m，1H，NCH 2-Ar)，3.19(s，3H，OCH 3)，2.68(d，1H，J＝12.8Hz，Ar-CH 2N)，2.70-2.62(m，1H，NCH 2-Ar)，2.18(s.3H，NCH 3)，2.01(s.4H，NCH 3；NCH 2CH 2N)，1.79(s，7H，C(CH 3) 2Ph；NCH 2CH 2N)，1.72(s，4H，C(CH 3) 2Ph；)，1.63-133(m，2H，NCH 2CH 2N)，1.28-1.22(m，2H，C(CH 3) 2Ph)，0.41(s，1H，N(Si(CH 3) 3) 2)；Anal.Calc.for?C 43H 63N 3O 2Si 2Zn：C，66.59；H，8.19；N，5.42.Found：C，66.45；H，8.21；N，5.22％.
Embodiment 7
Synthetic complex compound C3
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(3; 5-di-t-butyl-2-hydroxybenzyl)-N; N '-dimethylated propyl diethylenetriamine (L4) (0.441g); toluene 20mL, adds Zn[Si (NMe under room temperature 3) 2] 2(0.385g), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and after a couple of days, easily precipitates white powder material 476mg, and productive rate is 71.58%.
1H?NMR(C 6D 6，400MHz)：δ7.62(s，1H，J＝2.4Hz，ArH)，7.09-7.01(m，1H，ArH)，6.92(d，1H，J＝2.4Hz，ArH)，6.85(d，1H，J＝2.4Hz，ArH)，6.74(t，1H，J＝7.2Hz，ArH)，6.44(d，1H，J＝8.0Hz，ArH)，4.32-4.30(m，2H，Ar-CH 2N)，4.29-4.27(m，1H，NCH 2-Ar)，3.18(s，3H，OCH 3)，2.78-2.73(m，2H，CH 2CH 2CH 2)，2.39-2.36(m，1H，NCH 2-Ar)，2.19(s，3H，NCH 3)，2.10(s，3H，NCH3)，1.81(s，9H，C(CH 3) 3，1.60-1.55(m，1H，NCH 2CH 2CH 2N)，1.45(s，9H，C(CH 3) 3，1.29-1.12(m，2H，NCH 2CH 2CH 2N)，0.78-0.73(m，1H，NCH 2CH 2CH 2N)，0.48(s，1H，N(Si(CH 3) 3) 2)；Anal.Calc.for?C 34H 62N 3O 2Si 2Zn·1/3tol：C，62.53；H，9.18；N，6.08.Found：C，62.60；H，8.67；N，5.67％.
Embodiment 8
Synthetic complex compound C4
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(the chloro-2-hydroxybenzyl of 3,5-bis-)-N, N '-dimethyl-ethylenediamine (L1) (0.383g); toluene 20mL, adds Mg[Si (NMe under room temperature 3) 2] 2(0.345g), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and after a couple of days, obtains white general light flesh pink solid 296mg, and productive rate is 52.02%.
1H?NMR(C 6D 6，400MHz)：δ7.52(d，1H，J＝2.0Hz，ArH)，6.96(t，1H，J＝7.2Hz，ArH)，6.79(d，1H，J＝2.0Hz，ArH)，6.76(d，1H，J＝7.6Hz，ArH)，6.70(t，1H，J＝7.2Hz，ArH)，6.56(d，1H，J＝7.2Hz，ArH)，4.21(dd，2H，J 1＝12.0Hz，J 2＝8.0Hz，NCH 2-Ar)，4.14(s，3H，OCH 3)，2.43(d，1H，J＝12.0Hz，Ar-CH 2N)，2.30(td，1H，J 1＝12.8Hz，J 2＝4.0Hz，NCH 2CH 2N)，2.14(s，3H，NCH 3)，2.10(d，1H，J＝12.0Hz，Ar-CH 2N)，1.89(dd，1H，J 1＝14.4Hz，J 2＝1.8Hz，NCH 2CH 2N)，1.77(td，1H，J 1＝14.0Hz，J 2＝2.4Hz，NCH 2CH 2N)，1.36(s，3H，NCH 3)，0.92(dd，1H，J 1＝12.8Hz，J 2＝2.4Hz，NCH 2CH 2N)，0.263(s，18H，N(Si(CH 3) 3) 2)；Anal.Calc.for?C 25H 41C 12MgN 3O 2Si 2：C，52.96；H，7.29；N，7.41.Found：C，52.65；H，7.07；N，7.17％.
Embodiment 9
Synthetic complex compound C5
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(3; 5-di-t-butyl)-2-hydroxybenzyl)-N; N '-dimethyl-ethylenediamine (L2) (0.426g); toluene 20mL, adds Mg[Si (NMe under room temperature 3) 2] 2(0.345g), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and after a couple of days, obtains water white transparency styloid, drains to obtain white general faint yellow solid 201mg, and productive rate is 32.11%.
