CN100383152C - Akoxy rare earth cluster compound and use thereof - Google Patents
Akoxy rare earth cluster compound and use thereof Download PDFInfo
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- CN100383152C CN100383152C CNB200510022574XA CN200510022574A CN100383152C CN 100383152 C CN100383152 C CN 100383152C CN B200510022574X A CNB200510022574X A CN B200510022574XA CN 200510022574 A CN200510022574 A CN 200510022574A CN 100383152 C CN100383152 C CN 100383152C
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Abstract
The present invention discloses an alkoxy heteronuclear polymetallic cluster compound containing rare earth metal and alkali metal, and the molecular formula of the cluster compound is Ln2 (OCH2 CH2 NMe2) 12 (OH) 2 Na8; in the formula, Ln is the rare earth metal, and Me is a methyl group. The cluster compound of the present invention can catalyze the ring opening polymerization and the copolymerization of epsilon-caprolactone and cyclic carbonate by extremely high activity under a mild condition. Meanwhile, the activity life of the cluster compound is long; after the polymerization of a first portion of monomers ends, an active chain can still continue to polymerize a second portion of monomers and even a third portion of monomers, and can serve as a catalyst to initiate the block copolymerization of two different kinds of cyclic lactone.
Description
Technical field
The present invention relates to a class alkoxy rare-earth duster compound, and the application in the ring-opening polymerization of lactone.
Background technology
Aliphatic polyester and polycarbonate are class Biodegradable Polymers, and good intermiscibility is arranged, and the slowly-releasing that can be used for medicine is put, and prepare degradable packaging film.Cyclic lactone, the ring-opening polymerization of cyclic carbonate ester are the approach that makes things convenient for of synthetic fat polyester and polycarbonate.A lot of alkoxide compounds can this kind polyester of catalysis ring-opening polymerization.
U.S. Pat 5,028, but 667 the controlled ring-opening polymerization of alkoxyl group yttrium and alkoxy rare-earth compound high reactivity ground catalysis 6-caprolactone, valerolactone is disclosed.After, also reported in succession in the document to contain rare earth-sulphur, rare earth-carbon, compound such as rare earth-nitrogen key and bivalent rare earth organic compound can be as initiators, cause the ring-opening polymerization of 6-caprolactone, cyclic carbonate ester, can be with the different active catalytic 6-caprolactones and the ring-opening polymerization of carbonic ether.Yet, have highly active rare earth duster compound and have only a class so far, the isopropoxy rare earth duster compound Ln of the same nuclear that promptly above-mentioned United States Patent (USP) was once reported as the initiator of lactone ring opening polymerization
5O (O
iPr)
13, wherein Ln is Y and rare earth element.This is the rare earth alkoxyl group duster compound of a class neutral alkali-free metal.This class duster compound is to pass through LnCL
3With NaO
iThe reaction of Pr directly obtains.In this duster compound, contain 5 rare earth metals, 13 isopropoxies and 1 Sauerstoffatom, the coordination by rare earth-oxygen forms.
Seeking that some are new, have highly active catalyzer for the ring-opening polymerization of lactone, is the focus that those skilled in the art are concerned about.
Summary of the invention
The object of the invention provides the new alkoxy rare-earth duster compound of a class, has high reactivity for lactone ring opening polymerization.
For achieving the above object, the technical solution used in the present invention is: a class alkoxy rare-earth duster compound, its molecular formula is
Ln
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8
In the formula, Ln is a rare earth metal, and Me is a methyl.
In the technique scheme, the structure of described duster compound is to link to each other by the alkoxyl group bridge between described 2 rare earth metals and 8 sodium, simultaneously existence end alkoxyl group.
The present invention discloses the application of above-mentioned alkoxy rare-earth duster compound in the lactone ring opening polymerization reaction.
Alkoxy rare-earth duster compound of the present invention promptly can be used for the ring-opening polymerization of catalysis 6-caprolactone, cyclic carbonate ester, also can be used for the copolymerization and the block copolymerization of catalysis 6-caprolactone and carbonic ether.
Alkoxy rare-earth duster compound of the present invention can adopt following method preparation:
In the reaction flask of handling through dehydration and deoxidation, argon shield adds sodium Metal 99.5 and an amount of THF down, adds a certain amount of anhydrous N, N-dimethyl amido ethanol with syringe; be swift in response and carry out; after not having tangible bubble to produce, stirring at room, tube sealing is standby.Get anhydrous LnCl again
3(Ln is a rare earth metal) places the reaction flask of handling through dehydration and deoxidation, adds THF, after the stirring at room, it joined NaOCH
2CH
2NMe
2Tetrahydrofuran solution in, add NaOH again, in 40 ℃ of oil baths behind the stirring reaction, the centrifugal precipitation of removing, the clear liquid vacuum is taken out the THF that desolvates, add the extraction of an amount of toluene, and heat centrifugally, clear liquid is transferred in the reaction flask again, tube sealing, clear crystal is separated out in crystallization under the what room temperature.Be required alkoxy rare-earth duster compound.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the present invention proposes a class novel contain rare earth metal and alkali-metal alkoxyl group heteronuclear multi-metal cluster compound, ring-opening polymerization and copolymerization thereof that it can high activity catalysis 6-caprolactone, cyclic carbonate ester under mild conditions.
