CN101591349A - Nitrogen-bridged bis aryloxy yttrium is to dibenzyl oxygen compound and preparation and application - Google Patents
Nitrogen-bridged bis aryloxy yttrium is to dibenzyl oxygen compound and preparation and application Download PDFInfo
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- CN101591349A CN101591349A CNA200910032425XA CN200910032425A CN101591349A CN 101591349 A CN101591349 A CN 101591349A CN A200910032425X A CNA200910032425X A CN A200910032425XA CN 200910032425 A CN200910032425 A CN 200910032425A CN 101591349 A CN101591349 A CN 101591349A
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Abstract
The invention discloses nitrogen-bridged bis aryloxy yttrium to dibenzyl oxygen compound and preparation and application, described bridged linkage bis aryloxy rare earth metal title complex be nitrogen-bridged bis aryloxy yttrium to the dibenzyl oxygen compound, its chemical formula is: p-C
6H
4[CH
2OYL (THF)]
2Wherein, Y represents the rare earth metal yttrium; L represents nitrogen-bridged bis aryloxy part, L=Me
2NCH
2CH
2N{CH
2-(2-O-C
6H
2-R-3,5)
2, wherein 3 of aromatic ring and 5 have alkyl substituent R, and R is selected from the saturated alkyl of C1～C4; The nitrogen-bridged bis aryloxy yttrium of double activity center of the present invention type is synthetic easy to the dibenzyl oxygen compound, not only can be under mild conditions as single component catalyst high reactivity, the controllably ring-opening polymerization of catalysis 6-caprolactone and L-rac-Lactide; Can also cause this two kinds of monomeric copolymerizations, obtain ABA block polymer.
Description
Technical field
The present invention relates to a kind of rare earth metal complex, be specifically related to a kind of with nitrogen-bridged bis aryloxy be assistant ligand, by yttrium complex and catalytic applications thereof to double activity center's type of benzyloxy bridging.
Background technology
Aliphatic polyester is a class 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.Polycaprolactone has high resolution, and low melting point, and can be compatible with multiple polymers can be used as softening agent of polymkeric substance etc. (referring to Deanin, R.D., Zhang, Z.B.J.Vinyl Technol.1984,6,18).Poly(lactic acid) also is widely used in controlled drug delivery system (referring to Zhang, X.C. because of its characteristic; McAuley, K.B.; Goss en, 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: 1. Beumer, G.J.et al J.Biomed.Mater.Res.1994,28,545; 2. Mooney, D.J.; Park, S.; Kaufmane, P.M.et al J.Biomed.Mater.Res.1995,29,959) etc. the aspect.Their multipolymer, particularly segmented copolymer then can be cut out by molecule and satisfy more property and require (referring to 1. Drumright, R.E.; Gruber, P.R.; Henton, D.E.Adv.Mater.2000,12,1841; 2. Uhrich, K.E.; Cannizzaro, S.M.and Langer, R.S.; Shakesheff, K.M.Chem.Rev.1999,99,3181).In view of some wide application prospect of aliphatic polyester, relevant research has obtained people's extensive concern.
Ring-opening polymerization is the short-cut method of synthetic fat adoption ester, and ring-opening copolymerization then is that aliphatic polyester is carried out the most effectual way of chemically modified (referring to 1. Albertsson, A.C.; Varma, I.K.Biomacromolecules 2003,4, and 1466; 2. Odile, D.C.; Blanca, M.V.; Didier, B.Chem.Rev.2004,104,6147).People have developed the ring-opening polymerization that a lot of catalyst system 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.