1H?NMR(C 6D 6，400MHz)：δ7.74(s，1H，ArH)，7.27(s，1H，ArH)，7.09(t，1H，J＝8.4Hz，ArH)，6.91(d，1H，J＝8.4Hz，ArH)，6.78(t，1H，J＝7.2Hz，ArH)，6.66(t，1H，J＝7.2Hz，ArH)，4.63(d，1H，J＝12.0Hz，Ar-NCH 2)，4.45(d，1H，J＝12.0Hz，Ar-CH 2N)，4.27(s，3H，OCH 3)，2.96(d，1H，J＝12.0Hz，Ar-CH 2N)，2.78(t.1H，J＝12.4Hz，NCH 2CH 2N)，2.54(dd，1H，J 1＝14.4Hz，J 2＝2.4Hz，NCH 2CH 2N)，2.41(s，3H，NCH 3)，2.02(t，1H，J＝12.4Hz，NCH 2CH 2N)，1.84(s，9H，C(CH 3) 3)，1.59(s，9H，C(CH 3) 3)，1.57(s，3H，NCH 3)，1.09(d，1H，J＝12.0Hz，NCH 2CH 2N)，0.42(s，18H，N(Si(CH 3) 3) 2)；Anal.Calc.for?C 33H 59MgN 3O 2Si 2：C，64.74；H，9.74；N，6.78.Found：C，65.20；H，9.81；N，6.78.
Embodiment 10
Synthetic complex compound C6
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(3; 5-di-t-butyl)-2-hydroxybenzyl)-N; N '-dimethyl-ethylenediamine (L2) (0.426g); toluene 20mL, adds Mg[N (SiHMe under room temperature 2) 2] 2(0.289g, 1.00mmol), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and after a couple of days, obtains water white transparency styloid, drains to obtain white general faint yellow solid 330mg, and productive rate is 77.35%.
1H?NMR(C 6D 6，400MHz)：δ7.40(d，1H，J＝2.4Hz，ArH)，7.00(d，2H，J＝2.8Hz，ArH)，6.73(t，1H，J＝8.4Hz，ArH)，6.67(t，1H，J＝14.3Hz，ArH)，6.52(d，1H，J＝14.3Hz，ArH)，4.40(d，1H，J＝12.0Hz，Ar-NCH 2)，4.14(s，3H，OCH 3)，4.08(d，1H，J＝12.0Hz，Ar-N?CH 2)，2.79(d，1H，J＝12.0Hz，Ar-NCH 2)，2.50-2.37(m，3H，NCH 2CH 2N)，2.31(s，3H，NCH 3)，2.14(d，1H，J＝12.0Hz，Ar-NCH 2)，1.95-1.77(m，1H，NCH 2CH 2N)，1.71(s，9H，C(CH 3) 3)，1.57(s，3H，NCH 3)，1.50(s，9H，C(CH 3) 3)，0.45(s，3H，N(SiH(CH 3) 2) 2)，0.44(s，3H，N(SiH(CH 3) 2) 2)，0.41(s，3H，N(SiH(CH 3) 2) 2)，0.40(s，3H，N(SiH(CH 3) 2) 2)； 13C?NMR(C 6D 6，100MHz)：164.6，157.5，136.9，133.9，131.8，130.3，126.1，124.3，124.1，123.1，122.4，113.7，(All，Ar-C)，66.0(OCH 3)，60.9(Ar-CH 2N)，59.6(NCH 2-Ar)，59.1(NCH 2CH 2N)，51.8(NCH 2CH 2N)，49.3(NCH 3)，41.3(NCH 3)，35.5(C(CH 3) 3)，34.2(C(CH 3) 3)，32.5(C(CH 3) 3)，30.2(C(CH 3) 3)，4.8(N(SiH(CH 3) 2) 2)，4.7(N(SiH(CH 3) 2) 2).Anal.Calcd.for?C 31H 55MgN 3O 2Si 2：C，63.95；H，9.52；N，7.22.Found：C，63.84；H，9.30；N，7.21％.
Embodiment 11
Synthetic complex compound C7
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(3; 5-dicumyl)-2-hydroxybenzyl)-N; N '-dimethyl-ethylenediamine (L3) (0.551g); toluene 20mL, adds Mg[Si (NMe under room temperature 3) 2] 2(0.345g), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and after a couple of days, obtains water white transparency styloid, drains to obtain white general faint yellow solid 370mg, and productive rate is 49.33%.
