CN102617618A - Rare-earth metal amino coordination compound, and preparation method and application thereof - Google Patents
Rare-earth metal amino coordination compound, and preparation method and application thereof Download PDFInfo
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- CN102617618A CN102617618A CN2012100460951A CN201210046095A CN102617618A CN 102617618 A CN102617618 A CN 102617618A CN 2012100460951 A CN2012100460951 A CN 2012100460951A CN 201210046095 A CN201210046095 A CN 201210046095A CN 102617618 A CN102617618 A CN 102617618A
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- earth metal
- piperazine
- rare earth
- amido
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Abstract
The invention discloses a piperazine bridged bi-aryloxy rare-earth metal amino coordination compound. The general formula of the piperazine bridged bi-aryloxy rare-earth metal amino coordination compound is [OArNNArO]LnX (THF). In the formula, Ln is rare-earth metal and is selected from one of neodymium, samarium, ytterbium or yttrium, and X is an amino group and is selected from one of trimethyl silylamino, dimethyl silylamino or N-trimethyl silicon anilino. [OArNNArO]=C4H8N2[1,4-(2-O-3-R1-5-R2-C6H2CH2-)2], wherein R1 and R2 are respectively selected from one of methyl or tertiary butyl. The piperazine bridged bi-aryloxy rare-earth metal amino coordination compound is synthesized conveniently and is high in yield. The piperazine bridged bi-aryloxy rare-earth metal amino coordination compound can serve as a single-component catalyst to catalyze ring-opening polymerization of L-lactide with high activity under the mild conditions, and polylactide with high molecular weight and moderate molecular weight distribution is obtained.
Description
Technical field
The present invention relates to contain heterocyclic bridged bis aryloxy rare earth metal title complex, be specifically related to a kind of piperazine alkyl bridged linkage bis aryloxy rare earth metal amido title complex and catalysis use thereof.
Background technology
Aliphatic polyester is one type of Biodegradable Polymers, and it promptly can be degraded under physiological condition, and degraded product is nontoxic.Therefore, it is as the compatible material of biological tissue, has obtained application (referring to Hayashi, T.Prog.Polym.Sci., 1994,19,663) clinically.POLYACTIC ACID has high resolution, lower melting point, and can be compatible with multiple polymers can be used as the softening agent of polymkeric substance etc., its characteristic and be widely used in controlled drug delivery system (referring to Zhang, X.C.; McAuley, K.B.; Gossen, M.F.A.J.Control.Release 1995,34,175), the orthopaedics immobilization material is (referring to Bergsm, J.E.; RoZem, F.R.; Bos, R.M.et al Joral.Maxillofac.Surg.1993,51,666) and tissue engineering bracket material (referring to: Beumer, G.J.et al J.Biomed.Mater.Res.1994,28,545; Mooney, D.J.; Park, S.; Kaufmane, P.M.et al J.Biomed.Mater.Res.1995,29,959) etc. the aspect.
Polylactide is generally by the metal complexes L of single active center
mMR (referring to: 1. Dechy-Cabaret, O.; Mrtin-Vaca, B.; Bourissou, D.Chem.Rev.2004,104,6147; 2. Chisholm, M.; Zhou, Z.J.Mater.Chem.2004,14,3081; 3. Wu, J.; Yu, T.; Chen, C.; Lin, C.Coord.Chem.Rev.2006,250,602.) ring-opening polymerization through rac-Lactide obtains.At metal complexes L
mAmong the MR, L
mBe assistant ligand, its steric effect and electronic effect affect the reactivity worth of title complex; R is an initiating group, and it affects the reactive behavior of title complex.R can be alkoxyl group, aryloxy and amido, alkyl etc.Reasonable combination through assistant ligand, central metal and initiating group can filter out highly active metal catalyst.
Ring-opening polymerization is the short-cut method of synthetic fat adoption ester.People have developed the ring-opening polymerization that a lot of catalystsystem are used for cyclic ester, and used catalyzer can be alkoxy compound, alkylate, amino-complex and the hydroborates etc. of main group metal, transition metal and rare earth metal.Some rare earth metal complexs wherein have definite structure because of it and can be used as single component catalyst and use and to receive much concern.Be used for rac-Lactide polymeric single-component rare-earth metal catalyst and bridging amidino groups and bridged linkage bis aryloxy rare earth metal title complex arranged (referring to 1. Wang, J.F.; Cai, T.; Yao, Y.M.; Zhang, Y.; Shen, Q.Dalton Trans., 2007,5275; 2. Cai, C.X.; Amgoune, A.; Lehmann, C.W.; Carpentier, J.F.Chem.Commun.2004,330; 3. Kerton, F.M.; Whitwood, A.C.; Willans, C.E.Dalton Trans.2004,2237; 4. Amgoune, A.; Thomas, C.M.; Ilinca, S.; Roisnel, T.; Carpentier, J.-F.Angew.Chem., Int.Ed.2006,45,2782; 5. Amgoune, A.; Thomas, C.M.; Roisnel, T.; Carpentier; J.F.
J.2006; 12,169; 6. Delbridge, E.E.; Dugah, D.T.; Nelson, C.R.; Skelton, B.W.; White, A.H.Dalton Trans.2007,143; 7. Liu, X.L.; Shang, X.M.; Tang, T.; Hu, N.H.; Pei, F.K.; Cui D.M.; Chen X.S.; Jing, X.B.Organometallics 2007,26, and 2747.) etc.
Up to now; The relevant bridged linkage bis aryloxy rare earth metal title complex of bibliographical information is in the application of catalysis cyclic esters ring-opening polymerization; The bridged linkage bis aryloxy part mainly is that amido bridged linkage bis aryloxy and sulphur bridge that carbon bridged linkage bis aryloxy, side arm contain the sub-prothetic group of supplying power join bis aryloxy ligand rare earth metallic compound (1. Yao, Y.M.; Xu, X.P.; Liu, B.; Zhang, Y.; Shen, Q.Inorg.Chem.2005,44,5133; 2. Xu, X.P.; Yao, Y.M.; Hu, M.Y.; Zhang, Y.; Shen, Q.J.Polym.Sci.:Part A:Polym.Chem.2006,44,4409; 3. Cai, C.X.; Amgoune, A.; Lehmann, C.W.; Carpentier, J.F.Chem.Commun.2004,330; 4. Kerton, F.M.; Whitwood, A.C.; Willans, C.E.Dalton Trans.2004,2237; 5. Yao, Y.M.; Ma, M.T.; Xu, X.P.; Zhang, Y.; Shen, Q.; Wong, W.T.Organometallics 2005,24, and 4014; 6. Amgoune, A.; Thomas, C.M.; Ilinca, S.; Roisnel, T.; Carpentier, J.-F.Angew.Chem., Int.Ed.2006,45,2782; 7. Amgoune, A.; Thomas, C.M.; Roisnel, T.; Carpentier; J.F.