2. the present invention is very long as the active lifetime that catalyzer uses, and after first part of monomer polymerization finished, living chain still can continue to make second part of monomer even the 3rd part of monomer polymerization.
3. duster compound of the present invention can also cause the block copolymerization of two kinds of different rings lactones as catalyzer.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: Ln
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8The synthetic Ln=Yb Nd Sm of title complex
In the reaction flask of handling through dehydration and deoxidation, argon shield adds metal Na and an amount of THF down, adds a certain amount of anhydrous N, N-dimethyl amido ethanol with syringe; be swift in response and carry out; after not having tangible bubble to produce, stirring at room 24 hours, tube sealing is standby.Take by weighing anhydrous LnCl again
33mmol, (Ln=Yb Nd Sm wherein is with YbCl
3Be example, take by weighing 0.838g), place the reaction flask of handling through dehydration and deoxidation, add 30ml THF, stirring at room joins NaOCH with it after half an hour
2CH
2NMe
2In the tetrahydrofuran solution (18mmol), the NaOH that adds 0.12g (3mmol) again, stirring reaction is after 24 hours in 40 ℃ of oil baths, and the centrifugal precipitation of removing is taken out the THF that desolvates with the clear liquid vacuum, add an amount of toluene extraction, and heating centrifugally, clear liquid is transferred in the reaction flask again, tube sealing, clear crystal is separated out in crystallization under the what room temperature.Productive rate 80%.
Embodiment two: Yb
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8The ring-opening polymerization of catalysis 6-caprolactone
With catalyzer Yb
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Be made into 1 * 10
-5The toluene solution of M concentration in the round-bottomed flask of the dehydration and deoxidation applying argon gas of strictness, adds 0.6ml 6-caprolactone and 5.55ml toluene successively, places 0 ℃ of ice-water bath to stir, and adds the toluene solution of 0.45ml catalyzer with syringe.Behind the 60min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NHCl-ethanol.Polymkeric substance is dry under vacuum, the 0.60g that weighs, transformation efficiency 100%.
Product adopts gel permeation chromatography (GPC) analysis: Mn=4360, PD=1.45.
Embodiment three: Nd
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8The ring-opening polymerization of catalysis 6-caprolactone
With catalyst n d
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Be made into 1 * 10
-5The toluene solution of M concentration in the round-bottomed flask of the dehydration and deoxidation applying argon gas of strictness, adds 1ml 6-caprolactone and 9.89ml toluene successively, places under 24 ℃ of room temperatures and stirs, and adds the toluene solution of 0.11ml catalyzer with syringe.Behind the 3min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NH Cl-ethanol.Polymkeric substance is dry under vacuum, the 1.03g that weighs, transformation efficiency 100%.
Gpc analysis: Mn=22900, PD=2.208.
Embodiment four: Nd
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8The ring-opening polymerization of catalysis cyclic carbonate ester
With catalyst n d
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Be made into 1 * 10
-5The toluene solution of M concentration in the round-bottomed flask that strict dehydration and deoxidation argon filling was handled, adds the toluene of 0.6728g TMC and 6.15ml.Place under the room temperature and stir, add the toluene solution of 0.44ml catalyzer then with syringe.Behind the 3min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NHCl-ethanol.Polymkeric substance is dry under vacuum, the 0.576g that weighs, transformation efficiency 85.6%.
Gpc analysis: Mn=10844, PD=1.91.
Embodiment five: Sm
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Catalysis 6-caprolactone and carbonic ether copolymerization
With catalyst S m
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Be made into 1 * 10
-5The toluene solution of M concentration in the round-bottomed flask that strict dehydration and deoxidation argon filling was handled, adds the toluene of 0.72g TMC, 0.78ml 6-caprolactone and 13.64ml.Place under the room temperature and stir, add the toluene solution of 0.36ml catalyzer then with syringe.Behind the 3min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NHCl-ethanol.Polymkeric substance is dry under vacuum, the 1.17g that weighs, transformation efficiency 78%.
Gpc analysis: Mn=12576, PD=1.509.
