CN101327449A - Ion liquid carried Salen metallic catalyst and preparation method - Google Patents

Ion liquid carried Salen metallic catalyst and preparation method Download PDF

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CN101327449A
CN101327449A CNA2008100630049A CN200810063004A CN101327449A CN 101327449 A CN101327449 A CN 101327449A CN A2008100630049 A CNA2008100630049 A CN A2008100630049A CN 200810063004 A CN200810063004 A CN 200810063004A CN 101327449 A CN101327449 A CN 101327449A
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ion liquid
salen
metallic catalyst
ion
liquid supported
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CN101327449B (en
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王勇
王从敏
李浩然
郭丽萍
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The present invention relates to a Salen metal catalyst supported by ionic liquid and a preparation method thereof. Alkyl is used for substituting functionalization ionic liquid with side chain containing minus NH2 group to be reacted with substituted salicylaldehyde to obtain salicylaldehyde ligand supported by the ionic liquid; the salicylaldehyde ligand supported by the ionic liquid is reacted with metal salt containing metal ion Cr<3 plus> or Co<3 plus> to obtain the Salen metal catalyst supported by the ionic liquid. The catalyst is simple for preparing, is stable in water and air and also has good thermal stability at the same time.

Description

Ion liquid supported Salen metallic catalyst and preparation method
Technical field
The present invention relates to the synthetic method of a class Salen metallic catalyst, particularly relate to ion liquid supported Salen metallic catalyst of a class and preparation method thereof.
Background technology
As everyone knows, be that the Salen catalyst in activated centre is at carbon dioxide copolymerization reaction (Acc.Chem.Res., 2004,37,836-844 with the metal; J.Am.Chem.Soc., 2005,127,14026-14038), oxidation reaction (US4970347, US4046813, CN1425642) etc. use very extensive in the course of reaction, but under most of situation, Salen metal species catalyst also has its intrinsic shortcoming, with Salen metal species catalyst carbon dioxide and epoxide copolyreaction is example, although Salen metal species catalyst has overcome organic zinc class catalyst (J.Polym.Sci.Part B:Polym.Let., 1969,7,287-292, with terres rares catalyst (CN 85104956) to problems such as water and air sensitivities, but existing Salen metallic catalyst catalytic efficiency is not high, reaction time is longer, the polycarbonate-based material molecule amount for preparing is less, and these problems have seriously limited its industrial applications.Therefore, development of new high efficiency, Salen metallic catalyst easy to operate, cheap and easy to get are the research directions of present carbon dioxide copolymerization catalyst.
Summary of the invention
The purpose of this invention is to provide novel ion liquid supported Salen metallic catalyst of a class and preparation method thereof, especially, the ion liquid supported Salen metallic catalyst of this class can change its solubility property in water and other organic solvents by the anion that changes combination with it.Such ion liquid supported Salen metallic catalyst preparation is simple relatively, and heat endurance is preferably arranged simultaneously.
The invention provides ion liquid supported Salen metallic catalyst, its structural formula is as follows:
Figure A20081006300400031
In the formula: R 1, R 2, R 3, R 4, R 5Be H, Me, Et, Pr or Bu; The metal M ion is Co 3+Or Cr 3+Anion Y -Be BF 4 -, PF 6 -, Cl -, Br -, F -, PO 4 3-, SO 4 2-, NO 3 -, CH 3COO -In a kind of.
The preparation method who the invention provides ion liquid supported Salen metallic catalyst is to replace side chain with alkyl and contain-NH 2Group functionalization's ionic liquid and substituted salicylic aldehydes reaction prepare ion liquid supported SalenH 2Part (a); SalenH 2Part again with metal ion Cr 3+Or Co 3+Reacting metal salt, prepare ion liquid supported Salen metallic catalyst (b); Reaction equation is as follows:
In the formula: R 1, R 2, R 3, R 4, R 5Be H, Me, Et, Pr, Bu etc., M is Co 3+Or Cr 3+Deng, Y -Be BF 4 -, PF 6 -, Cl -, Br -, F -, PO 4 3-, SO 4 2-, NO 3 -, CH 3COO -Deng.
Be used for an ionic liquid that carries the Salen metallic catalyst among the present invention and can replace quaternary ammonium type for imidazole type, pyridine type and alkyl.
Alkyl replacement side chain contains-NH among the present invention 2Group functionalization's the ionic liquid and the mol ratio of substituted salicylic aldehydes are between 1: 10～10: 1.
SalenH among the present invention 2Part and metal ion Cr 3+Or Co 3+The mol ratio of slaine be between 1: 10～10: 1.
Intermediate ion liquid of the present invention props up the SalenH that carries 2Part (a) synthesis reaction temperature is between 0 ℃～200 ℃, and preferably between 5 ℃～80 ℃, the solvent that is suitable for this reaction is a methyl alcohol, ethanol, isopropyl alcohol, acetone, acetonitrile, chloroform etc.