J.2006; 12,169; 8. Delbridge, E.E.; Dugah, D.T.; Nelson, C.R.; Skelton, B.W.; White, A.H.Dalton Trans.2007,143; 9. Zhou, H.; Guo, H.D.; Yao, Y.M.; Zhang, Y.; Shen, Q.Inorg.Chem.2007,46,958) etc., and for containing heterocyclic bridged bis aryloxy rare earth metal title complex thing as the report of single component catalyst catalysis L-rac-Lactide ring-opening polymerization also fewer (1. Zhang, Z.J.; Xu, X.P.; Sun, S.; Yao, Y.M.; Zhang, Y.; Shen, Q.Chem.Commun.2009,7414; 2. Zhang, Z.J.; Xu, X.P.; Li, W.Y.; Yao, Y.M.; Zhang, Y.; Shen Q.; Luo, Y.J.Inorg.Chem.2009,48,5715.).We find that one type of preparation is simpler, (wherein Ln is a rare earth metal to more cheap piperazine bridged linkage bis aryloxy rare earth metal amido title complex [OArNNArO] LnX (THF) of price; Be selected from: neodymium (Nd); Samarium (Sm); A kind of in ytterbium (Yb) or the yttrium (Y), X is an amine groups, is selected from trimethyl silicane amido (N (SiMe
3)
2), dimethyl-silicon amido (N (SiHMe
2)
2) or trimethyl silicon based phenyl amido (N (SiMe
3) Ph) and in a kind of; [OArNNArO]=C
4H
8N
2[1,4-(2-O-3-R
1-5-R
2-C
6H
2CH
2-)
2], R is selected from a kind of in the methyl or the tertiary butyl) can obtain the polylactide of HMW, moderate molecular weight distribution in the ring-opening polymerization of high reactivity ground catalysis L-rac-Lactide under the mild conditions.
Summary of the invention
Goal of the invention of the present invention provides a kind of piperazine bridged linkage bis aryloxy rare earth metal amido title complex, as the catalyzer of catalysis L-rac-Lactide ring-opening polymerization.
For reaching the foregoing invention purpose, the technical scheme that the present invention adopts is: a kind of piperazine bridged linkage bis aryloxy rare earth metal amido title complex, and the general formula of said piperazine bridged linkage bis aryloxy rare earth metal amido title complex is as follows: [OArNNArO] LnX (THF); In the formula, Ln is a rare earth metal, is selected from: a kind of in neodymium (Nd), samarium (Sm), ytterbium (Yb) or the yttrium (Y), X is an amine groups, is selected from trimethyl silicane amido (N (SiMe
3)
2), dimethyl-silicon amido (N (SiHMe
2)
2) or trimethyl silicon based phenyl amido (N (SiMe
3) Ph) and in a kind of; [OArNNArO]=C
4H
8N
2[1,4-(2-O-3-R
1-5-R
2-C
6H
2CH
2-)
2], R
1, R
2Be selected from a kind of in the methyl or the tertiary butyl respectively separately; The chemical structural formula of said piperazine bridged linkage bis aryloxy rare earth metal amido title complex is as follows:
The preparation method of above-mentioned piperazine bridged linkage bis aryloxy rare earth metal amido title complex may further comprise the steps:
(1) under anhydrous and oxygen-free protection of inert gas condition, according to mol ratio 0.9～1.1: 1 gets LnX
3(THF)
nWith piperazine bridging bis-phenol [OArNNArO] H
2, being dissolved in and reacting in aromatic solvent or the ether solvent 10～24 hours, temperature of reaction is-20～50 ℃, and is no more than the boiling point of solvent; N=0,1 or 2.
(2) except that desolvating, add a small amount of hexane extraction residuum, the centrifugal deposition of removing concentrates clear liquid, under 5～-30 ℃, obtains the crystal of [OArNNArO] LnX (THF).
In the technique scheme, in the step (1), the factor that choice of Solvent need be considered comprises: solubility property, do not participate in the reaction and boiling point should not be too low; In the optimized technical scheme, when n=0, said solvent is a THF; When n=1 or 2, said solvent is selected from a kind of in aromatic solvent or the ether solvent, and said aromatic solvent is: benzene or toluene, said ether solvent is: THF, ether or glycol dimethyl ether.
The reaction process of synthesizing piperazine bridged linkage bis aryloxy rare earth metal amido title complex is as follows:
In the technique scheme, the productive rate of piperazine bridged linkage bis aryloxy rare earth metal amido title complex is 70%～90%.
In the technique scheme, in the step (1), said piperazine bridging bis-phenol (OArNNArO) H
2In [OArNNArO]=C
4H
8N
2[1,4-(2-O-3-R
1-5-R
2-C
6H
2CH
2-)
2]; But preparing method's reference of this compound: Farwell, J.D.; Hitchcock, P.B.; Lappert, M.F.; Luinstra, G.A.; Protchenko, A.V.; Wei, X.H.J.Organomet.Chem.2008,693,1861-1869, its chemical structural formula is as follows:
Described LnX
3(THF)
nIn, Ln is a rare earth metal, is selected from: a kind of in neodymium, samarium, ytterbium or the yttrium; X is an amine groups, is selected from trimethyl silicane amido (N (SiMe
3)
2), dimethyl-silicon amido (N (SiHMe
2)
2) or trimethyl silicon based phenyl amido (N (SiMe
3) Ph) and in a kind of; N=0,1 or 2.
