CN102153597A - Asymmetric multi-hock type monophenoloxo magnesium complex as well as preparation method and application thereof - Google Patents

Asymmetric multi-hock type monophenoloxo magnesium complex as well as preparation method and application thereof Download PDF

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CN102153597A
CN102153597A CN2011100426369A CN201110042636A CN102153597A CN 102153597 A CN102153597 A CN 102153597A CN 2011100426369 A CN2011100426369 A CN 2011100426369A CN 201110042636 A CN201110042636 A CN 201110042636A CN 102153597 A CN102153597 A CN 102153597A
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magnesium
lactide
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马海燕
张星宇
宋绍迪
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East China University of Science and Technology
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Abstract

The invention discloses an asymmetric multi-hock type monophenoloxo magnesium complex as well as a preparation method and application thereof. The preparation method comprises the following steps: reacting an asymmetric multi-hock type monophenol ligand L with a magnesium metal organic compound; and then collecting a target product from crude reaction products. The magnesium complex disclosed by the invention contains the asymmetric multi-hock type monophenol ligand, is an efficient lactone ring-opening polymerized catalyst, and can be used for ring-opening polymerization of lactide, caprolactone and the like. The magnesium complex of the asymmetric multi-hock type monophenoloxo ligand has the obvious advantages of no toxicity and no innocuity, available raw materials, simple synthesis routes, relatively stable property and high catalytic activity, and is easy to separate and purify; and the polylactone obtained by catalysis has high molecular weight and can meet the demand of industrial departments. The structure of the complex has the following general formula shown in the specification.

Description

Asymmetric multiple tooth pawl type list phenol oxygen base magnesium complex and its production and application
Technical field
The present invention relates to the MAGNESIUM METAL complex compound that a class contains asymmetric multiple tooth pawl type list phenol oxygen ylidene ligands, and this class complex compound application in lactone ring opening polymerization.
Background technology
Because " white pollution " problem that the polyolefin product non-degradable brings is more and more serious, the Biodegradable polymeric material is regarded as environment amenable polyolefin product surrogate gradually.The seventies in 20th century, the researchist notices that the degradable poly ester material has the advantage of many polyolefin products that match in excellence or beauty, and begin gradually polyester material is applied to curable product such as aspect (Angew.Chem.Int.Ed. such as suture line, various medical support and medical fibre, 2004,43,1078).In the last thirty years, synthetic, produce and the processing degradable polyester aspect obtained the progress of advancing by leaps and bounds, the biodegradable polyesters material has been played important pushing effect from the widespread use of initial biological medicine device food Package material till now.
In the current polyester research field, polylactide and polycaprolactone and their multipolymer be study relative more several, have biodegradability, good biocompatibility, plasticity-, easy advantage such as machine-shaping, be regarded as the most promising Biodegradable material, in health care, all there is the potential using value in fields such as daily necessities, food product pack, clothes.
By the ring-opening polymerization of internal ester monomer in the presence of metal catalyst, can obtain high-molecular weight polylactide and polycaprolactone easily, the microtexture of resulting polymers and performance are then determined (Polym.Rev., 2008,48 by the stereoselectivity that catalyzer shows when the polymerization, 11), therefore, design synthesizing new metal complex catalyst is in order to realize the upright structure controllable polymerization of lactone open loop, make it to produce the polylactone of various special constructions and performance, become current research focus.Wherein, the magnesium metal complex is ring-opening polymerization of lactone by catalysis effectively, and magnesium metal ion look shallow, low toxicity, and exploitation magnesium metal complex catalyst still is that medical field is all significant to the environment protection cause.
1996, Chisholm group synthesized magnesium complex (Chem.Commun., 1996,853) with three pyrazolyl boron hydrogen hydride compounds and three indazolyl boron hydrogen hydride compounds as part, because the steric hindrance of part is bigger, has effectively suppressed the reunion of magnesium complex.The polymerization of this series magnesium complex catalysis L-rac-Lactide, resulting polymers molecular weight (M n) and transformation efficiency (below 90%) linear, and molecular weight distribution scope less (PDI=1.10-1.25) is indicated as controllable polymerization.2002, Coates has been combined into the magnesium complex (J.Am.Chem.Soc. that contains the beta-diimine part for a short time, 2002,124,15239), at 20 ℃, [Mg]: under [rac-LA]=1: 200 condition, just can make monomer all be converted into polylactide in two minutes, the zinc complex that contains with the spline structure part then needs 33 minutes, shows that the magnesium complex that contains the beta-diimine part has very high catalytic activity.The same year, Chisholm group has also synthesized the magnesium complex (Inorg.Chem. that contains the beta-diimine part, 2002,41,2785), cause the polymerization of rac-rac-Lactide in tetrahydrofuran (THF), same catalytic activity is also very high, can make monomer conversion reach 95% in 5 minutes, obtain the molecular weight distribution broad (PDI=1.47) of polymkeric substance.2005, people such as Lin generate magnesium complex (Polymer by steric hindrance bigger diphenols part and normal-butyl magnesium direct reaction in THF or ether solvent, 2005,46,5909), such magnesium complex is in the toluene that adds benzylalcohol, but the controllable polymerization of catalysis caprolactone, obtain the polymkeric substance (PDI=1.06-1.10) of narrow molecular weight distributions, when the polymerization of catalysis L-rac-Lactide, also can obtain the narrower polylactide of molecular weight distribution.