Embodiment six: Sm
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Catalyzed carbon acid esters and 6-caprolactone block copolymerization
With catalyst S m
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Be made into 1 * 10
-5The toluene solution of M concentration in the round-bottomed flask that strict dehydration and deoxidation argon filling was handled, adds the toluene of 0.7g TMC and 13ml.Place under the room temperature and stir, add the toluene solution of 0.68ml catalyzer then with syringe.Behind the 3min, add the 0.76ml 6-caprolactone, behind the continuation polyase 13 min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NHCl-ethanol.Polymkeric substance is dry under vacuum, the 1.27g that weighs, transformation efficiency 87%.
Gpc analysis: Mn=10731, Mw=17907, PD=1.669.
Embodiment seven: Sm
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Catalysis 6-caprolactone and carbonate blocks copolymerization
With catalyst S m
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Be made into 1 * 10
-5The toluene solution of M concentration in the round-bottomed flask that strict dehydration and deoxidation argon filling was handled, adds the toluene of 0.78ml 6-caprolactone and 13.28ml.Place under the room temperature and stir, add the toluene solution of 0.72ml catalyzer then with syringe.Behind the 3min, add 0.72g TMC, behind the continuation polyase 13 min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NH Cl-ethanol.Polymkeric substance is dry under vacuum, the 1.35g that weighs, transformation efficiency 90%.
Gpc analysis: Mn=11234, Mw=26999, PD=2.403.
Embodiment eight: Sm
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Catalysis 6-caprolactone polymerization (segmentation adds monomer)
With catalyst S m
2(OCH
2CH
2NMe
2)
12(OH)
2Na
8Be made into 1 * 10
-5The toluene solution of M concentration in the round-bottomed flask that strict dehydration and deoxidation argon filling was handled, adds the toluene of 0.6ml 6-caprolactone and 9.77ml.Place under the room temperature and stir, add the toluene solution of 0.23ml catalyzer then with syringe.Behind the 3min, add the 0.6ml 6-caprolactone again, behind the continuation polyase 13 min, add the 0.6ml 6-caprolactone once more, behind the polyase 13 min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NHCl-ethanol.Polymkeric substance is dry under vacuum, the 3.0g that weighs, transformation efficiency 100%.
Gpc analysis: Mn=43265, Mw=120361, PD=2.782.
Claims (1)
1. the preparation method of an alkoxy rare-earth duster compound, the molecular formula of described alkoxy rare-earth duster compound is Ln
2(OCH
2CH
2NMe
2)
12(OH)
2Na8, in the formula, Ln is a rare earth metal, Me is a methyl; Get anhydrous LnCl
3Place the reaction flask of handling through dehydration and deoxidation, add THF, after the stirring at room, it is joined NaOCH
2CH
2NMe
2Tetrahydrofuran solution in, it is characterized in that: add NaOH again, in 40 ℃ of oil baths behind the stirring reaction, the centrifugal precipitation of removing, the clear liquid vacuum is taken out the THF that desolvates, add the toluene extraction, and heat centrifugally, clear liquid is transferred in the reaction flask again, tube sealing, clear crystal is separated out in crystallization under the what room temperature, is required alkoxy rare-earth duster compound.
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|---|---|---|---|
| CNB200510022574XA CN100383152C (en) | 2005-12-13 | 2005-12-13 | Akoxy rare earth cluster compound and use thereof |
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|---|---|
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| CN100383152C true CN100383152C (en) | 2008-04-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422196C (en) * | 2006-09-21 | 2008-10-01 | 苏州大学 | Alkoxy rare-earth potassium multi-metal cluster compound and use thereof |
| CN100424087C (en) * | 2006-09-21 | 2008-10-08 | 苏州大学 | Alkoxy rare-earth potassium multi-metal cluster compound and use thereof |
| CN101664699B (en) * | 2009-09-14 | 2011-08-10 | 苏州大学 | Catalyzer used for preparing acidamide compound and application thereof |
| CN105001271B (en) * | 2015-07-23 | 2017-08-08 | 安徽大学 | Neodymium/sodium mixed bimetallic complex and preparation method and application thereof |
| CN104961777B (en) * | 2015-07-23 | 2017-10-31 | 安徽大学 | Rare earth/sodium mixed bimetal complex and preparation method and application thereof |
| CN106632434B (en) * | 2016-12-23 | 2018-08-28 | 安徽大学 | Tert-butoxy rare earth/sodium hetero bimetallic complex and preparation method and application thereof |
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Non-Patent Citations (1)
| Title |
|---|
| 官能化烷氧稀土配合物的合成、结构和催化己内酯开环聚合的研究. 周玉芳.硕士学位论文. 2003 * |
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