LnX wherein
3(THF)
n(X=N (SiMe
3)
2, preparation method n=0) can be referring to document (Donald, C.B.; Joginder, S.G.J.Chem.Soc., Dalton Trans.1973,1021.); Be specially:
(a) in the two neck flasks of handling through dehydration and deoxidation, add NaH (3.6g) and THF (50mL), under argon shield, add two (trimethyl silicane) amine (20.7mL; 100mmol); The reaction starting stage has a large amount of hydrogen to emit, and notes in time venting, accident so as to avoid an accident;
(b) 50 ℃ of oil baths were approximately reacted two days, and system becomes the khaki color turbid solution, stops heating, and the cooling back is centrifugal, and clear liquid is NaN (SiMe
3)
2Tetrahydrofuran solution, it is subsequent use to demarcate concentration with the standard salt acid solution; In the Schlenk bottle of handling through dehydration and deoxidation, add YCl
3(20.48mmol), under the room temperature, add about 20mL THF, stirred overnight at room temperature while stirring;
(c) under agitation add 3.0 normal NaN (SiMe then with syringe
3)
2Tetrahydrofuran solution (61.44mmol) is to above-mentioned YCl
3The THF suspension liquid in, room temperature reaction spends the night.The oil pump removal of solvent under reduced pressure is used n-hexane extraction then, the centrifugal NaCl that removes; Clear liquid concentrates and is placed on refrigerator cold-storage, obtains colourless acicular crystal, is Y [N (SiMe
3)
2]
3, Ln only needs when being neodymium (Nd), samarium (Sm), ytterbium (Yb) the YCl in the above-mentioned steps (b)
3The halogenide of being replaced by corresponding metal gets final product.
LnX wherein
3(THF)
n(X=N (HSiMe
2)
2, preparation method n=2) can be referring to document (Anwander, R.; Runte, O.; Eppinger, J.; Gerstberger, G.; Herdtweek, E.; Spiegler, M.J.Chem.Soc.Dalton Trans.1998,847); Be specially:
(a) in the Schlenk bottle of handling through dehydration and deoxidation, add YCl
3(1.95g 10.00mmol), under the room temperature, adds about 15mL THF, stirred overnight at room temperature while stirring;
(b) (4.00g 30.00mmol), adds the dilution of 10mL THF in the reaction flask of handling through dehydration and deoxidation, to add two (dimethyl-silicon) amine; Under the cryosel bath condition, slowly drip n-Butyl Lithium (23.81mL, 30.00mmol; 1.26M dropwised in hexane solution), about 15 minutes; Remove cryosel and bathe, about 1 hour of normal-temperature reaction joins the good YCl of above-mentioned activation with this reaction solution
3The THF suspension liquid in, room temperature reaction spends the night;
(c) oil pump removal of solvent under reduced pressure is used n-hexane extraction then, the centrifugal LiCl that removes; Clear liquid concentrates and is placed on refrigerator cold-storage, obtains colourless granule crystal, is Y [N (HSiMe
2)
2]
3(THF)
2, Ln only needs when being neodymium (Nd), samarium (Sm), ytterbium (Yb) the YCl in the above-mentioned steps (a)
3The halogenide of being replaced by corresponding metal gets final product.
LnX wherein
3(THF)
n(X=(SiMe
3) NC
6H
5, preparation method n=1) is specially:
(a) in two mouthfuls of flasks of dehydration and deoxidation, add aniline (9.13mL, 100mmol) and THF (80mL); (1.26M 79mL), drips off the back stirring at room 2 hours at-78 ℃ of hexane solutions that slowly drip n-BuLi; Be cooled to-78 ℃ then, add the 14mL trimethylchlorosilane;
(b) after 1 hour, be raised to room temperature-78 ℃ of insulations naturally, continuation stirring reaction half hour,, reaction solution becomes the turbid liquid of oyster white by light yellow clear liquid; Drain solvent and obtain pink turbid solution, underpressure distillation then, the cut of 90 ℃/3mmHg of collection is the trimethyl silicon based aniline HN of title product N-(SiMe
3) Ph, yield 85%;
1H NMR (400MHz, CDCl3, δ): 6.82-7.20 (m, 3H); 0.12 (s, 9H) (reference: Porskamp, P.A.T.W.; Zwanenburg, B.; Synthesis 1981,369);
(c) according to document (Schumann, H.; Winterfeld, J.; Rosenthal, E.C.E.; Hemling, H.; Esser, L.Z.Anorg.Allg.Chem.1995,621,122.), in the Schlenk bottle of handling through dehydration and deoxidation, with HN (SiMe
3) Ph (and 2.00mL 13.2mmol) is dissolved among the 15mL THF, slowly adds n-BuLi (10.5mL, 13.2mmol, 1.26M hexane solution) at 0 ℃, rise under the room temperature reaction 1h naturally after, join YbCl
3(1.23g, in THF 4.4mmol) (50mL) suspension liquid, solution colour is by the colourless scarlet that becomes, and solid disappears very soon; React after 48 hours, drain solvent, after the extracted in toluene of usefulness heat is removed LiCl; Gained centrifugate is placed on 5 ℃ of crystallizations through concentrating, and gets the scarlet crystal, is Yb [N (SiMe
3) Ph]
3(THF).
When Ln is neodymium (Nd), samarium (Sm) or yttrium (Y), only need the YbCl in the above-mentioned steps (c)
3The halogenide of being replaced by corresponding metal gets final product.
Above-mentioned piperazine bridged linkage bis aryloxy rare earth metal amido title complex can be used as the ring-opening polymerization that single component catalyst is applied to the L-rac-Lactide.Therefore, the present invention also protects the application of above-mentioned piperazine bridged linkage bis aryloxy rare earth metal amido title complex as the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide.
Using above-mentioned piperazine bridged linkage bis aryloxy rare earth metal amido title complex may further comprise the steps as the method for the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide:
(1) under the inert atmosphere of anhydrous and oxygen-free, the L-rac-Lactide is dissolved in the solvent, the solution that adds above-mentioned piperazine bridged linkage bis aryloxy rare earth metal amido title complex then under the vigorous stirring carries out ring-opening polymerization;
(2) termination reaction uses precipitation agent to be settled out polymkeric substance, and drying obtains gathering the L-rac-Lactide then.
In the technique scheme, in the step (1), the temperature of reaction of ring-opening polymerization is 30 ℃～90 ℃, and is no more than the boiling point of solvent, is preferably 50 ℃～70 ℃; The mol ratio of L-rac-Lactide and catalyzer is 300～2000: 1, and preferred range is 800～2000: 1, and advantage of the present invention is that catalyst levels is few.Catalyst levels not only can reduce cost less, but also can reduce the residual quantity of metal ion neutralization product, improves the quality of product; The polymeric time is 0.5～3 hour; Said solvent is selected from: a kind of in toluene, benzene, methylene dichloride or the THF.
In the technique scheme, catalyzer can directly be added in the polymerization system, but takes more convenient behind the wiring solution-forming.
In the technique scheme, the percent by volume of the methanol solution of hydrochloric acid is 4～6% in the step (2).