2009, Lin was combined into magnesium complex (Inorg.Chem., 2009 that contain NNO three tooth schiff base ligands for a short time, 48,728), polymerization has remarkably influenced to the substituting group on the Schiff's base to catalysis L-rac-Lactide, obtains the molecular weight distribution narrower (PDI=1.10) of polymkeric substance.2010, Otero has been combined into a series of magnesium complex (Inorg.Chem. that contain the tong-like cyclopentadienyl ligands for a short time, 2010,49,2859), the magnesium complex that wherein contains alkyl and alkoxyl group can be used as single active center's initiator efficiently, the various annular lactone generation of catalysis ring-opening polymerization in wide temperature range.Complex compound only needs several minutes just can obtain high molecular weight polymers when the ring-opening polymerization of catalysis caprolactone, obtains moderate molecular weight distribution (M n＞10 5, M w/ M n=1.45).Also can obtain the polymkeric substance of moderate molecular weight during the polymerization of complex catalysis rac-lactide, its molecular weight distribution then may diminish to M w/ M n=1.02.In addition, our group (CN101775042A) had also reported polydentate monophenoxy ligand magnesium complex in 2010, it has high catalytic activity, and resulting polymers has higher molecular weight and narrower molecular weight distribution, but its selectivity is general, only can the ring-opening polymerization of catalysis rac-lactide obtain showing slightly isotactic or the assorted partially PLA that advises.
In sum, the magnesium complex great majority of being reported at present are metal complexs of symmetric monokaryon or double-core, by end of the chain control carrying out polymerization, chain transfer or chain permutoid reaction take place in the polymerization process easily, and most these complex compounds are because the structure of part is more open, can not around metal center, form stable chirality coordination environment effectively and monomer coordination and insertion are not had selectivity, thereby obtain the polymkeric substance of random or assorted rule.People wish to develop active and selectivity is higher, cost is lower, can produce the compound with special purpose isotactic polymer, with the demand of polyisocyanate polyaddition production in satisfying.
Summary of the invention
One of the object of the invention is to disclose the complex compound of the asymmetric multiple tooth pawl type list phenol oxygen Base Metal magnesium of a class, to overcome the defective that prior art exists.
Two of the object of the invention is to disclose the preparation method of the complex compound of asymmetric multiple tooth pawl type list phenol oxygen Base Metal magnesium.
Three of the object of the invention is to disclose the complex compound of asymmetric multiple tooth pawl type list phenol oxygen Base Metal magnesium as the application of catalyzer in lactone ring opening polymerization.
Technical conceive of the present invention:
Compare with the divalent zinc positively charged ion, the divalence magnesium ion is the stronger positively charged ion of polarity, can more effectively activate the carbonyl (C=O) of lactone, therefore, the magnesium complex that contains the same structure part in theory should have higher catalytic activity than zinc complex aspect the ring-opening polymerization of lactone by catalysis.We use asymmetric multiple tooth pawl type list phenols part and introducing to have big sterically hindered initiating group, are expected to synthetic monokaryon phenol oxygen base magnesium complex with chiral metal center.By changing the substituting group on the part amido, on aromatic ring, introduce the length of different substituting groups and change carbochain and regulate part and metal center coordinate stability, the metal chirality still can effectively be kept under polymerizing condition, when polymerization, can discern chiral monomer better, thereby the raising stereoselectivity obtains the higher polylactone of degree of isotacticity.Experimental result shows that by changing ligand structure and polymerizing condition, this class magnesium compound can produce the polylactone that molecular weight is higher, molecular weight distribution is narrower, and the polymkeric substance degree of isotacticity is improved.
The complex compound of asymmetric multiple tooth pawl type list phenol oxygen Base Metal magnesium provided by the invention 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, branched structure, C 7～C 30The alkyl that list or polyaryl replace, halogen; X 1Be C 1～C 12The alkoxyl group of straight chain, branched structure, halogen; R 5Be ethylidene or propylidene; R 5During for ethylidene, X 2Be diethylin; R 5During for propylidene, X 2Be dimethylin; R 6Represent two (trimethyl silicon based) amido.
R 1～R 4Be hydrogen, C 1～C 10The alkyl of straight chain, branched structure, C 7～C 20The alkyl that list or polyaryl replace, halogen; X 1Be C 1～C 6The alkoxyl group of straight or branched structure, halogen.
R 1～R 4Be preferably hydrogen, methyl, the tertiary butyl, cumyl, trityl, halogen; X 1Be preferably methoxyl group, fluorine.