1H?NMR(C 6D 6，400MHz)：δ7.67(d，1H，J＝2.8Hz，ArH)，7.44(dd，2H，J 1＝8.4Hz，J 2＝1.2Hz，ArH)，7.30(dd，2H，J＝8.4Hz，J＝1.6Hz，ArH)，7.21(t，2H，J＝7.6Hz，ArH)，7.09(tt，1H，J＝7.2Hz，J＝1.2Hz，ArH)，6.99(td，1H，J 1＝7.2Hz，J 2＝1.2Hz，ArH)，6.93(d，1H，J＝2.8Hz，ArH)，6.80-6.68(m，4H，ArH)，6.63(t，1H，J＝7.2Hz，ArH)，6.47(dd，1H，J 1＝7.2Hz，J 2＝1.2Hz，ArH)，4.40(d，1H，J＝12.4Hz，Ar-NCH 2)，4.02(s，3H，OCH 3)，2.74(d，1H，J＝12.8Hz，Ar-CH 2N)，2.29(d，1H，J＝12.4Hz，N-CH 2Ar)，2.17(s.3H，NCH 3)，2.13(s.3H，NCH 3)，2.34-2.13(m，2H，NCH 2CH 2N)，1.83(s.3H，C(CH 3) 2Ph)，1.82(s.1H，C(CH 3) 2Ph)，1.79-1.74(m，1H，NCH 2CH 2N)，1.64(s.3H，C(CH 3) 2Ph)，1.57(d，1H，J＝12.4Hz，N-CH 2Ar)，1.32(s，3H，C(CH 3) 2Ph)，0.85-0.81(m，1H，NCH 2CH 2N)，0.24(s，1H，N(Si(CH 3) 3) 2)；Anal.Calc.for?C 43H 63MgN 3O 2Si 2：C，70.32；H，8.65；N，5.72.Found：C，69.84；H，8.56；N，5.58％.
Embodiment 12
Synthetic complex compound C8
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(3; 5-di-t-butyl)-2-hydroxybenzyl)-N; N '-dimethylated propyl diethylenetriamine (L4) (0.441g); toluene 20mL, adds Mg[Si (NMe under room temperature 3) 2] 2(0.345g), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and after a couple of days, obtains water white transparency styloid, drains to obtain white solid 294mg, and productive rate is 45.94%.
1H?NMR(toluene-d 8，400MHz，348K)：δ7.51(d，1H，ArH)，6.85(d，1H，J＝12.0Hz，ArH)，6.85(td，1H，J 1＝5.2Hz，J 2＝0.8Hz，ArH)，6.57(d，1H，J＝8Hz，ArH)，4.27(d，1H，J＝12.8Hz，Ar-CH 2N)，4.14(d，1H，J＝13.2Hz，NCH 2-Ar)，3.97(d，1H，J＝12.8Hz，Ar-CH 2N)，3.44(s，3H，OCH 3)，3.00(d，1H，J＝13.2Hz，NCH 2-Ar)，2.69(t，1H，J＝12.4Hz，NCH 2CH 2CH 2N)，2.48-2.38(m.1H，NCH 2CH 2CH 2N)，2.22(s，3H，NCH 3)，2.16(s，3H，NCH 3)，2.11-2.09(m.2H，NCH 2CH 2CH 2N)，1.76-1.70(m，1H，NCH 2CH 2CH 2N)，1.69(s，9H，C(CH 3) 3)，1.41(s，9H，C(CH 3) 3，1.09-0.95(m，1H，NCH 2CH 2CH 2N)，0.357(s，18H，N(Si(CH 3) 3) 2)； 13C?NMR(C 6D 6，100MHz)：162.6，158.9，158.9，137.7，134.5，133.7，130.4，129.3(tol.)，128.6(tol.)，125.8，125.7(tol.)，124.5，122.1，121.0，112.1，(All，Ar-C)，66.1(OCH 3)，59.0(Ar-CH 2N)，56.7(NCH 2-Ar)，55.3(NCH 2CH 2CH 2N)，54.0(NCH 2CH 2CH 2N)，46.2(NCH 3)，42.3(NCH 3)，35.6(C(CH 3) 3)，34.2(C(CH 3) 3)，32.4(C(CH 3) 3)，32.0(hex.)，30.1(C(CH 3) 3)，23.1(hex.)，21.7(NCH 2CH 2CH 2N)，21.5(tol.)，14.4(hex.)，7.5(N(Si(CH 3) 3) 2).Anal.Calcd.for?C 34H 61MgN 3O 2Si 2：C，65.41；H，9.85；N，6.73.Found：C，65.36；H，9.83；N，6.56％.
Embodiment 13
Synthetic complex compound C9
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(3; 5-di-t-butyl)-2-hydroxybenzyl)-N; N '-dimethyl-ethylenediamine (L2) (0.441g); toluene 20mL, adds Ca[N (SiMe under room temperature 3) 2] 2(THF) 2(0.504g, 1.00mmol), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and after a couple of days, obtains water white transparency styloid, drains to obtain white solid 395mg, and productive rate is 63.20%.