In the technique scheme, if no special instructions, all other chemical feedstockss are the commercial goods.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. piperazine bridged linkage bis aryloxy rare earth metal amido title complex according to the invention is synthetic convenient, and yield is high.
2. piperazine bridged linkage bis aryloxy rare earth metal amido title complex according to the invention can obtain the polylactide of HMW, moderate molecular weight distribution as the ring-opening polymerization of single component catalyst high reactivity ground catalysis L-rac-Lactide under the condition of gentleness.
Embodiment
Below in conjunction with instance the present invention is further described:
Embodiment one:
Referring to document (Donald, C.B.; Joginder, S.G.J.Chem.Soc., Dalton Trans.1973,1021.) preparation LnX
3(THF)
n(X=N (SiMe
3)
2, n=0), may further comprise the steps:
(a) in the two neck flasks of handling through dehydration and deoxidation, add NaH (3.6g) and THF (50mL), under argon shield, add two (trimethyl silicane) amine (20.7mL; 100mmol); The reaction starting stage has a large amount of hydrogen to emit, and notes in time venting, accident so as to avoid an accident;
(b) 50 ℃ of oil baths were approximately reacted two days, and system becomes the khaki color turbid solution, stops heating, and the cooling back is centrifugal, and clear liquid is NaN (SiMe
3)
2Tetrahydrofuran solution, it is subsequent use to demarcate concentration with the standard salt acid solution; In the Schlenk bottle of handling through dehydration and deoxidation, add YCl
3(20.48mmol), under the room temperature, add about 20mL THF, stirred overnight at room temperature while stirring;
(c) under agitation add 3.0 normal NaN (SiMe then with syringe
3)
2Tetrahydrofuran solution (61.44mmol) is to above-mentioned YCl
3The THF suspension liquid in, room temperature reaction spends the night.The oil pump removal of solvent under reduced pressure is used n-hexane extraction then, the centrifugal NaCl that removes; Clear liquid concentrates and is placed on refrigerator cold-storage, obtains colourless acicular crystal, is Y [N (SiMe
3)
2]
3, Ln only needs when being neodymium (Nd), samarium (Sm), ytterbium (Yb) the YCl in the above-mentioned steps (b)
3The halogenide of being replaced by corresponding metal gets final product.
Referring to document (Anwander, R.; Runte, O.; Eppinger, J.; Gerstberger, G.; Herdtweek, E.; Spiegler, M.J.Chem.Soc.Dalton Trans.1998,847) preparation LnX
3(THF)
n(X=N (HSiMe
2)
2, n=2), may further comprise the steps:
(a) in the Schlenk bottle of handling through dehydration and deoxidation, add YCl
3(1.95g 10.00mmol), under the room temperature, adds about 15mL THF, stirred overnight at room temperature while stirring;
(b) (4.00g 30.00mmol), adds the dilution of 10mL THF in the reaction flask of handling through dehydration and deoxidation, to add two (dimethyl-silicon) amine; Under the cryosel bath condition, slowly drip n-Butyl Lithium (23.81mL, 30.00mmol; 1.26M dropwised in hexane solution), about 15 minutes; Remove cryosel and bathe, about 1 hour of normal-temperature reaction joins the good YCl of above-mentioned activation with this reaction solution
3The THF suspension liquid in, room temperature reaction spends the night;
(c) oil pump removal of solvent under reduced pressure is used n-hexane extraction then, the centrifugal LiCl that removes; Clear liquid concentrates and is placed on refrigerator cold-storage, obtains colourless granule crystal, is Y [N (HSiMe
2)
2]
3(THF)
2, Ln only needs when being neodymium (Nd), samarium (Sm), ytterbium (Yb) the YCl in the above-mentioned steps (a)
3The halogenide of being replaced by corresponding metal gets final product.
Preparation LnX
3(THF)
n(X=(SiMe
3) NC
6H
5, n=1), specifically may further comprise the steps:
(a) in two mouthfuls of flasks of dehydration and deoxidation, add aniline (9.13mL, 100mmol) and THF (80mL); (1.26M 79mL), drips off the back stirring at room 2 hours at-78 ℃ of hexane solutions that slowly drip n-BuLi; Be cooled to-78 ℃ then, add the 14mL trimethylchlorosilane;
(b) after 1 hour, be raised to room temperature-78 ℃ of insulations naturally, continuation stirring reaction half hour,, reaction solution becomes the turbid liquid of oyster white by light yellow clear liquid; Drain solvent and obtain pink turbid solution, underpressure distillation then, the cut of 90 ℃/3mmHg of collection is the trimethyl silicon based aniline HN of title product N-(SiMe
3) Ph, yield 85%;
1H NMR (400MHz, CDCl3, δ): 6.82-7.20 (m, 3H); 0.12 (s, 9H);
(c) according to document (Schumann, H.; Winterfeld, J.; Rosenthal, E.C.E.; Hemling, H.; Esser, L.Z.Anorg.Allg.Chem.1995,621,122.), in the Schlenk bottle of handling through dehydration and deoxidation, with HN (SiMe
3) Ph (and 2.00mL 13.2mmol) is dissolved among the 15mL THF, slowly adds n-BuLi (10.5mL, 13.2mmol, 1.26M hexane solution) at 0 ℃, rise under the room temperature reaction 1h naturally after, join YbCl
3(1.23g, in THF 4.4mmol) (50mL) suspension liquid, solution colour is by the colourless scarlet that becomes, and solid disappears very soon; React after 48 hours, drain solvent, after the extracted in toluene of usefulness heat is removed LiCl; Gained centrifugate is placed on 5 ℃ of crystallizations through concentrating, and gets the scarlet crystal, is Yb [N (SiMe
3) Ph]
3(THF).
When Ln is neodymium (Nd), samarium (Sm) or yttrium (Y), only need the YbCl in the above-mentioned steps (c)
3The halogenide of being replaced by corresponding metal gets final product.
Embodiment two: preparation [OArNNArO] LnX (THF) (Ln=Y, X=N (SiMe
3)
2)
(1) with 2.0 mmole Y [N (SiMe
3)
2]
3Tetrahydrofuran solution slowly join and contain [OArNNArO] H
2Tetrahydrofuran solution (2.0 mmole), the system achromaticity and clarification continued stirring reaction 12 hours under 25 ℃ of conditions;
(2) take out and desolvate, add 20 milliliters of hexanes and add extraction heat, the centrifugal insolubles of removing, clear liquid shifts, and concentrates a little hexane, about 15 milliliters of surplus solution, 5 ℃ of condition hold over night are separated out colourless acicular crystal 1.31 grams (1.56 mmole), productive rate 78%.Ultimate analysis: C, 62.55; H, 9.54; N, 4.76.