Preferred compound is:
Figure BSA00000437813700032
Complex compound (I) the preparation method following steps of asymmetric multiple tooth pawl type list phenol oxygen base magnesium of the present invention:
Figure BSA00000437813700042
Asymmetric multiple tooth pawl type list phenols ligand compound and magnesium organometallics shown in the formula (II) are reacted in organic medium, generate asymmetric multiple tooth pawl type list phenol oxygen base magnesium compound, temperature of reaction is-10～80 ℃, preferred 20～40 ℃, reaction times is 8～96 hours, preferred 24～48 hours, from reaction product, collect target compound (I) then.
Described magnesium organometallics preferred two [two (trimethyl silicon based) amido] magnesium.
Asymmetric multiple tooth pawl type list phenols ligand compound and the metal-organic mol ratio of magnesium are 1: 0.5～1.5, preferred 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 the sherwood oil.
The application of asymmetric multiple tooth pawl type list phenol oxygen base magnesium compound is characterized in that, is used for the open loop homopolymerization or the copolymerization of lactone such as 6-caprolactone, rac-Lactide.
Asymmetric multiple tooth pawl type list phenol oxygen base magnesium compound of the present invention is a kind of catalyzer of lactone ring opening polymerization efficiently, make lactone such as 6-caprolactone, rac-Lactide at-39～130 ℃, preferred 20～110 ℃ of following polymerizations, catalyzer and monomer mole ratio are 1: 1～10000 during polymerization.The used solvent of polymerization is toluene, sherwood oil, normal hexane, tetrahydrofuran (THF), ether, glycol dimethyl ether, methylene dichloride, chloroform or does not use any solvent.
Under the condition that alcohol exists, make lactone such as 6-caprolactone, rac-Lactide at-39～130 ℃, polymerization under preferred 20～110 ℃ of conditions, catalyzer is 1: 1～10: 1～10000 with alcohol and monomeric mol ratio during polymerization, and the used solvent of polymerization is toluene, sherwood oil, normal hexane, tetrahydrofuran (THF), ether, glycol dimethyl ether, methylene dichloride, chloroform or does not use any solvent.
In the presence of alcohol or do not add alcohol, make 6-caprolactone and rac-Lactide at-39～130 ℃, copolymerization under preferred 20～110 ℃ of conditions, the used solvent of polymerization 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-39～130 ℃, preferred 20～110 ℃ of polymerizations, and 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 5min～48h; Catalyzer and monomer mole ratio are 1: 1～10000 during polymerization, preferred 1: 200～2000, and when alcohol existed, catalyzer, alcohol and monomer mole ratio were 1: 1～50: 50～10000, preferred 1: 1～20: 100～5000.
Catalyzer provided by the invention is nontoxic, and raw material 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 high molecular and narrow distribution.Can satisfy the needs of industrial sector, have a wide range of applications.Further specify the present invention below by embodiment, but the invention is not restricted to this.
Embodiment
Embodiment 1
Synthetic complex compound C1
Figure BSA00000437813700051
Under argon shield, in 100mL Schlenk bottle, add 4,6-di-t-butyl-2-{N-(2-methoxy-benzyl)-N-[(N ', N '-diethylin) ethyl] aminomethyl } phenol (0.443g), toluene 20mL adds Mg[Si (NMe under the room temperature 3) 2] 2(0.345g), stirring at room 24h puts into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.387g, 60.7%).
1H?NMR(C 6D 6，400MHz)：δ7.60(d，1H，J＝2.4Hz，ArH)，7.14-7.12(m，1H，ArH)，7.07-7.03(m，1H，ArH)，6.92(d，1H，J＝2.4Hz，ArH)，6.81(td，1H，J 1＝7.2Hz，J 2＝0.8Hz，ArH)，6.44(d，1H，J＝8Hz，ArH)，4.36(d，1H，J＝13.6Hz，ArCH 2N)，4.06(d，1H，J＝13.6Hz，ArCH 2N)，3.88(d，1H，J＝12.8Hz，NCH 2Ar)，3.60(d，2H，J＝12.8Hz，NCH 2Ar)，3.18(s，3H，OCH 3)，2.53-2.33(m，7H，NCH 2CH 2N，NCH 2CH 2N，NCH 2CH 3)，2.15-2.10(m，1H，NCH 2CH 3)，1.82(s，9H，C(CH 3) 3)，1.37(s，9H，C(CH 3) 3)，0.70(t，6H，J＝7.2Hz，NCH 2CH 3)，1.72-1.70(m，6H，C(CH 3) 2Ph)，0.57-0.60(m，6H，NCH 2CH 3)，0.45(s，18H，Si(N(CH 3) 2) 3)；Anal.Calcd.for?C 35H 63MgN 3O 2Si 2[(1/2C 7H 8)]：C，67.56；H，9.87；N，6.14.Found：C，67.57；H，9.83；N，6.03％.