1H?NMR(C 6D 6，400MHz)：δ7.51(d，1H，J＝2.8Hz，ArH)，6.85(d，1H，J＝2.4Hz，ArH)，6.76(td，1H，J 1＝5.2Hz，J 2＝1.2Hz，ArH)，6.65(t，1H，J＝7.6Hz，ArH)，6.57(d，1H，J＝8.0Hz，ArH)，6.50(dd，1H，J 1＝7.6Hz，J 1＝1.2Hz，ArH)，4.13-4.05(m，1H，J＝12.4Hz，Ar-NCH 2)，3.96(s，3H，OCH 3)，3.78(d，1H，J＝12.0Hz，N-CH 2Ar)，2.91(d，1H，J＝12.0Hz，Ar-NCH 2)，2.40-2.36(m，2H，NCH 2CH 2N)2.13-2.10(m，4H，NCH 3?and?N-CH 2Ar)，1.88-1.75(m，2H，NCH 2CH 2N)，1.75(s，9H，C(CH 3) 3)，1.50(s，9H，C(CH 3) 3)，1.47(s，3H，NCH 3)，0.29(s，18H，N(Si(CH 3) 3)2)； 13C?NMR(C 6D 6，100MHz)：165.3，156.5，136.9，133.2，130.7，126.6，124.8，124.3，123.6，123.1，114.2(All，Ar-C)，65.8(OCH 3)，59.6(Ar-CH 2N)，59.4(NCH 2-Ar)，58.8(NCH 2CH 2N)，52.7(NCH 2CH 2N)，46.7(NCH 3)，41.2(NCH 3)，35.6(C(CH 3) 3)，34.2(C(CH 3) 3)，32.5(C(CH 3) 3)，30.3(C(CH 3) 3)，6.2(N(Si(CH 3) 3) 2)；Anal.Calc.for?C 33H 59CaN 3O 2Si 2·3/8Tol：C，64.53；H，9.52；N，6.40；Found：C，64.54；H，9.21；N，6.52％.
Embodiment 14
Synthetic complex compound C10
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(3; 5-dicumyl)-2-hydroxybenzyl)-N; N '-dimethyl-ethylenediamine (L3) (0.551g); toluene 20mL, adds Ca[N (SiMe under room temperature 3) 2] 2(THF) 2(0.505g), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and after a couple of days, obtains water white transparency styloid, drains to obtain white general faint yellow solid 408mg, and productive rate is 53.33%.
1H?NMR(C 6D 6，400MHz)：δ7.66(d，1H，J＝2.4Hz，ArH)，7.47(d，2H，J＝7.2Hz，ArH)，7.43(d，2H，J＝7.6Hz，ArH)，7.23(t，2H，J＝7.6Hz，ArH)，7.12-7.10(m，1H，ArH)，6.94-6.87(m，4H，ArH)，6.69-6.60(m，2H，ArH)，6.53-6.50(m，2H，ArH)，3.85-3.64(m，1H，J＝12.4Hz，Ar-NCH 2)，3.64(s，3H，OCH 3)，2.78(d，1H，J＝12.0Hz，N-CH 2Ar)，2.57(d，1H，J＝12.4Hz，Ar-NCH 2)，2.16(s，3H，C(CH 3) 2Ph)，2.16-2.13(m，1H，N-CH 2Ar)，2.11-2.09(m，2H，NCH 2CH 2N)，2.00(s，3H，NCH 3)，1.84(s，6H，C(CH 3) 2Ph)，1.79-1.77(m，1H，NCH 2CH 2N)1.69(s，3H，NCH 3)，1.45-1.43(m，3H，C(CH 3) 2Ph)，0.36-0.35(m，1H，NCH 2CH 2N)，0.24(s，18H，N(Si(CH 3) 3) 2)；Anal.Calc.for?C 43H 63CaN 3O 2Si 2·0.33tol：C，69.57；H，8.36；N，5.45.Found：C，69.78；H，8.82；N，5.11％.
Embodiment 15
Synthetic complex compound C11
Under argon shield; in 100mL Schlenk bottle, add N-(2-methoxy-benzyl)-N '-(3; 5-di-t-butyl)-2-hydroxybenzyl)-N; N '-dimethylated propyl diethylenetriamine (L4) (0.441g); toluene 20mL, adds Ca[N (SiMe under room temperature 3) 2] 2(THF) 2(0.505g), stirring at room temperature 24h, puts into-20 DEG C of refrigerators after concentrating, and after a couple of days, obtains water white transparency styloid, drains to obtain white general faint yellow solid 408mg, and productive rate is 53.33%.