1HNMR (THF-d
8, 400MHz, ppm): 7.09 (d,
4J (H, H)=2.4Hz, 2H, ArH), 6.71 (d,
4J (H, H)=2.4Hz, 2H, ArH), 4.59 (d,
2J (H, H)=13.6Hz, 2H, ArCH
2), 3.78 (m, 2H, NCH
2CH
2N piperazidine ring), 3.54 (br, 4H, α-CH
2THF), 3.10 (d,
2J (H, H)=13.6Hz, 2H, ArCH
2), 2.99 (m, 2H, NCH
2CH
2N piperazidine ring), 2.52 (m, 2H, NCH
2CH
2N piperazidine ring), 1.96 (m, 2H, NCH
2CH
2N piperazidine ring), 1.69 (br, 4H, β-CH
2THF), 1.38 (s, 18H, C (CH
3)
3), 1.18 (s, 18H, C (CH
3)
3), 0.12 (s, 18H, TMS).
13C NMR (C
6D
6, 75MHz, ppm): δ 159.83,137.54,136.21,124.71,124.30,121.62 (Ar-C), 69.30 (THF-α-CH
2), 60.74 (ArCH
2N), 50.06,46.02 (N (CH
2)
2N), 35.69,34.18,32.11,30.80 (C (CH
3)
3), 25.43 (THF-β-CH
2), 6.19 (TMS). ir spectra (KBr, cm
-1): 2957 (s), 2906 (s), 2869 (s), 1607 (m), 1466 (s), 1441 (s); 1413 (s), 1362 (s), 1305 (s), 1237 (s), 1202 (m), 1164 (m); 1134 (m), 1028 (w), 935 (s), 879 (s), 833 (s). above digital proof purpose compound success.
Embodiment three: preparation [OArNNArO] LnX (THF) (Ln=Sm, X=N (SiMe
3)
2)
(1) with 2.0 mmole S m [N (SiMe
3)
2]
3Tetrahydrofuran solution slowly join and contain [OArNNArO] H
2Tetrahydrofuran solution (2.0 mmole), the system achromaticity and clarification continued stirring reaction 12 hours under 25 ℃ of conditions;
(2) take out and desolvate, add 20 milliliters of hexanes and add extraction heat, the centrifugal insolubles of removing, clear liquid shifts, and concentrates a little hexane, about 15 milliliters of surplus solution, 5 ℃ of condition hold over night are separated out colourless acicular crystal 1.54 grams (1.70 mmole), productive rate 85%.Ultimate analysis: C, 58.85; H, 8.14; N, 4.92.
1HNMR (C
6D
6, 400MHz, ppm): 13.24 (br, 1H, ArCH
2), 9.55 (br, 1H, ArCH
2), 8.56 (d,
4J (H, H)=2.4Hz, 2H, ArH), 8.15 (m, 2H, NCH
2CH
2N piperazidine ring), 7.91 (d,
4J (H, H)=2.4Hz, 2H, ArH), 3.37 (br, 4H, α-CH
2THF), 2.86 (m, 2H, NCH
2CH
2N piperazidine ring), 1.96 (s, 18H, C (CH
3)
3), 1.82 (m, 2H, NCH
2CH
2Npiperazidine ring), 1.57 (br, 1H, ArCH
2), 1.32 (br, 4H, β-CH
2THF; Overlap with ArCH
2Signal), 1.25 (br, 1H, ArCH
2), 1.20 (m, 2H, NCH
2CH
2N piperazidine ring), 0.55 (s, 18H, C (CH
3)
3) ,-0.74 (s, 18H, TMS). ir spectra (KBr, cm
-1): 2955 (s), 2907 (s), 2867 (s), 1605 (m), 1467 (s), 1442 (s); 1411 (s), 1363 (s), 1305 (s), 1237 (s), 1202 (m), 1165 (m); 1132 (m), 1028 (w), 935 (s), 880 (s), 834 (s). above digital proof purpose compound success.
Embodiment four: preparation [OArNNArO] LnX (THF) (Ln=Nd, X=N (SiMe
3)
2)
(1) with 2.0 mmole Nd [N (SiMe
3)
2]
3Tetrahydrofuran solution slowly join and contain [OArNNArO] H
2Tetrahydrofuran solution (2.0 mmole), the system achromaticity and clarification continued stirring reaction 12 hours under 25 ℃ of conditions;
(2) take out and desolvate, add 20 milliliters of hexanes and add extraction heat, the centrifugal insolubles of removing, clear liquid shifts, and concentrates a little hexane, about 15 milliliters of surplus solution, 5 ℃ of condition hold over night are separated out blue needle-like crystal 1.43 grams (1.60 mmole), productive rate 80%.Ultimate analysis: C, 58.50; H, 8.68; N, 4.59. ir spectra (KBr, cm
-1): 2957 (s), 2905 (s), 2869 (s), 1606 (m), 1467 (s), 1441 (s); 1413 (s), 1361 (s), 1303 (s), 1237 (s), 1202 (m), 1166 (m); 1134 (m), 1026 (w), 934 (s), 879 (s), 834 (s). above digital proof purpose compound success.
Embodiment five: preparation [OArNNArO] LnX (THF) (Ln=Y, X=N (HSiMe
2)
2)
(1) with 2.0 mmole Y [N (HSiMe
2)
2]
3(THF)
3Tetrahydrofuran solution slowly join and contain [OArNNArO] H
2Tetrahydrofuran solution (2.0 mmole), the system achromaticity and clarification continued stirring reaction 12 hours under 25 ℃ of conditions;
(2) take out and desolvate, add 20 milliliters of hexanes and add extraction heat, the centrifugal insolubles of removing, clear liquid shifts; Concentrate a little hexane, about 15 milliliters of surplus solution adds about 1 milliliter of THF again; 5 ℃ of condition hold over night are separated out clear crystal 1.22 grams (1.5 mmole), productive rate 75%.Ultimate analysis: C, 62.28; H, 9.01; N, 5.29.