Embodiment 2
Synthetic complex compound C2
Figure BSA00000437813700061
Under argon shield, in 100mL Schlenk bottle, add 4,6-dicumyl-2-{N-(2-methoxy-benzyl)-N-[(N ', N '-diethylin) ethyl] aminomethyl } phenol (0.579g), toluene 20mL adds Mg[Si (NMe under the room temperature 3) 2] 2(0.345g), stirring at room 24h puts into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.444g, 58.4%).
1H?NMR(C 6D 6，400MHz)：δ7.62(s，1H，ArH)，7.57(d，2H，J＝6.8Hz，ArH)，7.37(d，2H，J＝7.2Hz，ArH)，7.16(s，3H，ArH)，7.09-7.00(m，4H，ArH)，6.92(d，1H，J＝6.8Hz，ArH)，6.84(s，1H，ArH)，6.72(t，1H，J＝7.2Hz，ArH)，6.42(d，1H，J＝8Hz，ArH)，4.47(d，1H，J＝13.6Hz，ArCH 2N)，3.87-3.84(m，1H，ArCH 2N)，3.72-3.57(m，2H，ArCH 2N)，3.08(s，3H，OCH 3)，2.42-2.38(m，1H，NCH 2CH 2N)，2.31-2.28(m，1H，NCH 2CH 2N)，2.25-2.12(m，6H，NCH 2CH 2N，NCH 2CH 3，C(CH 3) 2Ph)，2.08-2.03(m，1H，NCH 2CH 3)，1.95-1.93(m，2H，NCH 2CH 3)，1.80(s，3H，C(CH 3) 2Ph)，1.72-1.70(m，6H，C(CH 3) 2Ph)，0.57-0.60(m，6H，NCH 2CH 3)，0.45(s，18H，Si(N(CH 3) 2) 3).Anal.Calc.for?C 45H 67MgN 3O 2Si 2[(1/3C 7H 8)]：C，71.67；H，8.86；N，5.30.Found：C，72.14；H，8.93；N，5.66％.
Embodiment 3
Synthetic complex compound C3
Figure BSA00000437813700062
Under argon shield, in 100mL Schlenk bottle, add 4,6-di-t-butyl-2-{N-(2-is fluorine-based)-N-[(N ', N '-diethylin) ethyl] aminomethyl } phenol (0.411g), toluene 20mL adds Mg[Si (NMe under the room temperature 3) 2] 2(0.345g), stirring at room 24h puts into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.415g, 66.5%).
1H?NMR(C 6D 6，400MHz)：δ7.61(s，1H，ArH)，7.20-7.17(m，1H，ArH)，6.89-6.84(m，2H，ArH)，6.70-6.78(m，2H，ArH)，6.82-6.71(m，2H，ArH)，4.35(d，1H，J＝14.0Hz，ArCH 2N)，4.05(d，1H，J＝14Hz，ArCH 2N)，3.56(q，2H，J＝12.8Hz，CH 2-CH 3)，2.72-2.59(m，1H，NCH 2Ar)，2.49-2.45(m，1H，J＝12.4Hz，NCH 2Ar)，2.38-2.30(m，4H，NCH 2CH 2，N)，2.16-2.11(m，1H，NCH 2CH 3)，2.09-2.00(m，1H，NCH 2CH 3)，1.81(s，9H，C(CH 3) 3)，1.39(s，9H，C(CH 3) 3)，0.82-0.80(m，3H，NCH 2CH 3)，0.50(s，18H，Si(N(CH 3) 2) 3)，0.46-0.39(m，3H，NCH 2-CH 3)；Anal.Calc.forC 34H 60FMgN 3OSi 2[(1/6C 7H 8)]：C，65.82；H，9.64；N，6.71.Found：C，65.84；H，9.71；N，6.79％.
Embodiment 4
Synthetic complex compound C4
Figure BSA00000437813700071
Under argon shield; in 100mL Schlenk bottle, add 4,6-dicumyl-2-{N-(the 3-tertiary butyl-5 methyl-2-methoxy-benzyl)-N-[(N ', N '-dimethyl) propyl group] aminomethyl } phenol (0.635g); toluene 20mL adds Mg[Si (NMe under the room temperature 3) 2] 2(0.345g), stirring at room 24h puts into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.386g, 47.2%).
1H?NMR(400MHz，C 6D 6)：δ7.53(m，1H，Ar-H)，7.41-7.43(m，2H，Ar-H)，7.31-7.32(m，2H，Ar-H)，7.06-7.13(m，5H，Ar-H)，6.94-7.02(m，2H，Ar-H)，6.78(s，1H，Ar-H)，6.61(s，1H，Ar-H)，4.24(d， 2J＝13.2Hz，1H，Ar-CH 2)，3.97(d， 2J＝14.0Hz，1H，Ar-CH 2)，3.67(d， 2J＝13.2Hz，1H，Ar-CH 2)，3.36(s，3H，Ar-OCH 3)，3.36(d， 2J＝14.0Hz，1H，Ar-CH 2，overlapped?by?Ar-OCH 3signal)，2.30-2.33(m，1H，NCH 2CH 2CH 2N)，2.21(m，1H，NCH 2CH 2CH 2N)，2.14(s，3H，Ar-CH 3)，2.08(s，3H，cumyl-CH 3)，1.90(s，3H，cumyl-CH 3)，1.85(s，3H，cumyl-CH 3)，1.78(m，2H，NCH 2CH 2CH 2N)，1.78(m，1H，NCH 2CH 2CH 2N?overlapped?by?NCH 2CH 2CH 2N?signal)1.64(s，3H，cumyl-CH 3)，1.62(s，6H，N(CH 3) 2)，1.49(m，1H，NCH 2CH 2CH 2N)，1.36(s，9H，C(CH 3) 3)，0.44(s，18H，SiCH 3)；Anal.Calcd.for?C 49H 75N 3O 2Si 2Mg：C，71.89；H，9.23；N，5.13.Found：C，71.39；H，9.07；N，4.85％.