Recently, the bridged linkage bis aryloxy rare earth metal title complex has flexible and changeable structure because of it and can be used as single component catalyst and uses and to receive much concern.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, and the bridged linkage bis aryloxy part mainly is that the carbon bridged linkage bis aryloxy is (referring to 1. Yao, Y.M.; Xu, X.P.; 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), side arm contains the nitrogen-bridged bis aryloxy of the sub-prothetic group of powering (referring to 1. Cai, C.X.; Amgoune, A.; Lehmann, C.W.; Carpentier, J.F.Chem.Commun.2004,330; 2. Kerton, F.M.; Whitwood, A.C.; Willans, C.E.Dalton Trans.2004,2237; 3. Yao, Y.M.; Ma, M.T.; Xu, X.P.; Zhang, Y.; Shen, Q.; Wong, W.T.Organometallics 2005,24, and 4014; 4. Amgoune, A.; Thoma s, 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.Chem.Eur.J.2006,12,169; 6. Zhou, H.; Guo, H.D.; Yao, Y.M.; Zhang, Y.; Shen, Q.Inorg.Chem.2007,46,958; 7. Dyer, H.E.; Huijser, S.; Schwarz, A.D.; Wang, C.; Duchateau, R.; Mountford, P.Dalton Trans.2008,32; 8. Carpentier, J.F.Macromolecules 2009,42,987) and sulphur bridge connection bis aryloxy part (referring to 1. Ma, H.Y.; Okuda, J.Macromolecules 2005,38, and 2665; 2. Ma, H.Y.; Spaniol, T.P.; Okuda, J.Angew.Chem.Int.Ed.2006,45,7818; Konkol, M.; Spaniol, T.P.; Kondracka, M.; Okuda, J.Dalton Trans.2007,4095) etc.Up to now, yet there are no the nitrogen-bridged bis aryloxy rare earth metal title complex of double activity center's type as single component catalyst catalysis 6-caprolactone and controlled all (being total to) polymeric of L-rac-Lactide report.
Summary of the invention
The object of the invention provides the nitrogen-bridged bis aryloxy rare earth metal title complex of a kind of double activity center type.
For achieving the above object, the technical solution used in the present invention is: a kind of nitrogen-bridged bis aryloxy yttrium is to the dibenzyl oxygen compound, and the chemical formula of described title complex is:
p-C
6H
4[CH
2OYL(THF)]
2；
Wherein, Y represents the rare earth metal yttrium; L represents nitrogen-bridged bis aryloxy part, L=Me
2NCH
2CH
2N{CH
2-(2-O-C
6H
2-R-3,5)
2, wherein 3 of aromatic ring and 5 have alkyl substituent R, and R is selected from the saturated alkyl of C1～C4;
Above-mentioned nitrogen-bridged bis aryloxy yttrium is to containing two rare earth metals, two nitrogen-bridged bis aryloxies and one to benzyloxy in the dibenzyl oxygen compound.
The present invention provides simultaneously and has prepared the method for above-mentioned nitrogen-bridged bis aryloxy yttrium to the dibenzyl oxygen compound, may further comprise the steps:
(1) under the anhydrous and oxygen-free condition, be to get nitrogen-bridged bis aryloxy rare earth metal hexichol aminate LYNPh at 2: 1 according to the molar weight ratio
2(THF) with to two benzylalcohols, be solvent with the tetrahydrofuran (THF), under the room temperature reaction more than 12 hours;
(2) solvent removed in vacuo adds normal hexane in the residuum, separate out clear crystal after leaving standstill, and centrifugal back recrystallization obtains described nitrogen-bridged bis aryloxy yttrium to dibenzyl oxygen compound p-C
6H
4[CH
2OYL (THF)]
2Crystal;
Above-mentioned nitrogen-bridged bis aryloxy rare earth metal hexichol aminate LYNPh
2(THF) preparation method is referring to Yao, Y.M.; Ma, M.T.; Xu, X.P.; Zhang, Y.; Shen, Q.; Wong, W.T.Organometallics 2005,24, and 4014.
Another object of the present invention is to provide of the application of above-mentioned nitrogen-bridged bis aryloxy yttrium to the dibenzyl oxygen compound.
For achieving the above object, the technical solution used in the present invention is:
Above-mentioned nitrogen-bridged bis aryloxy yttrium may further comprise the steps the method for the controlled ring-opening polymerization of dibenzyl oxygen compound catalysis 6-caprolactone:
(1) under the anhydrous and oxygen-free condition, adds the toluene solution of catalyzer in the time of the toluene solution of stirring 6-caprolactone;
(2) after polymerization is finished,, use the industrial spirit precipitation polymers with the alcohol termination reaction of the hydrochloric acid that contains 5% mass percent.
In the technique scheme, polymerization temperature is a room temperature, and polymerization time is adjusted according to the molecular weight of required polymkeric substance.
