CN100422196C - Alkoxy rare-earth potassium multi-metal cluster compound and use thereof - Google Patents
Alkoxy rare-earth potassium multi-metal cluster compound and use thereof Download PDFInfo
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- CN100422196C CN100422196C CNB2006100961574A CN200610096157A CN100422196C CN 100422196 C CN100422196 C CN 100422196C CN B2006100961574 A CNB2006100961574 A CN B2006100961574A CN 200610096157 A CN200610096157 A CN 200610096157A CN 100422196 C CN100422196 C CN 100422196C
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Abstract
The present invention discloses one kind of alkoxy RE-Na-K polymetal cluster compound in the chemical expression of Ln2Na8K8[OCH2CH2N(CH3)2]18(OH)4, where, Ln expresses RE metal. The present invention also discloses the application of the alkoxy RE-Na-K polymetal cluster compound as catalyst for lactone ring-opening polymerization. The alkoxy RE-Na-K polymetal cluster compound has very high activity of catalyzing the ring polymerization and copolymerization of epsilon-caprolactone and cyclic carbonate in mild conditions, and may be used as catalyst for initiating the random copolymerization and block copolymerization of two kinds of cyclic lactone. As catalyst, it has very long active life.
Description
Technical field
The present invention relates to a class alkoxy rare-earth duster compound, particularly a class alkoxy rare-earth potassium multi-metal cluster compound and the application in the ring-opening polymerization of lactone thereof.
Background technology
Aliphatic polyester and polycarbonate are class Biodegradable Polymers, and excellent biological compatibility is arranged, and can be used for the slowly-releasing of medicine.The ring-opening polymerization of cyclic lactone, cyclic carbonate ester is the approach that makes things convenient for of synthetic fat polyester and polycarbonate.
A lot of alkoxide compounds can this class cyclic lactone of catalysis, the ring-opening polymerization of cyclic carbonate ester, 1991, United States Patent (USP) 5,028, but 667 announced the controlled ring-opening polymerization of alkoxyl group yttrium and alkoxy rare-earth compound high reactivity ground catalysis 6-caprolactone, valerolactone.After, reported in succession also in the document that some contain rare earth-sulphur, rare earth-carbon, compound such as rare earth-nitrogen key and bivalent rare earth organic compound can be used as initiator, cause the ring-opening polymerization of 6-caprolactone, cyclic carbonate ester.Yet have only two class rare earth duster compounds to can be used as the initiator of lactone ring opening polymerization so far: the first kind is exactly the isopropoxy rare earth duster compound Ln of the same nuclear of United States Patent (USP) report in 1991
5O (O
iPr)
13, wherein Ln is a 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.Contain 5 rare earth metals in this duster compound, 13 isopropoxies and 1 Sauerstoffatom are by the coordination formation of rare earth and oxygen; Second class is the applicant disclosed heteronuclear alkoxyl group duster compound Ln that contains rare earth metal and Alkali-Metal Na in Chinese invention patent application CN1789272A
2Na
8[OCH
2CH
2N (CH
3)
2]
12(OH)
2, wherein Ln is a rare earth metal, contains rare earth metal, Alkali-Metal Na, alkoxyl group and hydroxyl in this class duster compound, links to each other by the alkoxyl group bridge between each metal.
Once had document (Hamitou.A., Jerome.R., Teyssie.P.H., Journal of PolymerScience., 1997,15,1035-1041) report structural formula be (RO)
nM
2OM
1The alkoxyl group compound that heterocaryotizes be the highly active lactone ring opening polymerization catalyzer of a class, wherein M
1Be Zn, Co, Mo, Fe, Cr and Mn; M
2Be Al (III) and Ti (IV); R just is, XOR uncle-alkoxyl group.But do not see the multi-metal cluster compound that contains rare earth metal and alkali metallic sodium potassium report as yet as the lactone ring opening polymerization catalyzer.
Summary of the invention
The object of the invention provides a class and has highly active new alkoxy rare-earth duster compound for lactone ring opening polymerization.