Embodiment 5
Synthetic complex compound C5
Figure BSA00000437813700081
Under argon shield, in 100mL Schlenk bottle, add 4-methyl-6-trityl group-2-{N-(2-methoxy-benzyl) N-[(N ', N '-dimethyl) propyl group] aminomethyl } phenol (0.585g), toluene 20mL adds Mg[Si (NMe under the room temperature 3) 2] 2(0.345g), stirring at room 24h puts into-20 ℃ of refrigerators after concentrating, and gets clear crystal (0.661g, productive rate 76.3%).
MS(m/z)：539(34，[M-CPh 3] +)，463(20，[M-MgN(SiMe 3) 2-[o-MeOPhCH 2]] +)，361(100，[M-MgN(SiMe 3) 2-MeOPhCH 2-N(CH 2) 3N(CH 3) 2] +)，347(10，[M-MgN(SiMe 3) 2-MeOPhCH 2-N(CH 2) 3N(CH 3) 2-CH 2] +)，285(38，[M-[o-Ph 3C-o-CH 2-p-CH 3PhO]-o-MeO?PhCH 2N] +)；221(15，[M-MgN(SiMe 3) 2-[o-Ph 3C-o-CH 2-p-CH 3PhO]] +)，121(38，[M-MgN(SiMe 3) 2-[o-Ph 3C-o-CH 2-p-CH 3PhO]-N(CH 2) 3N(CH 3) 2] +)，91(25，[PhCH 2] +)，72(8，[(CH 2) 2N(CH 3) 2] +)，58(23，[CH 2N(CH 3) 2] +).Anal.Calcd.for?C 46H 61N 3O 2Si 2Mg[(C 7H 8)]：C，73.97；H，8.08；N，4.88.Found：C，73.32；H，7.78；N，4.91％.
Embodiment 6
Under argon shield, in the 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, [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 at 60 ℃ of vacuum-drying 16h.Monomer conversion 77%.
Embodiment 7
Under argon shield, in the 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, [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 at 60 ℃ of vacuum-drying 16h.Monomer conversion 96%.
Embodiment 8
Under argon shield, in the 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, [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 at 60 ℃ of vacuum-drying 16h.Monomer conversion 97%.
Embodiment 9
Under argon shield, in the 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, [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 at 60 ℃ of vacuum-drying 16h.Monomer conversion 98%, number-average molecular weight 2.4 * 10 4G/mol, PDI=1.57, degree of isotacticity P m=0.49.
Embodiment 10
Under argon shield, in the 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, [Mg] 0=0.005M, [Mg] 0: [ iPrOH] 0: [rac-LA] 0=1: 1: 200, stirring at room reaction 15min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 96%, number-average molecular weight 4.6 * 10 4G/mol, PDI=2.08, degree of isotacticity P m=0.55.
Embodiment 11
Under argon shield, in the 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, [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 at 60 ℃ of vacuum-drying 16h.Monomer conversion 81%.
Embodiment 12
Under argon shield, in the 20mL bottle, add the THF solution of 0.4mL rac-rac-Lactide, the toluene 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, [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 at 60 ℃ of vacuum-drying 16h.Monomer conversion 97%.
Embodiment 13
Under argon shield, in the 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, [Mg] 0=0.005M, [Mg] 0: [rac-LA] 0=1: 200, stirring at room reaction 45min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 98%, number-average molecular weight 2.8 * 10 4G/mol, PDI=1.50, degree of isotacticity P m=0.48.
Embodiment 14
Under argon shield, in the 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, [Mg] 0=0.005M, [Mg] 0: [rac-LA] 0=1: 200, stirring at room reaction 45min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 98%, number-average molecular weight 2.8 * 10 4G/mol, PDI=1.50, degree of isotacticity P m=0.48.
Embodiment 15
Under argon shield, in the 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, [Mg] 0=0.005M, [Mg] 0: [ iPrOH] 0: [rac-LA] 0=1: 1: 200, stirring at room reaction 45min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 96%, number-average molecular weight 2.4 * 10 4G/mol, PDI=1.53, degree of isotacticity P m=0.59.