Above-mentioned nitrogen-bridged bis aryloxy yttrium may further comprise the steps the method for the controlled ring-opening polymerization of dibenzyl oxygen compound catalysis L-rac-Lactide:
(1) under the anhydrous and oxygen-free condition, adds the toluene solution of catalyzer in the time of the toluene solution of stirring L-rac-Lactide;
(2) after polymerization is finished,, use the industrial spirit precipitation polymers with the alcohol termination reaction of the hydrochloric acid that contains 5% mass percent.
In the technique scheme, polymerization temperature is 60～80 ℃, and polymerization time is adjusted according to the molecular weight of required polymkeric substance.
Above-mentioned nitrogen-bridged bis aryloxy yttrium may further comprise the steps the method for dibenzyl oxygen compound catalysis L-rac-Lactide and the controlled ring opening copolymer of 6-caprolactone:
(1) under the anhydrous and oxygen-free condition, under 60～80 ℃, add the toluene solution of catalyzer when stirring the toluene solution of L-rac-Lactide, carry out ring-opening polymerization;
(2) add 6-caprolactone, continue polymerization;
(3) after polymerization is finished, with the alcohol termination reaction of the hydrochloric acid that contains 5% mass percent, use the industrial spirit precipitation polymers, resulting polymers is an ABA block polymer, and wherein A is the 6-caprolactone single-unit, and B is a L-rac-Lactide single-unit.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. nitrogen-bridged bis aryloxy yttrium catalyzer of the present invention can obtain high molecular (M as single component catalyst high reactivity, controllably catalysis 6-caprolactone and the ring-opening polymerization of L-rac-Lactide under mild conditions
n＞10
4), the polycaprolactone (M that molecular weight distribution is narrower
w/ M
n=1.18-1.28) and polylactide (M
w/ M
n=1.21-1.28).
2. the nitrogen-bridged bis aryloxy yttrium catalyzer that provides of the present invention can obtain high molecular (M as the copolymerization of single component catalyst high reactivity ground catalysis L-rac-Lactide and 6-caprolactone under mild conditions
n＞10
4), the ABA block polymer (M that molecular weight distribution is narrower
w/ M
n=1.28-1.38, A=6-caprolactone, B=L-rac-Lactide).
3. nitrogen-bridged bis aryloxy yttrium catalyzer of the present invention can be with the two kinds of monomeric homopolymerizations of mode catalysis and the copolymerization thereof of controllable polymerization, controllable polymerization is better than general ring-opening polymerization, is embodied in that polymericular weight can be regulated and control (measured value of polymkeric substance number-average molecular weight and theoretical value are also more approaching) by the mol ratio of monomer and catalyzer, can add monomer to carry out the molecular weight distribution of stage feeding polymerization, polymkeric substance narrower in batches.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: p-C
6H
4[CH
2OYL (THF)]
2Synthesizing of (3,5 substituting group being a methyl on the aromatic ring of L)
At LYNPh
2(THF) in the THF solution of (3.42 grams, 5 mmoles), add two benzylalcohol p-C
6H
4(CH
2OH)
2(0.35 gram, 2.5 mmoles), it is colourless that the system color keeps substantially, and reaction is spent the night under the room temperature.Take out most of solvent, add 20 ml n-hexane standing over night, separate out a large amount of clear crystals, centrifugal removal clear liquid, solid are used the mixed solvent recrystallization of normal hexane and tetrahydrofuran (THF) again, separate out a large amount of clear crystal 2.56 grams (2.20 mmoles, 88%).
Embodiment two: p-C
6H
4[CH
2OYL (THF)]
2Synthesizing of (3,5 substituting group being the tertiary butyl on the aromatic ring of L)
At LYNPh
2(THF) in the THF solution of (4.26 grams, 5 mmoles), add two benzylalcohol p-C
6H
4(CH
2OH)
2(0.35 gram, 2.5 mmoles), it is colourless that the system color keeps substantially, and reaction is spent the night under the room temperature.Take out most of solvent, add 20 ml n-hexane standing over night, separate out a large amount of clear crystals, centrifugal removal clear liquid, solid are used the mixed solvent recrystallization of normal hexane and tetrahydrofuran (THF) again, separate out a large amount of clear crystal 3.42 grams (2.28 mmoles, 91%).