Intermediate ion liquid of the present invention props up Salen metallic catalyst (b) synthesis reaction temperature that carries between 10 ℃～150 ℃, and preferably between 30 ℃～80 ℃, the solvent that is suitable for this reaction is a methyl alcohol, ethanol, and isopropyl alcohol etc., the Salen central metallic ions is Cr 3+Or Co 3+Deng.
Among the present invention, can change the solubility property of ion liquid supported Salen catalyst by the anion that changes supported ionic liquid.Work as Y -Be PF 6 -During ion, the ion liquid supported catalysts for preparing is hydrophobic; Work as Y -Be BF 4 -, Cl -, Br -, F -, PO 4 3-, SO 4 2-, NO 3 -, CH 3COO -During a kind of in the ion, the ion liquid supported catalysts for preparing is a hydrophily.
The specific embodiment
Following embodiment will more comprehensively describe the present invention.
Embodiment 1
A. the ion liquid supported schiff base ligand of triethylamine hexafluorophosphate is synthetic
Taking by weighing triethylamine 0.05mol (14.5g) is dissolved in and places the 500ml four-hole bottle that stirring arm, constant pressure funnel, reflux condensing tube and thermometer are housed, nitrogen protection in the 200ml methyl alcohol.The reflux condensing tube outlet inserts bubbler.Be dissolved in 0.05mol (5.4g) salicylide in the 80ml absolute ethyl alcohol and put into constant pressure funnel, under 75 ℃, drip 1h gradually, reflux and stir 4h.Slowly be cooled to below 5 ℃ and stir 1h.Vacuum filtration is used absolute ethanol washing 3-4 time, vacuum drying.Obtain the ion liquid supported schiff base ligand of triethylamine hexafluorophosphate (a), productive rate is more than 90%.
B. the ion liquid supported Salen metallic catalyst (b) of triethylamine hexafluorophosphate is synthetic
The schiff base ligand (a) that 4.7g (0.02mol) is ion liquid supported is dissolved in the 500ml four-hole round-bottomed flask of packing in the 200ml absolute ethyl alcohol.With 5.3g (0.0204mol) CrCl 36H2O is dissolved in the 100ml constant pressure funnel of packing in the 80ml absolute ethyl alcohol, inserts four-hole bottle, nitrogen protection, and 70 ℃ slowly drip 1h down.Dropwise the back and continue stirring and refluxing 4h.Decompression distillation obtains pressed powder after removing and desolvating, and puts into the vacuum drying oven drying, productive rate 85.6% after the acetone washing.
Embodiment 2
A. the ion liquid supported part of butyl-pyridinium four hexafluorophosphates is synthetic
Taking by weighing butyl-pyridinium four hexafluorophosphate ionic liquid 0.05mol (14.1g) is dissolved in and places the 500ml four-hole bottle that stirring arm, constant pressure funnel, reflux condensing tube and thermometer are housed, nitrogen protection in the 200ml methyl alcohol.The reflux condensing tube outlet inserts bubbler.Be dissolved in 0.05mol (5.4g) salicylide in the 80ml absolute ethyl alcohol and put into constant pressure funnel, under 75 ℃, drip 1h gradually, reflux and stir 4h.Slowly be cooled to below 5 ℃ and stir 1h.Vacuum filtration is used absolute ethanol washing 3-4 time, vacuum drying.Obtain the ion liquid supported Salen part (a) of butyl-pyridinium four hexafluorophosphates, productive rate is more than 90%.
B. the ion liquid supported Salen metallic catalyst (b) of butyl-pyridinium four hexafluorophosphates is synthetic
The part that 0.01mol is ion liquid supported is dissolved in the 500ml four-hole round-bottomed flask of packing in the 200ml absolute ethyl alcohol.0.0204mol CrCl36H2O is dissolved in the 100ml constant pressure funnel of packing in the 80ml absolute ethyl alcohol, inserts four-hole bottle, nitrogen protection, 75 ℃ slowly drip 1h down.Dropwise the back and continue stirring and refluxing 3h.Decompression distillation obtains pressed powder after removing and desolvating, and puts into the vacuum drying oven drying, productive rate 85.5% after the acetone washing.
Embodiment 3-6
Preparation method with reference to embodiment 1 step a contains-NH 2Group ionic liquid (a) obtains ion liquid supported SalenH with the substituted salicylic aldehydes reaction 2Synthetic reaction sees Table 1 under part (b) different solvents and the different temperatures
Embodiment Ionic liquid (a) Reaction dissolvent Reaction temperature ℃ Productive rate
3 Tripropyl amine (TPA) nitrate functional-type ionic liquid Methyl alcohol 55 94％
4 Methylimidazole nitrate functional-type ionic liquid Isopropyl alcohol 150 91％
5 Tripropyl amine (TPA) nitrate functional-type ionic liquid Ethanol 90 93％
6 Pyridinium tetrafluoroborate salt functional-type ionic liquid Chloroform 70 95％
Embodiment 7-9
With reference to the preparation method of embodiment 1 step 3, SalenH 2Part (b) and reacting metal salt prepare that synthetic reaction sees Table 3 under ion liquid supported Salen metallic catalyst (c) different metal salt, solvent and the different temperatures
Embodiment Ion liquid supported SalenH 2Part (b) Slaine Reaction dissolvent Reaction temperature ℃ Productive rate
7 The Salen part that tripropyl amine (TPA) nitrate functional-type is ion liquid supported CrCl 3·6H 2O Isopropyl alcohol 30 83.5％
8 The Salen part that methylimidazole nitrate functional-type is ion liquid supported CrCl 3·6H 2O Ethanol 50 89％
9 The Salen part that methylimidazole nitrate functional-type is ion liquid supported Co(OAc) 2·4H 2O Isopropyl alcohol 80 86％