For achieving the above object, the technical solution used in the present invention is that a kind of alkoxy rare-earth alkali metal cluster compound has following chemical formula and forms:
Ln
2Na
8K
8[OCH
2CH
2N(CH
3)
2]
18(OH)
4
Wherein, Ln represents rare earth metal.
Rare earth metal mentioned above is meant ytterbium, the samarium in the lanthanon.
In the technique scheme, described duster compound contains 18 alkoxyl groups, links to each other by the alkoxyl group bridge between described each metal.
The present invention ask for protection simultaneously above-mentioned alkoxy rare-earth potassium multi-metal cluster compound in lactone ring opening polymerization reaction as Application of Catalyst.
Contain two rare earth metals, eight Alkali-Metal Na and eight basic metal K, 18 alkoxyl groups and four hydroxyls in the duster compound in the technique scheme, link to each other by the alkoxyl group bridge between each metal.It can be under mild conditions with the ring-opening polymerization and the copolymerization thereof of high active catalytic 6-caprolactone, cyclic carbonate ester.
Alkoxy rare-earth potassium multi-metal cluster compound of the present invention can adopt following method preparation:
In the reaction flask of handling through dehydration and deoxidation, argon shield adds metal K 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 an amount of anhydrous rare earth trichloride again, place the reaction flask of handling through dehydration and deoxidation, add THF, stirring at room joins the KOCH of above-mentioned acquisition with it after half an hour
2CH
2N (CH
3)
2Tetrahydrofuran solution in, add NaOH again, treating different things alike, 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 and THF extraction, and heating centrifugally, clear liquid is transferred in the reaction flask again, tube sealing, clear crystal is separated out in crystallization under room temperature.Be required duster compound.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the present invention has provided the new alkoxy rare-earth potassium multi-metal cluster compound of a class, it can be under mild conditions with the ring-opening polymerization and the copolymerization thereof of high active catalytic 6-caprolactone, cyclic carbonate ester.From embodiment as can be seen, under 20 ℃ of the room temperatures, 6-caprolactone monomer and catalyst molar ratio are 15000, and transformation efficiency can reach 100%, the transformation frequency of catalyzer (turnover frequency TOF) 9 * 10 in the 1min
5Mole of monomer/mol catalyst hour, and catalyzer TOF=2.4 * 10 among the prior art CN1789272A
5Mole of monomer/mol catalyst hour; Under the similarity condition, carbonate monomer and catalyst molar ratio are 8000, and transformation efficiency can reach 90.9% in the 1min, and its activity is also than the duster compound Ln that only contains accordingly Na
2Na
8[OCH
2CH
2N (CH
3)
2]
12(OH)
2High.
2. duster compound of the present invention can be used as random copolymerization and the block copolymerization that catalyzer causes two kinds of different rings lactones.
3. active lifetime was very long when duster compound of the present invention used as catalyzer, and after first part of monomer polymerization finished, living chain still can continue to make second part of monomer polymerization.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: Ln
2Na
8K
8[OCH
2CH
2N (CH
3)
2]
18(OH)
4The synthetic Ln=YbSm of duster compound
In the reaction flask of handling through dehydration and deoxidation (is example with Ln=Yb); argon shield adds metal K and an amount of THF down; add 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 YbCl again
30.84g (3mmol) place the reaction flask of handling through dehydration and deoxidation, add 30ml THF, stirring at room joins KOCH with it after half an hour
2CH
2N (CH
3)
2In the tetrahydrofuran solution (27mmol), the NaOH that adds 0.24g (6mmol) again, treating different things alike, 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 and THF extraction, and heating centrifugally, clear liquid is transferred in the reaction flask again, tube sealing, clear crystal is separated out in crystallization under room temperature.Productive rate 78%.