Embodiment 16
Under argon shield, in the 20mL bottle, add the toluene solution of 1mmol L-rac-Lactide, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [L-LA] 0=0.5M, [Mg] 0=0.0025M, [Mg] 0: [L-LA] 0=1: 200, stirring at room reaction 1min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 99%.
Embodiment 17
Under argon shield, in the 20mL bottle, add the toluene solution of 1mmol L-rac-Lactide, the toluene solution 1mL of the described catalyzer C2 that reinjects, [L-LA] 0=1.25M, [Mg] 0=0.00125M, [Mg] 0: [L-LA] 0=1: 1000, stirring at room reaction 3min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 78%.
Embodiment 18
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol L-rac-Lactide, the toluene solution 1mL of the described catalyzer C2 that reinjects, [L-LA] 0=1.0M, [Mg] 0=0.0002M, [Mg] 0: [L-LA] 0=1: 5000, stirring at room reaction 10min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 29%.
Embodiment 19
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol L-rac-Lactide, the toluene solution 1mL of the described catalyzer C2 that reinjects, [L-LA] 0=1.0M, [Mg] 0=0.0002M, [Mg] 0: [L-LA] 0=1: 5000, stirring at room reaction 3h.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 60%.
Embodiment 20
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol L-rac-Lactide, the toluene solution 1mL of the described catalyzer C2 that reinjects, [L-LA] 0=2.5M, [Mg] 0=0.0005M, [Mg] 0: [L-LA] 0=1: 5000, stirring at room reaction 3h.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 20%.
Embodiment 21
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol L-rac-Lactide, the toluene solution 1mL of the described catalyzer C2 that reinjects, [L-LA] 0=1.0M, [Mg] 0=0.0001M, [Mg] 0: [L-LA] 0=1: 10000, stirring at room reaction 28h.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 1%.
Embodiment 22
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol L-rac-Lactide, the toluene solution 1mL of the described catalyzer C2 that reinjects, [L-LA] 0=5.0M, [Mg] 0=0.0005M, [Mg] 0: [L-LA] 0=1: 10000, stirring at room reaction 8min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 39%.
Embodiment 23
Under argon shield, in the 20mL bottle, add the toluene solution of 1mmol caprolactone, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [ε-CL] 0=0.5M, [Mg] 0=0.0025M, [Mg] 0: [ε-CL] 0=1: 200, stirring at room reaction 30s.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 99%.
Embodiment 24
Under argon shield, in the 20mL bottle, add the toluene solution of 1mmol caprolactone, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [ε-CL] 0=1.0M, [Mg] 0=0.001M, [Mg] 0: [ε-CL] 0=1: 1000, stirring at room reaction 3min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 96%.
Embodiment 25
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol caprolactone, the toluene solution 1.0mL of the described catalyzer C2 that reinjects, [ε-CL] 0=2.5M, [Mg] 0=0.0025M, [Mg] 0: [ε-CL] 0=1: 1000, stirring at room reaction 2min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 100%.
Embodiment 26
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol caprolactone, the toluene solution 1.0mL of the described catalyzer C2 that reinjects, [ε-CL] 0=1.0M, [Mg] 0=0.0005M, [Mg] 0: [ε-CL] 0=1: 2000, stirring at room reaction 5min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 78%.
Embodiment 27
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol caprolactone, the toluene solution 1.0mL of the described catalyzer C2 that reinjects, [ε-CL] 0=5.0M, [Mg] 0=0.001M, [Zn] 0: [ε-CL] 0=1: 5000, stirring at room reaction 10min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 41%.
Embodiment 28
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol caprolactone, the toluene solution 1.0mL of the described catalyzer C2 that reinjects, [ε-CL] 0=1.0M, [Mg] 0=0.0001M, [Mg] 0: [ε-CL] 0=1: 10000, stirring at room reaction 28h.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 1%.
Embodiment 29
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol caprolactone, the toluene solution 1.0mL of the described catalyzer C2 that reinjects, [ε-CL] 0=5.0M, [Mg] 0=0.0005M, [Mg] 0: [ε-CL] 0=1: 10000, stirring at room reaction 8min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 6%.
Embodiment 30
Under argon shield, in the 20mL bottle, add the toluene solution of 2mmol caprolactone, the toluene solution 1.0mL of the described catalyzer C2 that reinjects, [ε-CL] 0=10.0M, [Mg] 0=0.0005M, [Mg] 0: [ε-CL] 0=1: 20000, stirring at room reaction 7h.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 4%.
Embodiment 31
Under argon shield, in the 20mL bottle, add the toluene solution of 1mmol caprolactone and 1mmol rac-Lactide, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [ε-CL] 0=1M, [rac-LA] 0=1M, [Mg] 0=0.005M, [Mg] 0: [ε-CL] 0: [rac-LA] 0=1: 200: 200, stirring at room reaction 10min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Caprolactone monomer transformation efficiency 5%, lactide monomer transformation efficiency 98%.