1H NMR (C
6D
6, 300MHz): 7.53 (d,
4J (H, H)=2.1Hz, 2H, ArH), 6.89 (d,
4J (H, H)=2.1Hz, 2H, ArH), 5.09 (m, 2H, Si-H), 4.65 (d,
2J (H, H)=13.2Hz, 2H, ArCH
2), 3.95 (br, 4H, α-CH
2THF), 3.52 (m, 2H, NCH
2CH
2N piperazidine ring), 2.86 (m, 2H, NCH
2CH
2N piperazidine ring), 2.78 (d,
2J (H, H)=13.2Hz, 2H, ArCH
2), 1.77 (m, 2H, NCH
2CH
2N piperazidine ring), 1.65 (s, 18H, C (CH
3)
3), 1.45 (m, 2H, NCH
2CH
2N piperazidine ring; Overlap with THF signal), 1.42 (br, 4H, β-CH
2THF), 1.40 (s, 18H, C (CH
3)
3), 0.32 (d, J=2.7,12H, TMS).
13C NMR (C
6D
6, 75MHz, ppm): δ 160.05,136.91,136.68,125.02,124.11,122.35 (Ar-C), 70.31 (THF-α-CH
2), 60.16 (ArCH
2N), 51.62,45.28 (N (CH
2)
2N), 35.55,34.19,32.18,30.75 (C (CH
3)
3), 25.39 (THF-β-CH
2), 5.06 (TMS). ir spectra (KBr, cm
-1): 2961 (s), 2902 (s), 2871 (s), 1605 (m), 1460 (s), 1443 (s); 1413 (s), 1366 (s), 1300 (s), 1239 (s), 1205 (m), 1161 (m); 1138 (m), 1024 (w), 935 (s), 876 (s), 835 (s). above digital proof purpose compound success.
Embodiment six: preparation [OArNNArO] LnX (THF) (Ln=Yb, X=N (HSiMe
2)
2)
(1) with 2.0 mmole Yb [N (HSiMe
2)
2]
3(THF)
3Tetrahydrofuran solution slowly join and contain [OArNNArO] H
2Tetrahydrofuran solution (2.0 mmole), the system achromaticity and clarification continued stirring reaction 12 hours under 25 ℃ of conditions;
(2) take out and desolvate, add 20 milliliters of hexanes and add extraction heat, the centrifugal insolubles of removing, clear liquid shifts; Concentrate a little hexane, about 15 milliliters of surplus solution adds about 1 milliliter of THF again; 5 ℃ of condition hold over night are separated out clear crystal 1.42 grams (1.58 mmole), productive rate 79%.Ultimate analysis: C, 56.34; H, 8.56; N, 4.63. ir spectra (KBr, cm
-1): 2955 (s), 2902 (s), 2869 (s), 1603 (m), 1477 (s), 1444 (s); 1413 (s), 1365 (s), 1308 (s), 1232 (s), 1208 (m), 1163 (m); 1134 (m), 1027 (w), 934 (s), 883 (s), 835 (s). above digital proof purpose compound success.
Embodiment seven: preparation [OArNNArO] LnX (THF) (Ln=Y, X=N (SiMe
3) Ph)
(1) with 2.0 mmole Y [N (SiMe
3) (C
6H
5)]
3(THF) tetrahydrofuran solution slowly joins and contains [OArNNArO] H
2Tetrahydrofuran solution (2.0 mmole), the system achromaticity and clarification continued stirring reaction 12 hours under 25 ℃ of conditions;
(2) take out and desolvate, add 20 milliliters of hexanes and add extraction heat, the centrifugal insolubles of removing, clear liquid shifts, and concentrates a little hexane, about 15 milliliters of surplus solution, 5 ℃ of condition hold over night are separated out clear crystal 1.22 grams (1.44 mmole), productive rate 72%.
1H NMR (C
6D
6, 400MHz): 7.56 (d,
4J (H, H)=2.4Hz, 2H, ArH), 7.05-6.90 (m, 4H, Ph-H), 6.83 (d,
4J (H, H)=2.4Hz, 2H, ArH), 6.70-6.50 (m, 1H, Ph-H), 4.27 (d,
2J (H, H)=12.8Hz, 2H, ArCH
2Overlap with THF signal), 4,27 (br, 4H, α-CH
2THF), 2.81 (m, 2H, NCH
2CH
2N piperazidine ring), 2.54 (d,
2J (H, H)=12.8Hz, 2H, ArCH
2Overlap with NCH
2CH
2N piperazidine ring signal), 2.49 (m, 2H, NCH
2CH
2N piperazidine ring), 1.74 (s, 18H, C (CH
3)
3), 1.50 (br, 4H, β-CH
2THF; Overlap with NCH
2CH
2N piperazidine ring signal), 1.45 (m, 2H, NCH
2CH
2N piperazidine ring; Overlap with C (CH
3)
3) signal), 1.42 (s, 18H, C (CH
3)
3), 0.95 (m, 2H, NCH
2CH
2N piperazidine ring), 0.36 (s, 9H, TMS).
13C NMR (C
6D
6, 100MHz, ppm): δ 160.35,159.59,137.15,136.79,130.43,125.05,125.04,122.78,122.44,117.92 (Ar-C and Ph-C), 70.77 (THF-α-CH
2), 60.88 (ArCH
2N), 51.17,46.06 (N (CH
2)
2N), 35.66,34.18,32.16,30.88 (C (CH
3)
3), 25.34 (THF-β-CH
2), 2.87 (TMS). ir spectra (KBr, cm
-1): 2953 (s), 2908 (s), 2872 (s), 1611 (m), 1478 (s), 1447 (s); 1410 (s), 1367 (s), 1308 (s), 1233 (s), 1205 (m), 1167 (m); 1131 (m), 1025 (w), 935 (s), 880 (s), 837 (s). above digital proof purpose compound success.
Embodiment eight: preparation [OArNNArO] LnX (THF) (Ln=Yb, X=N (SiMe
3) (C
6H
5))
(1) with 2.0 mmole Yb [N (SiMe
3) (C
6H
5)]
3(THF) tetrahydrofuran solution slowly joins and contains [OArNNArO] H
2Tetrahydrofuran solution (2.0 mmole), the system achromaticity and clarification continued stirring reaction 12 hours under 25 ℃ of conditions;
(2) take out and desolvate, add 20 milliliters of hexanes and add extraction heat, the centrifugal insolubles of removing, clear liquid shifts, and concentrates a little hexane, about 15 milliliters of surplus solution, 5 ℃ of condition hold over night are separated out yellow crystals 1.49 grams (1.6 mmole), productive rate 80%.Ultimate analysis: C, 60.52; H, 8.03; N, 4.59. ir spectra (KBr, cm
-1): 2959 (s), 2910 (s), 2864 (s), 1601 (m), 1479 (s), 1447 (s); 1418 (s), 1357 (s), 1293 (s), 1230 (s), 1204 (m), 1160 (m); 1137 (m), 1029 (w), 930 (s), 885 (s), 834 (s). above digital proof purpose compound success.