Claims (5)

1, a kind of ion liquid supported Salne metallic catalyst, its structural formula is expressed as follows:
Figure A2008100630040002C1
In the formula: R 1, R 2, R 3, R 4, R 5Be H, Me, Et, Pr or Bu; Metal ions M is Co 3+Or Cr 3+, anion Y -Be BF 4 -, PF 6 -, Cl -, Br -, F -, PO 4 3-, SO 4 2-, NO 3 -Or CH 3COO -
2, according to the described ion liquid supported Salen metallic catalyst of claim 1, it is characterized in that: work as Y -Be PF 6 -During ion, be the hydrophobicity catalyst; Work as Y -Be BF 4 -, Cl -, Br -, F -, PO 4 3-, SO 4 2-, NO 3 -, CH 3COO -During a kind of in the ion, be the hydrophily catalyst.
3, the preparation method of the described ion liquid supported Salen metallic catalyst of claim 1 is characterized in that: replace side chain with alkyl and contain-NH 2The functionalized ionic liquid of group and substituted salicylic aldehydes reaction prepare ion liquid supported SalenH 2Part (a); SalenH 2Part (a) again with metal ion Cr 3+Or Co 3+Reacting metal salt, prepare ion liquid supported Salen metallic catalyst (b); Reaction equation is as follows:
Figure A2008100630040002C2
In the formula: R 1, R 2, R 3, R 4, R 5Be H, Me, Et, Pr or Bu; Metal ions M is Co 3+Or Cr 3+, anion Y -Be BF 4 -, PF 6 -, C1 -, Br -, F -, PO 4 3-, SO 4 2-, NO 3 -Or CH 3COO -
4, preparation method according to claim 3 is characterized in that: prepare in the reaction of ion liquid supported salicylide part (a), organic solvent is a methyl alcohol, ethanol, and isopropyl alcohol, acetone, acetonitrile, a kind of in the chloroform, reaction temperature is between 10-150 ℃.
5, preparation method according to claim 3 is characterized in that: prepare in the reaction of ion liquid supported Salen metallic catalyst (b), organic solvent is a methyl alcohol, ethanol, and a kind of in the isopropyl alcohol, the Salen central metallic ions is Cr 3+Or Co 3+
CN2008100630049A 2008-07-10 2008-07-10 Ion liquid carried Salen metallic catalyst and preparation method Expired - Fee Related CN101327449B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940947A (en) * 2010-07-05 2011-01-12 沈阳化工大学 Method for preparing polystyrene resin-immobilized Salon-Co (III) catalyst
CN105949451A (en) * 2016-07-14 2016-09-21 中国科学院过程工程研究所 Method for preparing polycarbonate through basic ionic liquid catalysis
CN106190216A (en) * 2016-07-20 2016-12-07 昆明理工大学 The technique of M (salen) catalysis paper catalytically liquefying biomass in a kind of ionic liquid

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940947A (en) * 2010-07-05 2011-01-12 沈阳化工大学 Method for preparing polystyrene resin-immobilized Salon-Co (III) catalyst
CN101940947B (en) * 2010-07-05 2011-12-21 沈阳化工大学 Method for preparing polystyrene resin-immobilized Salon-Co (III) catalyst
CN105949451A (en) * 2016-07-14 2016-09-21 中国科学院过程工程研究所 Method for preparing polycarbonate through basic ionic liquid catalysis
CN106190216A (en) * 2016-07-20 2016-12-07 昆明理工大学 The technique of M (salen) catalysis paper catalytically liquefying biomass in a kind of ionic liquid

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