Embodiment 32
Under argon shield, in the 20mL bottle, add the toluene solution of 1mmol caprolactone and 1mmol L-rac-Lactide, the toluene solution of 0.1mL Virahol, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [ε-CL] 0=1M, [L-LA] 0=1M, [ iPrOH] 0=0.05M, [Mg] 0=0.05M, [Mg] 0: [ iPrOH] 0: [ε-CL] 0: [L-LA] 0=1: 1: 200: 200, stirring at room reaction 5min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Caprolactone monomer transformation efficiency 6%, lactide monomer transformation efficiency 98%.
Embodiment 33
Under argon shield, in the 20mL bottle, add 1mmol caprolactone toluene solution, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [ε-CL] 0=0.5M, [Mg] 0=0.001M, [Mg] 0: [ε-CL] 0=1: 500, stirring at room reaction 5min adds 1mmol L-rac-Lactide, [L-LA] again 0=2.0M, [Mg] 0: [L-LA] 0=1: 2000, stirring at room reaction 3h.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Caprolactone monomer transformation efficiency 96%, lactide monomer transformation efficiency 64%.
Embodiment 34
Under argon shield, in the 20mL bottle, add 1mmol caprolactone toluene solution, the toluene solution 0.5mL of the described catalyzer C2 that reinjects, [ε-CL] 0=1.0M, [Mg] 0=0.001M, [Mg] 0: [ε-CL] 0=1: 1000, stirring at room reaction 5min adds 1mmol L-rac-Lactide, [L-LA] again 0=1.0M, [Mg] 0: [L-LA] 0=1: 1000, stirring at room reaction 3h.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Caprolactone monomer transformation efficiency 91%, lactide monomer transformation efficiency 50%.
Embodiment 35
Under argon shield, in the 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, [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 at 60 ℃ of vacuum-drying 16h.Monomer conversion 71%.
Embodiment 36
Under argon shield, in the 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, [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 at 60 ℃ of vacuum-drying 16h.Monomer conversion 93%.
Embodiment 37
Under argon shield, in the 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, [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 at 60 ℃ of vacuum-drying 16h.Monomer conversion 64%.
Embodiment 38
Under argon shield, in the 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, [Mg] 0=0.005M, [Mg] 0: [rac-LA] 0=1: 200, stirring at room reaction 45min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 99%, number-average molecular weight 1.3 * 10 4G/mol, PDI=1.61, degree of isotacticity P m=0.49.
Embodiment 39
Under argon shield, in the 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, [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 at 60 ℃ of vacuum-drying 16h.Monomer conversion 98%, number-average molecular weight 1.4 * 10 4G/mol, PDI=1.39, degree of isotacticity P m=0.65.
Embodiment 40
Under argon shield, in the 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 reaction 45min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 89%, degree of isotacticity P m=0.40.
Embodiment 41
Under argon shield, in the 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 reaction 35min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 82%.
Embodiment 42
Under argon shield, in the 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 reaction 15min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 75%.
Embodiment 43
Under argon shield, in the 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 reaction 45min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 97%.
Embodiment 44
Under argon shield, in the 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 reaction 30min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 95%.
Embodiment 45
Under argon shield, in the 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 reaction 15min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 87%.
Embodiment 46
Under argon shield, in the 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 reaction 30min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 91%, degree of isotacticity P m=0.52.
Embodiment 47
Under argon shield, in the 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 reaction 15min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 89%, degree of isotacticity P m=0.54.
Embodiment 48
Under argon shield, in the 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 reaction 35min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 71%, degree of isotacticity P m=0.38.
Embodiment 49
Under argon shield, in the 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 reaction 15min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 55%.
Embodiment 50
Under argon shield, in the 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 reaction 30min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 72%, degree of isotacticity P m=0.39.
Embodiment 51
Under argon shield, in the 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 reaction 15min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 55%.
Embodiment 52
Under argon shield, in the 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 reaction 45min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 96%.
Embodiment 53
Under argon shield, in the 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 reaction 30min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 77%, degree of isotacticity P m=0.46.
Embodiment 54
Under argon shield, in the 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 reaction 15min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 98%.
Embodiment 55
Under argon shield, in the 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 reaction 5min.With wet oil ether termination reaction, after the filtration with polymkeric substance at 60 ℃ of vacuum-drying 16h.Monomer conversion 84%, degree of isotacticity P m=0.57.

Claims (10)

1. the MAGNESIUM METAL complex compound (I) of an asymmetric multiple tooth pawl type list phenol oxygen ylidene ligands is characterized in that having following general formula:
Figure FSA00000437813600011
In the formula (I):
R 1～R 4Represent hydrogen respectively, C 1～C 20The alkyl of straight chain, branched structure, C 7～C 30The alkyl that list or polyaryl replace, halogen;
X 1Be C 1～C 12The alkoxyl group of straight chain, branched structure, halogen;
R 5Be ethylidene or propylidene;
R 5During for ethylidene, X 2Be diethylin; R 5During for propylidene, X 2Be dimethylin;
R 6Represent two (trimethyl silicon based) amido.