Embodiment nine: [OArNNArO] LnX (THF) (Ln=Y, X=N (SiMe
3)
2) ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add L-rac-Lactide 0.46 gram (3.20 mmole); Add 3.00 milliliters of toluene with syringe, after 60 ℃ of oil bath constant temperature stir 5 minutes, add 0.20 milliliter of the toluene solution (0.0535 mmole milliliter-1) of catalyzer with syringe; Polymerase 10 .5 hour, with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, gets polylactide 0.44 to constant weight after the vacuum-drying and restrains productive rate 95%.The theoretical molecular of polymkeric substance is 4.10 ten thousand [M
n(calcd)=144 * 300 * 95%], GPC actual measurement number-average molecular weight (M
n) be 2.86 ten thousand, MWD (M
w/ M
n) be 1.52.
Embodiment ten: [OArNNArO] LnX (THF) (Ln=Sm, X=N (SiMe
3)
2) ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add L-rac-Lactide 0.52 gram (3.61 mmole); Add 3.38 milliliters of toluene with syringe, after 60 ℃ of oil bath constant temperature stir 5 minutes, add 0.23 milliliter of (0.0196 mmole milliliter of toluene solution of catalyzer with syringe
-1), polymerization 1 hour is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, gets polylactide 0.51 to constant weight after the vacuum-drying and restrains productive rate 98%.The theoretical molecular of polymkeric substance is 11.29 ten thousand [M
n(calcd)=144 * 800 * 98%], GPC actual measurement number-average molecular weight (M
n) be 6.18 ten thousand, MWD (M
w/ M
n) be 1.46.
Embodiment 11: [OArNNArO] LnX (THF) (Ln=Sm, X=N (SiMe
3)
2) ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add L-rac-Lactide 0.55 gram (3.82 mmole); Add 3.63 milliliters of toluene with syringe, after 60 ℃ of oil bath constant temperature stir 5 minutes, add 0.19 milliliter of (0.0196 mmole milliliter of toluene solution of catalyzer with syringe
-1), polyase 13 hour is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, gets polylactide 0.48 to constant weight after the vacuum-drying and restrains productive rate 87%.The theoretical molecular of polymkeric substance is 12.53 ten thousand [M
n(calcd)=144 * 1000 * 87%], GPC actual measurement number-average molecular weight (M
n) be 6.23 ten thousand, MWD (M
w/ M
n) be 1.48.
Embodiment 12: [OArNNArO] LnX (THF) (Ln=Nd, X=N (SiMe
3)
2) ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add L-rac-Lactide 0.56 gram (3.89 mmole); Add 3.68 milliliters of toluene with syringe, after 60 ℃ of oil bath constant temperature stir 5 minutes, add 0.21 milliliter of (0.0185 mmole milliliter of toluene solution of catalyzer with syringe
-1), polymerase 10 .5 hour, with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, gets polylactide 0.54 to constant weight after the vacuum-drying and restrains productive rate 96%.The theoretical molecular of polymkeric substance is 13.82 ten thousand [Mn (calcd)=144 * 1000 * 96%], and GPC actual measurement number-average molecular weight (Mn) is 7.07 ten thousand, and MWD (Mw/Mn) is 1.62.
Embodiment 13: [OArNNArO] LnX (THF) (Ln=Nd, X=N (SiMe
3)
2) ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add L-rac-Lactide 0.68 gram (4.72 mmole); Add 4.59 milliliters of toluene with syringe, after 60 ℃ of oil bath constant temperature stir 5 minutes, add 0.13 milliliter of (0.0185 mmole milliliter of toluene solution of catalyzer with syringe
-1), polyase 13 hour is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, gets polylactide 0.58 to constant weight after the vacuum-drying and restrains productive rate 85%.The theoretical molecular of polymkeric substance is 24.48 ten thousand [M
n(calcd)=144 * 2000 * 85%], GPC actual measurement number-average molecular weight (M
n) be 7.77 ten thousand, MWD (M
w/ M
n) be 1.55.
Embodiment 14: [OArNNArO] LnX (THF) (Ln=Y, X=N (SiHMe
2)
2) ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add L-rac-Lactide 0.50 gram (3.47 mmole); Add 3.10 milliliters of toluene with syringe, after 60 ℃ of oil bath constant temperature stir 5 minutes, add 0.10 milliliter of (0.0347 mmole milliliter of toluene solution of catalyzer with syringe
-1), polymerization 1 hour is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, gets polylactide 0.47 to constant weight after the vacuum-drying and restrains productive rate 94%.The theoretical molecular of polymkeric substance is 13.54 ten thousand [M
n(calcd)=144 * 1000 * 94%], GPC actual measurement number-average molecular weight (M
n) be 6.75 ten thousand, MWD (M
w/ M
n) be 1.48.
Embodiment 15: [OArNNArO] LnX (THF) (Ln=Yb, X=N (SiHMe
2)
2) ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add L-rac-Lactide 0.44 gram (3.06 mmole); Add 3.07 milliliters of toluene with syringe, after 60 ℃ of oil bath constant temperature stir 5 minutes, add 0.27 milliliter of (0.0142 mmole milliliter of toluene solution of catalyzer with syringe
-1), polymerization 1 hour is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, gets polylactide 0.41 to constant weight after the vacuum-drying and restrains productive rate 93%.The theoretical molecular of polymkeric substance is 11.29 ten thousand [M
n(calcd)=144 * 800 * 98%], GPC actual measurement number-average molecular weight (M
n) be 5.75 ten thousand, MWD (M
w/ M
n) be 1.55.
Embodiment 16: [OArNNArO] LnX (THF) (Ln=Y, X=N (SiMe
3) Ph) ring-opening polymerization of catalysis L-rac-Lactide
In the reaction flask of handling through dehydration and deoxidation; Under argon shield, add L-rac-Lactide 0.60 gram (4.17 mmole); Add 4.12 milliliters of toluene with syringe, after 60 ℃ of oil bath constant temperature stir 5 minutes, add 0.18 milliliter of (0.0193 mmole milliliter of toluene solution of catalyzer with syringe
-1), polymerization 1 hour is with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, gets polylactide 0.52 to constant weight after the vacuum-drying and restrains productive rate 87%.The theoretical molecular of polymkeric substance is 15.03 ten thousand [M
n(calcd)=144 * 1200 * 87%], GPC actual measurement number-average molecular weight (M
n) be 8.24 ten thousand, MWD (M
w/ M
n) be 1.55.