Embodiment two: Yb
2Na
8K
8[OCH
2CH
2N (CH
3)
2]
18(OH)
4The ring-opening polymerization of catalysis 6-caprolactone
Catalyzer is made into 5 * 10
-6The toluene solution of volumetric molar concentration in the round-bottomed flask of the dehydration and deoxidation applying argon gas of strictness, adds 1.00ml 6-caprolactone and 9.88ml toluene successively, places under 20 ℃ of room temperatures and stirs, and adds the toluene solution that contains the 0.12ml catalyzer with syringe.Behind the 1min, the HCl-ethanol termination with 2N goes out polymkeric substance with a large amount of ethanol sedimentations at last.Polymkeric substance is dry under vacuum, the 1.03g that weighs, transformation efficiency 100%.Gpc analysis: number-average molecular weight (Mn)=79259, molecular weight distributing index (weight-average molecular weight/number-average molecular weight Mw/Mn)=1.90.
Embodiment three: Sm
2Na
8K
8[OCH
2CH
2N (CH
3)
2]
18(OH)
4The ring-opening polymerization of catalysis 6-caprolactone
Catalyzer is made into 2.5 * 10
-6The toluene solution of volumetric molar concentration in the round-bottomed flask of the dehydration and deoxidation applying argon gas of strictness, adds 1.00ml 6-caprolactone and 9.64ml toluene successively, places under 20 ℃ of room temperatures and stirs, and adds the toluene solution of 0.36ml catalyzer with syringe.Behind the 1min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NHCl-ethanol.Polymkeric substance is dry under vacuum, the 1.03g that weighs, transformation efficiency 100%.Gpc analysis: number-average molecular weight (Mn)=51891, molecular weight distributing index (weight-average molecular weight/number-average molecular weight Mw/Mn)=2.74.
Embodiment four: Yb
2Na
8K
8[OCH
2CH
2N (CH
3)
2]
18(OH)
4The ring-opening polymerization of catalysis cyclic carbonate ester
Catalyzer is made into 5 * 10
-6The toluene solution of volumetric molar concentration in the round-bottomed flask that strict dehydration and deoxidation argon filling was handled, adds the toluene of 0.44g TMC and 4.10ml.Place under the room temperature and stir, add the toluene solution of 0.11ml catalyzer then with syringe.Behind the 1min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NHCl-ethanol.Polymkeric substance is dry under vacuum, the 0.40g that weighs, transformation efficiency 90.9%.Gpc analysis: number-average molecular weight (Mn)=29047, molecular weight distributing index (weight-average molecular weight/number-average molecular weight Mw/Mn)=2.08.
Embodiment five: Yb
2Na
8K
8[OCH
2CH
2N (CH
3)
2]
18(OH)
4Catalysis 6-caprolactone and carbonic ether copolymerization
Catalyzer is made into 5 * 10
-6The toluene solution of volumetric molar concentration in the round-bottomed flask that strict dehydration and deoxidation argon filling was handled, adds the toluene of 0.44g TMC, 0.476ml 6-caprolactone and 8.60ml.Place under the room temperature and stir, add the toluene solution of 0.21ml catalyzer then with syringe.Behind the 1min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NHCl-ethanol.Polymkeric substance is dry under vacuum, the 0.73g that weighs, transformation efficiency 80.5%.Gpc analysis: number-average molecular weight (Mn)=26164, molecular weight distributing index (weight-average molecular weight/number-average molecular weight Mw/Mn)=1.97.
Embodiment six: Yb
2Na
8K
8[OCH
2CH
2N (CH
3)
2]
18(OH)
4Catalysis 6-caprolactone and carbonate blocks copolymerization
Catalyzer is made into 5 * 10
-6The toluene solution of volumetric molar concentration in the round-bottomed flask that strict dehydration and deoxidation argon filling was handled, adds the toluene of 0.41ml 6-caprolactone and 5.94ml.Place under the room temperature and stir, add the toluene solution of 0.18ml catalyzer then with syringe.Behind the 1min, add 0.38g TMC, behind the continuation polymerization 1min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NHCl-ethanol.Polymkeric substance is dry under vacuum, the 0.57g that weighs, transformation efficiency 72.5%.Gpc analysis: number-average molecular weight (Mn)=24822, molecular weight distributing index (weight-average molecular weight/number-average molecular weight Mw/Mn)=1.65.