2. the MAGNESIUM METAL complex compound of asymmetric multiple tooth pawl type list phenol oxygen ylidene ligands according to claim 1 is characterized in that R 1～R 4Be hydrogen, C 1～C 10The alkyl of straight chain, branched structure, C 7～C 20The alkyl that list or polyaryl replace, halogen; X 1Be C 1～C 6The alkoxyl group of straight or branched structure, halogen.
3. the MAGNESIUM METAL complex compound of asymmetric multiple tooth pawl type list phenol oxygen ylidene ligands according to claim 1 is characterized in that R 1～R 4Be preferably hydrogen, methyl, the tertiary butyl, cumyl, trityl, halogen; X 1Be preferably methoxyl group, fluorine.
4. the preparation method of the MAGNESIUM METAL complex compound (I) of each described asymmetric multiple tooth pawl type list phenol oxygen ylidene ligands of claim 1～3 comprises the steps:
Figure FSA00000437813600012
Asymmetric multiple tooth pawl type list phenol ligand compound and magnesium organometallics shown in the formula (II) are reacted in organic medium, generate the MAGNESIUM METAL complex compound of asymmetric multiple tooth pawl type list phenol oxygen ylidene ligands, temperature of reaction is-10～80 ℃, reacted 24～48 hours, and from reaction product, collected target compound (I) then; Said magnesium organometallics is preferably two [two (trimethyl silicon based) amido] magnesium.
5. method according to claim 4 is characterized in that, asymmetric multiple tooth pawl type list phenol ligand compound and the metal-organic mol ratio of magnesium are: 1: 0.5～1: 1.5.
6. method according to claim 4 is characterized in that described solvent is selected from one or more in tetrahydrofuran (THF), ether, glycol dimethyl ether, toluene, normal hexane and the sherwood oil.
7. the application of the MAGNESIUM METAL complex compound of each described asymmetric multiple tooth pawl type list phenol oxygen ylidene ligands of claim 1～3 is characterized in that, is used for the open loop homopolymerization or the copolymerization of catalyzing lactone such as 6-caprolactone, rac-Lactide.
8. application according to claim 7, it is characterized in that, MAGNESIUM METAL complex compound with each described asymmetric multiple tooth pawl type list phenol oxygen ylidene ligands of claim 1～3 is a catalyzer, in the presence of alcohol or do not add alcohol, makes 6-caprolactone polymerization under-39～130 ℃ condition; The used solvent of polymerization is selected from one or both in toluene, sherwood oil, normal hexane, tetrahydrofuran (THF), ether, glycol dimethyl ether, methylene dichloride or the chloroform, or does not use solvent; Described alcohol is one or more in methyl alcohol, ethanol, Virahol, the trimethyl carbinol, the benzylalcohol.
9. application according to claim 7, it is characterized in that, MAGNESIUM METAL complex compound with each described asymmetric multiple tooth pawl type list phenol oxygen ylidene ligands of claim 1～3 is a catalyzer, in the presence of alcohol or do not add alcohol, makes rac-Lactide polymerization under-39～130 ℃ of conditions; The used solvent of polymerization is selected from one or both in toluene, sherwood oil, normal hexane, tetrahydrofuran (THF), ether, glycol dimethyl ether, methylene dichloride or the chloroform, or does not use solvent; Described alcohol is one or more in methyl alcohol, ethanol, Virahol, the trimethyl carbinol, the benzylalcohol.
10. application according to claim 7, it is characterized in that, MAGNESIUM METAL complex compound with each described asymmetric multiple tooth pawl type list phenol oxygen ylidene ligands of claim 1～3 is a catalyzer, in the presence of alcohol or do not add alcohol, makes the copolymerization under-39～130 ℃ of conditions of 6-caprolactone and rac-Lactide; The used solvent of polymerization is selected from one or both in toluene, sherwood oil, normal hexane, tetrahydrofuran (THF), ether, glycol dimethyl ether, methylene dichloride or the chloroform, or does not use solvent; Described alcohol is methyl alcohol, ethanol, Virahol, the trimethyl carbinol, benzylalcohol.
CN2011100426369A 2011-02-23 2011-02-23 Asymmetric multi-hock type monophenoloxo magnesium complex as well as preparation method and application thereof Pending CN102153597A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1302481A2 (en) * 1998-10-13 2003-04-16 Samsung General Chemicals Co., Ltd. Metallocene catalysts for olefin polymerization and method of polymerizing olefins using the metallocene catalysts
CN101775042A (en) * 2010-01-11 2010-07-14 华东理工大学 Novel polydentate monophenoxy ligand magnesium complex, and preparation method and applications thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1302481A2 (en) * 1998-10-13 2003-04-16 Samsung General Chemicals Co., Ltd. Metallocene catalysts for olefin polymerization and method of polymerizing olefins using the metallocene catalysts
CN101775042A (en) * 2010-01-11 2010-07-14 华东理工大学 Novel polydentate monophenoxy ligand magnesium complex, and preparation method and applications thereof

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Application publication date: 20110817