1H?NMR(C 6D 6，400MHz)：δ7.63(d，1H，J＝2.4Hz，ArH)，7.15(s，1H，ArH)，7.06(d，1H，J＝2.4Hz，ArH)，7.01-6.95(m，1H，ArH)，6.69(t，1H，J＝7.2Hz，ArH)，6.64(d，1H，J＝8.4Hz，ArH)，6.60(d，1H，J＝7.6Hz，ArH)，4.56(d，4H，J＝12.4Hz，Ar-NCH 2)，4.09(d，1H，J＝12.0Hz，N-CH 2Ar)，4.04(s，3H，OCH 3)，2.90(d，1H，J＝12.4Hz，Ar-NCH 2)，2.71(t，1H，J＝8.4Hz，NCH 2CH 2CH 2N)，2.59(d，1H，J＝12.0Hz，N-CH 2Ar)，2.39-2.32(m，1H，NCH 2CH 2CH 2N)，2.20(s.3H，NCH 3)，1.82(s，9H，C(CH 3) 3)，1.62-1.47(m，1H，NCH 2CH 2CH 2N)，1.47(s，9H，C(CH 3) 3)，1.44(s.3H，NCH 3)，1.38(d.1H，J＝13.2Hz，NCH 2CH 2CH 2N)，1.12-1.02(m，1H，NCH 2CH 2CH 2N)，0.69-0.62(m.1H，NCH 2CH 2CH 2N)，0.276(s，18H，N(Si(CH 3) 3) 2)； 13C?NMR(C 6D 6，100MHz)：164.6，156.7，136.4，133.6，133.2，130.9，129.3(tol.)，128.6(tol.)，126.8，125.7(tol)，124.3，124.1，123.4，123.0，114.6(All，Ar-C)，65.4(OCH 3)，61.4(Ar-CH 2N)，61.5(NCH 2-Ar)，60.2(NCH 2CH 2CH 2N)，55.4(NCH 2CH 2CH 2N)，43.2(NCH 3)，41.7(NCH 3)，35.7(C(CH 3) 2)，34.2(C(CH 3) 2，32.5(C(CH 3) 2)，32.0(hex.)，30.6(C(CH 3) 2)，23.1(hex.)，22.4(NCH 2CH 2CH 2N)，14.4(hex.)，6.8(N(Si(CH 3) 3) 2)；Anal.Calcd.for?C 34H 61CaN 3O 2Si 2：C，63.80；H，9.61；N，6.56.Found：C，63.77；H，9.68；N，6.53％.
Embodiment 14
Under argon shield, in 20mL 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, [Zn] 0=0.005M, [Zn] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 5min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 90%, number-average molecular weight 9.15 × 10 4g/mol, PDI=1.44, assorted normality P r=0.55.
Embodiment 15
Under argon shield, in 20mL 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, [Zn] 0=0.005M, [Zn] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 8min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 85%, number-average molecular weight 6.76 × 10 4g/mol, PDI=2.19, assorted normality P r=0.52.
Embodiment 16
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Zn] 0=0.005M, [Zn] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 3min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 97%, number-average molecular weight 1.88 × 10 4g/mol, PDI=1.49, assorted normality P r=0.53.
Embodiment 17
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C1 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Zn] 0=0.005M, [Zn] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 3min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 96%, number-average molecular weight 3.14 × 10 4g/mol, PDI=1.48, assorted normality P r=0.51.
Embodiment 18
Under argon shield, in 20mL 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, [Zn] 0=0.005M, [Zn] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 15min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 92%, number-average molecular weight 3.66 × 10 4g/mol, PDI=1.75, degree of isotacticity P m=0.53.
Embodiment 19
Under argon shield, in 20mL 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, [Zn] 0=0.005M, [Zn] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 40min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 98%, number-average molecular weight 3.26 × 10 4g/mol, PDI=3.34, degree of isotacticity P m=0.55.
Embodiment 20
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Zn] 0=0.005M, [Zn] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 5min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 89%, number-average molecular weight 2.10 × 10 4g/mol, PDI=1.72, degree of isotacticity P m=0.52.
Embodiment 21
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Zn] 0=0.005M, [Zn] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 8min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 98%, number-average molecular weight 2.04 × 10 4g/mol, PDI=1.74, degree of isotacticity P m=0.56.
Embodiment 22
Under argon shield, in 20mL 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, [Zn] 0=0.005M, [Zn] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 60min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 44%, number-average molecular weight 4.10 × 10 4g/mol, PDI=1.66, assorted normality P r=0.62.
Embodiment 23
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C3 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Zn] 0=0.005M, [Zn] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 1680min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 78%, number-average molecular weight 6.38 × 10 4g/mol, PDI=1.58, degree of isotacticity P m=0.51.
