CN103736469A - Ionic liquid bonded polysiloxane stationary phase and preparation method thereof - Google Patents
Ionic liquid bonded polysiloxane stationary phase and preparation method thereof Download PDFInfo
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- CN103736469A CN103736469A CN201310704099.9A CN201310704099A CN103736469A CN 103736469 A CN103736469 A CN 103736469A CN 201310704099 A CN201310704099 A CN 201310704099A CN 103736469 A CN103736469 A CN 103736469A
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Abstract
The invention discloses an ionic liquid bonded polysiloxane stationary phase. The ionic liquid bonded polysiloxane stationary phase has the structural general formula as shown in the specification, wherein R is one of the five groups of C8, Ph, i-C5, C18 and CN. The invention also provides a preparation method of the ionic liquid bonded polysiloxane stationary phase. The preparation method comprises the following steps: firstly, synthesizing polysiloxane of which the side chain contains an imidazolyl group; then, reacting with a halide to obtain the polysiloxane of which the side chain contains an ionic liquid group; finally, exchanging halogen anions into bis(trifluoromethanesulfonyl)imide anions. According to the stationary phase synthesis method, the reproducibility is simple and high, the coating stability, the thermal stability and the separation selectivity are high.
Description
Technical field
The present invention relates to a kind of synthetic method of ionic liquid bonding polysiloxanes chromatographic stationary phases, specifically refer to that main chain is polysiloxanes, the chromatographic stationary phases that side chain contains different imidazole type ion liquid groups.
Background technology
Ionic liquid (ionic liquids), claim again organic molten salt, ionic liquid at room temperature etc., be the ionic compound that one (is less than 100 ℃) and is liquid at normal temperatures, generally by the larger organic cation of volume and relatively little inorganic anion or the organic anion of volume, formed.Although Paul Walden etc. has just synthesized this liquid ionic compound as far back as 1914,, because its heat endurance is not good, fail to obtain deep research in chromatographic stationary phases field always.Until 1992, Wilkes etc. have synthesized take 1-ethyl-3-methylimidazole as cation, the novel ion liquid of stable in properties, and the research of ionic liquid aspect has just really caused people's concern.After this, containing cationic various ionic liquids such as imidazoles, pyridine, quaternary alkylphosphonium salt, constantly occur, the kind of anion is also increasing, has effectively shifted the application study of ionic liquid in fields such as synthetic, extract and separate and catalysis onto.
Along with deepening continuously of ionic liquid research, (the Anal.Chem.1999 such as Armstrong in 1999,71:3873-6) find, when ionic liquid is used as GC stationary phase, there is fixing mutually unexistent " two property " the Dual nature of tradition) " feature; be that same fixing relatively nonpolar, polar compound all has good separation selectivity, this feature has disclosed the great potential of ionic liquid in complex sample separates.This achievement, impels ionic liquid to become rapidly a focus of GC stationary phase research in nearly ten years.
Up to the present, fixing three classes that are broadly divided into mutually of ionic liquid of having reported, be small molecular ion liquid, mixture ionic liquid and ion liquid polymer, wherein mixture ionic liquid comprises the mixture (J.Chromatogr.A.2008 of different ionic liquid, 1182:119-127 and J.Sep.Sci.2010,33:79-87) and mixture (the Chinese J.Anal.Chem.2007 of the fixing phase of small molecular ion liquid and traditional polymer, 35:511-514 and J.Chinese U.2007,28:1260-1262) etc. two types.Supelco company in 2008, take dication small molecular ion liquid as fixing phase, takes the lead in having released commercial ion liquid chromatography post, up to the present, only has 7 kinds of models to select for user.Although the research of polymer ions stationary liquid phase is relatively less, from having been reported, this fixing in aspect tool advantages such as raising heat endurance, improvement painting stain performance and modification conveniences.From synthetic method, be two classes, a class is that ionic liquid is positioned at main polymer chain (Anaylcal methods, 2010,2,455-457); Another kind of be with polysiloxanes or polyethylene (Anal.Chem.2005,77,6453-6462) for skeleton, ion liquid based cumularsharolith is in the side chain of polymer.Wherein side chain is containing the fixing phase of polysiloxanes of ionic liquid, the synthetic method of having reported at present has two kinds, a kind of is the method that we propose, the i.e. first synthetic chloride polysiloxanes of side chain, then utilizes quaterisation in directly method (J.Sep.Sci.2010,3 of synthetic ionic liquid group of polysiloxanes side chain, 3159-3167 and J.Chromatogr.A, 2011,1218,833-841); Another kind method (Chromatographia, 2011,74,717-724) is take containing hydrogen silicone oil as raw material, by with the hydrosilylation of vinyl iminazole ionic liquid, by the ionic liquid group polysiloxanes that induces one.
Summary of the invention
The invention provides the fixing phase of a kind of ionic liquid bonding polysiloxanes, the general structure of the fixing phase of this ionic liquid bonding polysiloxanes is:
wherein R is C
8, Ph, i-C
5, C
18and the one in five kinds of groups of CN.