Embodiment three: p-C
6H
4[CH
2OYL (THF)]
2(3,5 substituting group is a methyl on the aromatic ring of L) controlled ring-opening polymerization of catalysis 6-caprolactone
In the polymerization bottle of dehydration and deoxidation band stirrer, add 0.60 milliliter of 6-caprolactone (5.42 mmole) with syringe, add 1.90 milliliters of toluene with syringe again, stir down 0.5 milliliter (6.02 * 10 of the toluene solution that adds catalyzer with syringe
-3The mmole milliliter
-1).Polymerization is 90 minutes under the room temperature, with the alcohol termination reaction that contains 5% hydrochloric acid, the industrial alcohol precipitation of polymkeric substance, gets polycaprolactone 0.61 to constant weight after the vacuum-drying and restrains yield 99%.The theoretical value average molecular weight of polymkeric substance is 20.11 ten thousand [M
n(calcd)=(M
wOf ε-CL) * [ε-CL]/[I] * (polymer yield)=114 * 1800 * 99%], GPC actual measurement number-average molecular weight (M
n) be 19.68 ten thousand, molecular weight distribution (M
w/ M
n) be 1.28.
Embodiment four: p-C
6H
4[CH
2OYL (THF)]
2The controlled ring-opening polymerization of (3,5 substituting group is a methyl on the aromatic ring of L) catalysis L-rac-Lactide
In the polymerization bottle of dehydration and deoxidation band stirrer, take by weighing 0.53 gram (3.68 mmole) rac-Lactide, adds 3.18 milliliters of toluene, under 70 ℃ of oil baths fully after the dissolving, with 0.5 milliliter (6.13 * 10 of the toluene solution of syringe adding catalyzer
-3The mmole milliliter
-1).Keep 70 ℃ of polymerizations 4 hours,, get polycaprolactone 0.52 to constant weight after the vacuum-drying and restrain yield 98% with the alcohol termination reaction that contains 5% hydrochloric acid, the industrial alcohol precipitation of polymkeric substance.The theoretical value average molecular weight of polymkeric substance is 16.95 ten thousand [M
n(calcd)=(M
wOf L-LA) * [ε-CL]/[I] * and (polymer yield)=144.13 * 1200 * 98%], GPC actual measurement number-average molecular weight (M
n) be 11.70 ten thousand, molecular weight distribution (M
w/ M
n) be 1.26.
Embodiment five: p-C
6H
4[CH
2OYL (THF)]
2The controlled copolymerization of (3,5 substituting group is a methyl on the aromatic ring of L) catalysis L-rac-Lactide and 6-caprolactone
In the polymerization bottle of dehydration and deoxidation band stirrer, take by weighing 0.55 gram (3.82 mmole) rac-Lactide, add 3.32 milliliters of toluene, after dissolving fully under 70 ℃ of oil baths, stir 0.5 milliliter of (the 0.038 mmole milliliter of toluene solution that adds catalyzer down with syringe
-1).Keep 70 ℃ of polymerizations 1 hour, under this temperature, add 0.42 milliliter of 6-caprolactone (3.8 mmole) again, keep 70 ℃ of polymerizations 1 hour with syringe, with the alcohol termination reaction that contains 5% hydrochloric acid, the industrial alcohol precipitation of multipolymer gets multipolymer 0.96 to constant weight after the vacuum-drying and restrains yield 98%.The theoretical value average molecular weight of polymkeric substance is 5.06 ten thousand [M
n(calcd)=(M
wOf ε-CL+M
wOf L-LA) * [M] GPC actual measurement number-average molecular weight (M/[I] * (polymer yield)=(114+144) * 200 * 98%],
n) be 5.16 ten thousand, molecular weight distribution (M
w/ M
n) be 1.28.Levy by the hydrogen stave, the mol ratio of L-rac-Lactide and 6-caprolactone is 200: 192.