Embodiment 24
Under argon shield, in 20mL 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, [Zn] 0=0.005M, [Zn] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 45min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 78%, number-average molecular weight 1.90 × 10 4g/mol, PDI=1.24, assorted normality P r=0.63.
Embodiment 25
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C3 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Zn] 0=0.005M, [Zn] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 45min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 85%, assorted normality P r=0.55.
Embodiment 26
Under argon shield, in 20mL 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 temperature reaction 30min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 91%, number-average molecular weight 3.86 × 10 4g/mol, PDI=1.66, assorted normality P r=0.62.
Embodiment 27
Under argon shield, in 20mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene 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 temperature reaction 105min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 96%, number-average molecular weight 2.69 × 10 4g/mol, PDI=1.66, degree of isotacticity P m=0.56.
Embodiment 28
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C4 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Mg] 0=0.005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 10min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 58%, number-average molecular weight 1.49 × 10 4g/mol, PDI=1.28, assorted normality P r=0.61.
Embodiment 29
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C4 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Mg] 0=0.005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 15min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 98%, number-average molecular weight 1.65 × 10 4g/mol, PDI=1.46, degree of isotacticity P m=0.55.
Embodiment 30
Under argon shield, in 20mL bottle, add the toluene solution of 1mmol rac-rac-Lactide, the toluene solution of 1mL Virahol, the toluene solution 1mL of the described catalyzer C4 that reinjects, [rac-LA] 0=0.5M, [ iprOH] 0=0.005M, [Mg] 0=0.0005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 1000, stirring at room temperature reaction 30min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 98%.
Embodiment 31
Under argon shield, in 20mL bottle, add 2mmol caprolactone, the toluene solution of 1mL Virahol, the toluene solution 1mL of the described catalyzer C4 that reinjects, [ε-CL] 0=1.0M, [ iprOH] 0=0.0005M, [Mg] 0=0.0005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 2000, stirring at room temperature reaction 1h.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 97%.
Embodiment 32
Under argon shield, in 25mL Schlenk bottle, add 2.5mmol 6-caprolactone, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C4 that reinjects, [Mg] 0: [ iprOH] 0: [ε-CL] 0=1: 1: 10000,130 DEG C of stirring reaction 2h.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 43%.
Embodiment 33
Under argon shield, in 20mL 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 temperature reaction 5min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 84%, number-average molecular weight 4.51 × 10 4g/mol, PDI=2.17, assorted normality P r=0.55.
Embodiment 34
Under argon shield, in 20mL 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 temperature reaction 25min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 97%, number-average molecular weight 3.85 × 10 4g/mol, PDI=2.10, degree of isotacticity P m=0.55.
Embodiment 35
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C5 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Mg] 0=0.005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 1min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 96%, number-average molecular weight 2.77 × 10 4g/mol, PDI=1.35, assorted normality P r=0.55.
Embodiment 36
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C5 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Mg] 0=0.005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 10min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 99%, number-average molecular weight 2.46 × 10 4g/mol, PDI=1.88, degree of isotacticity P m=0.56.
Embodiment 37
Under argon shield, in 20mL bottle, add the toluene solution of 0.5mL L-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C5 that reinjects, [L-LA] 0=1.0M, [Mg] 0=0.005M, [Mg] 0: [L-LA] 0=1: 200, stirring at room temperature reaction 10min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 95%.
Embodiment 38
Under argon shield, in 20mL bottle, add the toluene solution of the 6-caprolactone of 0.5mL 2M, the toluene solution 0.5mL of the described catalyzer C5 that reinjects, [ε-CL] 0=1.0M, [Mg] 0=0.005M, [Mg] 0: [ε-CL] 0=1: 200, stirring at room temperature reaction 10min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 98%.
Embodiment 39
Under argon shield, in 20mL bottle, add the toluene solution of the 6-caprolactone of 0.5mL 2M, the toluene solution 0.5mL of the described catalyzer C5 that reinjects, [ε-CL] 0=1.0M, [Mg] 0=0.005M, [Mg] 0: [ε-CL] 0=1: 200, stirring at room temperature is reacted 10min, then adds the rac-rac-Lactide of 1mmol, stirring at room temperature 20min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.6-caprolactone transformation efficiency is 99%, rac-lactide conversions 94%.
Embodiment 40
Under argon shield, in 20mL 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 temperature reaction 15min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 80%.
Embodiment 41
Under argon shield, in 20mL 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 temperature reaction 30min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 92%.
Embodiment 42
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C6 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Mg] 0=0.005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 5min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 96%.
Embodiment 43
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C6 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Mg] 0=0.005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 10min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 83%.
Embodiment 44
Under argon shield, in 20mL 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 temperature reaction 1min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 96%, number-average molecular weight 1.22 × 10 4g/mol, PDI=1.59, assorted normality P r=0.57.