Embodiment seven: Yb
2Na
8K
8[OCH
2CH
2N (CH
3)
2]
18(OH)
4Catalysis 6-caprolactone polymerization (segmentation adds monomer)
Catalyzer is made into 5 * 10
-6The toluene solution of volumetric molar concentration in the round-bottomed flask that strict dehydration and deoxidation argon filling was handled, adds the toluene of 1.00ml 6-caprolactone and 9.82ml.Place under the room temperature and stir, add the toluene solution of 0.18ml catalyzer then with syringe.Behind the 1min, add the 1.00ml 6-caprolactone again, behind the continuation polymerization 1min, stop, go out polymkeric substance with a large amount of ethanol sedimentations at last with 2NHCl-ethanol.Polymkeric substance is dry under vacuum, the 2.03g that weighs, transformation efficiency 100%.Gpc analysis: number-average molecular weight (Mn)=77819, molecular weight distributing index (weight-average molecular weight/number-average molecular weight Mw/Mn)=1.95.
Claims (3)
1. an alkoxy rare-earth potassium multi-metal cluster compound is characterized in that, has following chemical formula and forms:
Ln
2Na
8K
8[OCH
2CH
2N(CH
3)
2]
18(OH)
4
Wherein, Ln represents rare earth metal, is selected from Yb or Sm.
2. alkoxy rare-earth potassium multi-metal cluster compound according to claim 1 is characterized in that: the structure of described duster compound is for linking to each other by the alkoxyl group bridge between each metal.
The described alkoxy rare-earth potassium multi-metal cluster compound of claim 1 in lactone ring opening polymerization reaction as Application of Catalyst.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5028667A (en) * | 1989-09-29 | 1991-07-02 | E.I. Du Pont De Nemours And Company | Yttrium and rare earth compounds catalyzed lactone polymerization |
CN1789272A (en) * | 2005-12-13 | 2006-06-21 | 苏州大学 | Akoxy rare earth cluster compound and use thereof |
-
2006
- 2006-09-21 CN CNB2006100961574A patent/CN100422196C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5028667A (en) * | 1989-09-29 | 1991-07-02 | E.I. Du Pont De Nemours And Company | Yttrium and rare earth compounds catalyzed lactone polymerization |
US5028667B1 (en) * | 1989-09-29 | 1993-02-09 | Du Pont | |
CN1789272A (en) * | 2005-12-13 | 2006-06-21 | 苏州大学 | Akoxy rare earth cluster compound and use thereof |
Non-Patent Citations (6)
Title |
---|
Heteropolyagostic Interactions inLanthanide(III)Diisopropylamido Complexes. Evans W. J. et al.Inorg. Chem.,Vol.34 . 1995 |
Heteropolyagostic Interactions inLanthanide(III)Diisopropylamido Complexes. Evans W. J. et al.Inorg. Chem.,Vol.34 . 1995 * |
Synthetic and Structural Studies of Nonametallictert-Butoxide Mixed-Metal Complexes of Yttrium,Europium,and Sodium: X-ray Crystal Structures of a New Classof LnNa8(OR)10X Complexes (Ln=Y, Eu, R=CMe3, X=Cl, OH). Evans W. J. et al.J.Am.Chem.Soc.,Vol.115 . 1993 |
Synthetic and Structural Studies of Nonametallictert-Butoxide Mixed-Metal Complexes of Yttrium,Europium,and Sodium: X-ray Crystal Structures of a New Classof LnNa8(OR)10X Complexes (Ln=Y, Eu, R=CMe3, X=Cl, OH). Evans W. J. et al.J.Am.Chem.Soc.,Vol.115 . 1993 * |
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.苏州大学硕士学位论文. 2003 |
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.苏州大学硕士学位论文. 2003 * |
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