Embodiment six: p-C
6H
4[CH
2OYL (THF)]
2(3,5 substituting group is the tertiary butyl on the aromatic ring of L) controlled ring-opening polymerization of catalysis 6-caprolactone
In the polymerization bottle of dehydration and deoxidation band stirrer, add 0.60 milliliter of 6-caprolactone (5.42 mmole) with syringe, add 1.90 milliliters of toluene with syringe again, stir down 0.4 milliliter (7.53 * 10 of the toluene solution that adds catalyzer with syringe
-3The mmole milliliter
-1).Polymerization is 90 minutes under the room temperature, with the alcohol termination reaction that contains 5% hydrochloric acid, the industrial alcohol precipitation of polymkeric substance, gets polycaprolactone 0.61 to constant weight after the vacuum-drying and restrains yield 99%.The theoretical value average molecular weight of polymkeric substance is 20.11 ten thousand [M
n(calcd)=(M
wOf ε-CL) * [ε-CL]/[I] * (polymer yield)=114 * 1800 * 99%], GPC actual measurement number-average molecular weight (M
n) be 20.08 ten thousand, molecular weight distribution (M
w/ M
n) be 1.25.
Embodiment seven: p-C
6H
4[CH
2OYL (THF)]
2The controlled ring-opening polymerization of (3,5 substituting group is the tertiary butyl on the aromatic ring of L) catalysis L-rac-Lactide
In the polymerization bottle of dehydration and deoxidation band stirrer, take by weighing 0.56 gram (3.89 mmole) rac-Lactide, adds 3.38 milliliters of toluene, under 70 ℃ of oil baths fully after the dissolving, with 0.5 milliliter (6.48 * 10 of the toluene solution of syringe adding catalyzer
-3The mmole milliliter
-1).Keep 70 ℃ of polymerizations 4 hours,, get polycaprolactone 0.54 to constant weight after the vacuum-drying and restrain yield 97% with the alcohol termination reaction that contains 5% hydrochloric acid, the industrial alcohol precipitation of polymkeric substance.The theoretical value average molecular weight of polymkeric substance is 16.77 ten thousand [M
n(calcd)=(M
wOf L-LA) * [ε-CL]/[I] * and (polymer yield)=144.13 * 1200 * 97%], GPC actual measurement number-average molecular weight (M
n) be 12.16 ten thousand, molecular weight distribution (M
w/ M
n) be 1.25.
Embodiment eight: p-C
6H
4[CH
2OYL (THF)]
2The controlled copolymerization of (3,5 substituting group is the tertiary butyl on the aromatic ring of L) catalysis L-rac-Lactide and 6-caprolactone
In the polymerization bottle of dehydration and deoxidation band stirrer, take by weighing 0.52 gram (3.61 mmole) rac-Lactide, add 3.22 milliliters of toluene, after dissolving fully under 70 ℃ of oil baths, stir 0.4 milliliter of (the 0.045 mmole milliliter of toluene solution that adds catalyzer down with syringe
-1).Keep 70 ℃ of polymerizations 1 hour, under this temperature, add 0.40 milliliter of 6-caprolactone (3.62 mmole) again, keep 70 ℃ of polymerizations 1 hour with syringe, with the alcohol termination reaction that contains 5% hydrochloric acid, the industrial alcohol precipitation of multipolymer gets multipolymer 0.91 to constant weight after the vacuum-drying and restrains yield 97%.The theoretical value average molecular weight of multipolymer is 5.01 ten thousand [M
n(calcd)=(M
wOf ε-CL+M
wOf L-LA) * [M] GPC actual measurement number-average molecular weight (M/[I] * (polymer yield)=(114+144.13) * 200 * 97%],
n) be 5.11 ten thousand, molecular weight distribution (M
w/ M
n) be 1.27.Levy by the hydrogen stave, the mol ratio of L-rac-Lactide and 6-caprolactone is 200: 185.
Claims (8)
1. bridged linkage bis aryloxy rare earth metal title complex is characterized in that: described bridged linkage bis aryloxy rare earth metal title complex be nitrogen-bridged bis aryloxy yttrium to the dibenzyl oxygen compound, described nitrogen-bridged bis aryloxy yttrium to the chemical formula of dibenzyl oxygen compound is:
p-C
6H
4[CH
20YL(THF)]
2；
Wherein, Y represents the rare earth metal yttrium; L represents nitrogen-bridged bis aryloxy part, L=Me
2NCH
2CH
2N{CH
2-(2-O-C
6H
2-R-3,5)
2, wherein 3 of aromatic ring and 5 have alkyl substituent R, and R is selected from the saturated alkyl of C1～C4.