Claims (10)
1. a rare earth metal amido title complex is characterized in that, said rare earth metal amido title complex is a piperazine bridged linkage bis aryloxy rare earth metal amido title complex, and its general formula is: [OArNNArO] LnX (THF); In the formula, Ln is selected from: a kind of in neodymium, samarium, ytterbium or the yttrium; X is selected from: a kind of in trimethyl silicane amido, dimethyl-silicon amido or the trimethyl silicon based phenyl amido; [OArNNArO]=C
4H
8N
2[1,4-(2-O-3-R
1-5-R
2-C
6H
2CH
2-)
2], R
1, R
2Be selected from a kind of in the methyl or the tertiary butyl separately respectively; The chemical structural formula of said piperazine bridged linkage bis aryloxy rare earth metal amido title complex is as follows:
2. the preparation method of the said piperazine bridged linkage bis aryloxy rare earth metal of claim 1 amido title complex is characterized in that, may further comprise the steps:
(1) under anhydrous and oxygen-free protection of inert gas condition, according to mol ratio 0.9～1.1: 1 gets LnX
3(THF)
nWith piperazine bridging bis-phenol [OArNNArO] H
2, being dissolved in and reacting 10～24 hours in the solvent, temperature of reaction is-20～50 ℃, and is no more than the boiling point of solvent;
Wherein, Ln is selected from: a kind of in neodymium, samarium, ytterbium or the yttrium; X is selected from a kind of in trimethyl silicane amido, dimethyl-silicon amido or the trimethyl silicon based phenyl amido; N=0,1 or 2; Said piperazine bridging bis-phenol [OArNNArO] H
2Chemical structural formula as follows:
(2) except that desolvating, use the hexane extraction residuum, the centrifugal deposition of removing concentrates clear liquid, under-30 ℃～5 ℃, obtains the crystal of [OArNNArO] LnX (THF), is said piperazine bridged linkage bis aryloxy rare earth metal amido title complex.
3. according to the preparation method of the said piperazine bridged linkage bis aryloxy rare earth metal of claim 2 amido title complex, it is characterized in that in the step (1), when n=0, said solvent is a THF; When n=1 or 2, said solvent is selected from a kind of in aromatic solvent or the ether solvent, and said aromatic solvent is: benzene or toluene, said ether solvent is: THF, ether or glycol dimethyl ether.
4. the said piperazine bridged linkage bis aryloxy rare earth metal of claim 1 amido title complex is as the application of the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide.
5. application rights requires the method for 1 said piperazine bridged linkage bis aryloxy rare earth metal amido title complex as the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide, it is characterized in that, may further comprise the steps:
(1) under the inert atmosphere of anhydrous and oxygen-free, the L-rac-Lactide is dissolved in the solvent, the solution that adds piperazine bridged linkage bis aryloxy rare earth metal amido title complex then under the vigorous stirring carries out ring-opening polymerization;
(2) termination reaction uses precipitation agent to be settled out polymkeric substance, and drying obtains gathering the L-rac-Lactide then.
6. according to the method for the said application piperazine of claim 5 bridged linkage bis aryloxy rare earth metal amido title complex as the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide ester; It is characterized in that; In the step (1), the temperature of reaction of ring-opening polymerization is 30 ℃～90 ℃, and is no more than the boiling point of solvent.
7. according to the method for the said application piperazine of claim 6 bridged linkage bis aryloxy rare earth metal amido title complex as the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide; It is characterized in that; In the step (1), the temperature of ring-opening polymerization is 50 ℃～70 ℃, and is no more than the boiling point of solvent.
8. according to the method for the said application piperazine of claim 5 bridged linkage bis aryloxy rare earth metal amido title complex as the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide; It is characterized in that; In the step (1), the mol ratio of L-rac-Lactide and catalyzer is 300～2000: 1.
9. according to the method for the said application piperazine of claim 5 bridged linkage bis aryloxy rare earth metal amido title complex, it is characterized in that in the step (1), polymerization time is 0.5～3 hour as the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide.
10. according to the method for the said application piperazine of claim 5 bridged linkage bis aryloxy rare earth metal amido title complex as the ring-opening polymerization of single component catalyst catalysis L-rac-Lactide; It is characterized in that; In the step (1), said solvent is selected from: a kind of in toluene, benzene, methylene dichloride or the THF.
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| CN103087114A (en) * | 2013-01-30 | 2013-05-08 | 苏州大学 | Salalen-type rare-earth metal amide as well as preparation method and application thereof |
| CN103254247A (en) * | 2012-11-01 | 2013-08-21 | 苏州大学 | Preparation and application of p-phenylenediamine-bridged tetraaryloxy bimetallic rare earth amide |
| CN106588962A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Rare-earth metal organic compound, rare-earth catalyst composition, and their preparation methods and application |
| CN117229254A (en) * | 2023-11-15 | 2023-12-15 | 苏州大学 | Method for preparing L-lactide from poly-L-lactic acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254247A (en) * | 2012-11-01 | 2013-08-21 | 苏州大学 | Preparation and application of p-phenylenediamine-bridged tetraaryloxy bimetallic rare earth amide |
| CN103254247B (en) * | 2012-11-01 | 2015-10-21 | 苏州大学 | Preparation and application of p-phenylenediamine-bridged tetraaryloxy bimetallic rare earth amide |
| CN103087114A (en) * | 2013-01-30 | 2013-05-08 | 苏州大学 | Salalen-type rare-earth metal amide as well as preparation method and application thereof |
| CN103087114B (en) * | 2013-01-30 | 2016-06-22 | 苏州大学 | A kind of Salalen type rare-earth metal amide and its preparation method and application |
| CN106588962A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Rare-earth metal organic compound, rare-earth catalyst composition, and their preparation methods and application |
| CN117229254A (en) * | 2023-11-15 | 2023-12-15 | 苏州大学 | Method for preparing L-lactide from poly-L-lactic acid |
| CN117229254B (en) * | 2023-11-15 | 2024-04-05 | 苏州大学 | Method for preparing L-lactide from poly-L-lactic acid |
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