Embodiment 45
Under argon shield, in 20mL 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 temperature reaction 20min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 98%, number-average molecular weight 3.01 × 10 4g/mol, PDI=2.08, degree of isotacticity P m=0.56.
Embodiment 46
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C7 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Mg] 0=0.005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 1min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 96%, number-average molecular weight 1.22 × 10 4g/mol, PDI=1.59, assorted normality P r=0.57.
Embodiment 47
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C7 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Mg] 0=0.005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 5min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 99%, number-average molecular weight 2.50 × 10 4g/mol, PDI=1.64, degree of isotacticity P m=0.55.
Embodiment 48
Under argon shield, in 20mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C8 that reinjects, [rac-LA] 0=1.0M, [Mg] 0=0.005M, [Mg] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 60min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 85%, number-average molecular weight 0.92 × 10 4g/mol, PDI=3.00, assorted normality P r=0.66.
Embodiment 49
Under argon shield, in 20mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C8 that reinjects, [rac-LA] 0=1.0M, [Mg] 0=0.005M, [Mg] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 2190min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 84%, number-average molecular weight 0.97 × 10 4g/mol, PDI=2.03, degree of isotacticity P m=0.52.
Embodiment 50
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C8 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Mg] 0=0.005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 5min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 97%, number-average molecular weight 2.79 × 10 4g/mol, PDI=1.57, assorted normality P r=0.65.
Embodiment 51
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C8 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Mg] 0=0.005M, [Mg] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 20min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 96%, number-average molecular weight 1.84 × 10 4g/mol, PDI=2.03, degree of isotacticity P m=0.58.
Embodiment 52
Under argon shield, in 20mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C9 that reinjects, [rac-LA] 0=1.0M, [Ca] 0=0.005M, [Ca] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 20min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 42%.
Embodiment 53
Under argon shield, in 20mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C9 that reinjects, [rac-LA] 0=1.0M, [Ca] 0=0.005M, [Ca] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 60min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 79%.
Embodiment 54
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C9 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Ca] 0=0.005M, [Ca] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 10min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 99%.
Embodiment 55
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C9 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Ca] 0=0.005M, [Ca] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 10min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 96%, number-average molecular weight 1.84 × 10 4g/mol, PDI=2.03, degree of isotacticity P m=0.58.
Embodiment 56
Under argon shield, in 20mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C10 that reinjects, [rac-LA] 0=1.0M, [Ca] 0=0.005M, [Ca] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 3min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 73%, degree of isotacticity P m=0.54.
Embodiment 57
Under argon shield, in 20mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C10 that reinjects, [rac-LA] 0=1.0M, [Ca] 0=0.005M, [Ca] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 20min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 80%, degree of isotacticity P m=0.53.
Embodiment 58
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C10 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Ca] 0=0.005M, [Ca] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 3min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 95%, degree of isotacticity P m=0.55.
Embodiment 59
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C10 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Ca] 0=0.005M, [Ca] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 10min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 93%, number-average molecular weight 1.84 × 10 4g/mol, PDI=2.03, degree of isotacticity P m=0.53.
Embodiment 60
Under argon shield, in 20mL bottle, add the THF solution of 0.5mL rac-rac-Lactide, the THF solution 0.5mL of the described catalyzer C11 that reinjects, [rac-LA] 0=1.0M, [Ca] 0=0.005M, [Ca] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 60min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 50%, assorted normality P r=0.53.
Embodiment 61
Under argon shield, in 20mL bottle, add the toluene solution of 0.5mL rac-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C11 that reinjects, [rac-LA] 0=1.0M, [Ca] 0=0.005M, [Ca] 0: [rac-LA] 0=1: 200, stirring at room temperature reaction 5760min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 84%, degree of isotacticity P m=0.55.
Embodiment 62
Under argon shield, in 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the THF solution of 0.1mL Virahol, the THF solution 0.5mL of the described catalyzer C11 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Ca] 0=0.005M, [Ca] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 10min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 57%, degree of isotacticity P m=0.53.
Embodiment 63
Under argon shield, in 20mL bottle, add the toluene solution of 0.4mL rac-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C11 that reinjects, [rac-LA] 0=1.0M, [ iprOH] 0=0.005M, [Ca] 0=0.005M, [Ca] 0: [ iprOH] 0: [rac-LA] 0=1: 1: 200, stirring at room temperature reaction 15min.By wet oil ether termination reaction, after filtration by polymkeric substance at 60 DEG C of vacuum-drying 16h.Monomer conversion 89%, degree of isotacticity P m=0.53.