2. prepare the method for the described nitrogen-bridged bis aryloxy yttrium of claim 1, it is characterized in that: may further comprise the steps the dibenzyl oxygen compound:
(1) under the anhydrous and oxygen-free condition, be to get nitrogen-bridged bis aryloxy rare earth metal hexichol aminate LYNPh at 2: 1 according to the molar weight ratio
2(THF) with to two benzylalcohols, be solvent with the tetrahydrofuran (THF), under the room temperature reaction more than 12 hours;
(2) solvent removed in vacuo adds normal hexane in the residuum, separate out clear crystal after leaving standstill, and centrifugal back recrystallization obtains the crystal of described nitrogen-bridged bis aryloxy yttrium to the dibenzyl oxygen compound.
3. the described nitrogen-bridged bis aryloxy yttrium of claim 1 is to the application of dibenzyl oxygen compound as the controlled ring-opening polymerization catalyst of 6-caprolactone.
4. application rights requires 1 described nitrogen-bridged bis aryloxy yttrium to the controlled ring-opening polymerization method of dibenzyl oxygen compound catalysis 6-caprolactone, it is characterized in that: may further comprise the steps:
(1) under the anhydrous and oxygen-free condition, adds the toluene solution of catalyzer in the time of the toluene solution of stirring 6-caprolactone;
(2) after polymerization is finished,, use the industrial spirit precipitation polymers with the alcohol termination reaction of the hydrochloric acid that contains 5% mass percent.
5. the described nitrogen-bridged bis aryloxy yttrium of claim 1 is to the application of dibenzyl oxygen compound as the controlled ring-opening polymerization catalyst of L-rac-Lactide.
6. application rights requires 1 described nitrogen-bridged bis aryloxy yttrium to the controlled ring-opening polymerization method of dibenzyl oxygen compound catalysis L-rac-Lactide, it is characterized in that: may further comprise the steps:
(1) under the anhydrous and oxygen-free condition, under 60～80 ℃, adds the toluene solution of catalyzer when stirring the toluene solution of L-rac-Lactide;
(2) after polymerization is finished,, use the industrial spirit precipitation polymers with the alcohol termination reaction of the hydrochloric acid that contains 5% mass percent.
The described nitrogen-bridged bis aryloxy yttrium of claim 1 to the dibenzyl oxygen compound as L-rac-Lactide and the controlled ring opening copolymer Application of Catalyst of 6-caprolactone.
8. application rights requires the method for 1 described nitrogen-bridged bis aryloxy yttrium to dibenzyl oxygen compound catalysis L-rac-Lactide and the controlled ring opening copolymer of 6-caprolactone, it is characterized in that: may further comprise the steps:
(1) under the anhydrous and oxygen-free condition, under 60～80 ℃, add the toluene solution of catalyzer when stirring the toluene solution of L-rac-Lactide, carry out ring-opening polymerization;
(2) add 6-caprolactone, continue polymerization;
(3) after polymerization is finished, with the alcohol termination reaction of the hydrochloric acid that contains 5% mass percent, use the industrial spirit precipitation polymers, resulting polymers is an ABA block polymer, and wherein A is the 6-caprolactone single-unit, and B is a L-rac-Lactide single-unit.
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| CN104177386A (en) * | 2014-07-22 | 2014-12-03 | 苏州大学张家港工业技术研究院 | Nitrogen bridged triaryloxy rare-earth compound, and preparation method and application thereof |
| CN115612081A (en) * | 2022-10-25 | 2023-01-17 | 苏州大学 | Preparation method of cyclic poly (L-lactide) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104177386A (en) * | 2014-07-22 | 2014-12-03 | 苏州大学张家港工业技术研究院 | Nitrogen bridged triaryloxy rare-earth compound, and preparation method and application thereof |
| CN104177386B (en) * | 2014-07-22 | 2016-06-29 | 苏州大学张家港工业技术研究院 | A kind of nitrogen-bridged three aryloxy rare earth metal compounds and its preparation method and application |
| CN115612081A (en) * | 2022-10-25 | 2023-01-17 | 苏州大学 | Preparation method of cyclic poly (L-lactide) |
| CN115612081B (en) * | 2022-10-25 | 2023-05-12 | 苏州大学 | Preparation method of cyclic poly (L-lactide) |
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