Claims (10)

  1. The one mono-phenols part of kind salan (I) and with the complex compound of metallic zinc (II), magnesium (III), calcium (III), it is characterized in that thering is following general formula:
    In formula (I), (II), (III):
    R 1～R 2represent respectively hydrogen, C 1～C 20the alkyl of straight chain, branched structure, C 7～C 30the alkyl that list or polyaryl replace, halogen;
    R 3～R 4for methyl;
    X is methoxyl group;
    R 5for ethylidene or propylidene;
    R 6represent C 1～C 4alkyl, two (trimethyl silicon based) amido, two (dimethyl is silica-based) amido, isopropoxy.
  2. The mono-phenols part of class salan according to claim 1 (I) and with the complex compound of metallic zinc (II), magnesium (III), calcium (III), it is characterized in that R 1～R 2for hydrogen, C 1～C 10the alkyl of straight chain, branched structure, C 7～C 20the alkyl that list or polyaryl replace, halogen.
  3. The mono-phenols part of class salan according to claim 1 (I) and with the complex compound of metallic zinc (II), magnesium (III), calcium (III), it is characterized in that R 1～R 2be preferably hydrogen, methyl, the tertiary butyl, cumyl, chlorine.
  4. 4. the preparation method of the mono-phenols part of the class salan described in claim 1～3 any one (I) and metallic zinc complex compound (II) thereof, magnesium complex (III), calcium complex (III), comprises the steps:
    Be there is to western Buddhist alkali reaction in the diamines shown in the aromatic aldehyde shown in formula (IV) and formula (V), add again reductive agent reduction to obtain after new single secondary amine (VI), add and replace brooethyl phenol (VII), temperature of reaction is 60～75 DEG C, react 8～48 hours, then from reaction product, collect compound (I);
    The mono-phenols ligand compound of class salan shown in formula (I) is reacted in organic medium with zinc, magnesium, calcium organometallics, generate the mono-phenol oxygen of class salan base zinc, magnesium, calcium cpd, temperature of reaction is-10～80 DEG C, react 24～48 hours, then from reaction product, collect target compound (II) or (III).
  5. 5. method according to claim 4, is characterized in that, reductive agent is preferably sodium borohydride; Described organic medium is selected from one or both in tetrahydrofuran (THF), ether, glycol dimethyl ether, toluene, normal hexane and sherwood oil.
  6. 6. method according to claim 4, is characterized in that, zinc, magnesium, calcium organometallics are preferably respectively two [two (trimethyl silicon based) amido] zinc; Dibutyl magnesium, two [two (dimethyl is silica-based) amido] magnesium or two [two (trimethyl silicon based) amido] magnesium; Two (tetrahydrofuran (THF)s) close { two [two (trimethyl silicon based) amido] } calcium; The mono-phenols ligand compound of class salan and these metal-organic mol ratios are: 1: 0.5～1: 1.5.
  7. 7. the application of the mono-phenol oxygen of the class salan base zinc described in claim 1～3 any one, magnesium, calcium cpd, is characterized in that, for catalyzing lactone as open loop homopolymerization or the copolymerization of 6-caprolactone, rac-Lactide.
  8. 8. application according to claim 7, is characterized in that, taking the mono-phenol oxygen of the class salan described in claim 1～3 any one base zinc, magnesium, calcium cpd as catalyzer, alcohol exist under or do not add alcohol, make 6-caprolactone polymerization under the condition of-39～130 DEG C; Polymerization solvent used is selected from one or both in toluene, sherwood oil, normal hexane, tetrahydrofuran (THF), ether, glycol dimethyl ether, methylene dichloride or chloroform, or does not use solvent; Described alcohol is methyl alcohol, ethanol, Virahol, the trimethyl carbinol, benzylalcohol.
  9. 9. application according to claim 7, is characterized in that, taking the mono-phenol oxygen of the class salan described in claim 1～3 any one base zinc, magnesium, calcium cpd as catalyzer, alcohol exist under or do not add alcohol, make rac-Lactide polymerization under-39～130 DEG C of conditions; Polymerization solvent used is selected from one or both in toluene, sherwood oil, normal hexane, tetrahydrofuran (THF), ether, glycol dimethyl ether, methylene dichloride or chloroform, or does not use solvent; Described alcohol is methyl alcohol, ethanol, Virahol, the trimethyl carbinol, benzylalcohol.
  10. 10. application according to claim 7, it is characterized in that, taking the mono-phenol oxygen of the class salan described in claim 1～3 any one base zinc, magnesium, calcium complex as catalyzer, alcohol exist under or do not add alcohol, make the copolymerization under-39～130 DEG C of conditions of 6-caprolactone and rac-Lactide; Polymerization solvent used is selected from one or both in toluene, sherwood oil, normal hexane, tetrahydrofuran (THF), ether, glycol dimethyl ether, methylene dichloride or chloroform, or does not use solvent; Described alcohol is methyl alcohol, ethanol, Virahol, the trimethyl carbinol, benzylalcohol.
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