In the present invention, also provide the synthetic method of the fixing phase of above-mentioned ionic liquid bonding polysiloxanes to comprise the following steps:
(1), γ-(1-imidazoles) propyl group methyldiethoxysilane and dimethyldiethoxysilane are added in alkaline solution according to the mol ratio of 1:2.3, be warming up to 80 ℃ of reaction 12h, remove the ethanol generating in course of reaction, then add HMDO, the mol ratio of the HMDO adding and γ-(1-imidazoles) propyl group methyldiethoxysilane is 0.0333:1; Be warming up to 100 ℃ and at this temperature, continue reaction 48h, react rear decompression and removed the compound 1 that makes thickness after micromolecular compound, compound 1 contains the polysiloxanes of imidazole group for side chain, and its structural formula is as follows:
(2), compound 1 is fully dissolved in chloroform, add enough halides (X-R), wherein R is C
8, Ph, i-C
5, C
18and the one in five kinds of groups of CN; Then back flow reaction reduced pressure and removes chloroform after 48 hours, then the product of back flow reaction is dissolved in acetonitrile, adopt n-hexane extraction to remove excessive halides, after finally acetonitrile is removed in decompression, make compound 2, compound 2 is ionic liquid bonding polysiloxanes (PIL-R-X), and its structural formula is as follows:
(3), compound 2 is dissolved in ethanol, adds after two fluoroform sulfimide lithiums and react 24h under normal temperature, react rear decompression and removed ethanolic solution, then by product with carrene dissolving and be washed till and can't detect halogen ion residues with distilled water; Decompression is removed after carrene and distilled water, and vacuum drying makes faint yellow thick compound 3, and compound 3 is the fixing phase (PIL-R-NTf of ionic liquid bonding polysiloxanes
2), its structural formula is:
X-R used in step (2), wherein X represents Cl or Br.
The present invention has the following advantages: the reappearance of (1) method is good; (2) take side chain containing the polysiloxanes of imidazoles for synthetic platform, by with the quaterisation of halides, not only can synthesize the polysiloxanes that side chain contains ionic liquid group, and special groups contained in halides be introduced to this polymer simultaneously.(3) if make side chain contain the polysiloxanes halides reactions different from two kinds of imidazoles, can on same main chain, introduce two kinds of different ionic liquid groups.(4) for fixing phase time, painting stain performance is good, post effect is high, and maximum operation (service) temperature is not less than 300 ℃.(5) introduce opposed polarity group and can fix polarity and the separation selectivity of phase by Effective Regulation.
the specific embodiment
Below in conjunction with specific embodiment, the present invention is done to detailed specific description, but content that the present invention protects is not limited to following examples.
Embodiment 1
In the present embodiment, the fixing middle R mutually of obtained ionic liquid bonding polysiloxanes is C
18, its structural formula is:
1, PSOIm's is synthetic
In reaction bulb, add γ-(1-imidazoles) propyl group methyldiethoxysilane 4.84g and dimethyldiethoxysilane and 3.6g water, the mol ratio of γ-(1-imidazoles) propyl group methyldiethoxysilane and dimethyldiethoxysilane is 1:2.3.Add again 0.004g KOH, be warming up to approximately 80 ℃ of reaction 12h.Most of ethanol is removed in decompression, then add HMDO, the mol ratio of the HMDO adding and γ-(1-imidazoles) propyl group methyldiethoxysilane is 0.0333:1, at 100 ℃, continue reaction 48h, the product compound 1 that obtains thickness after little molecule is removed in decompression, compound 1 is for side chain is containing the polysiloxanes (PSOIm) of imidazole group, and its structural formula is as follows:
2, PIL-C
18-Br's is synthetic
3.1g compound 1 is dissolved in 10ml chloroform, adds 4g Br (CH
2)
17cH
3rear backflow 48 hours, removal of solvent under reduced pressure.Then add 20ml acetonitrile to dissolve, with n-hexane extraction three times (each 6ml), remove excessive bromoalkane, removal of solvent under reduced pressure obtains compound 2(PIL-C
18-Br), its structural formula is as follows:
3, PIL-C
18-NTf
2synthetic
By 2.9g PIL-C
18-Br is dissolved in 25ml ethanol and dissolves, and adds LiNTf
2about 2.0g, normal-temperature reaction 24h.Remove after ethanol, use CH
2cl
2about 20ml dissolves, and uses H
2o is washed till inspection and does not measure the residual (AgNO of Br-
3solution check), except obtaining faint yellow thick product P IL-C after desolventizing, vacuum drying
18-nTf
2.
In the present embodiment, R group is except being C
18can also be C outward,
8, Ph, i-C
5or CN group, preparation method is identical with the method in embodiment 1.
By the PIL-C obtaining in upper step
18-NTf
2prepare capillary chromatographic column, be specially:
(1) pretreatment of capillary column
New void column (12m × 0.25mm I.D.) is used respectively 5mL × 2 methyl alcohol and 5mL × 2 dichloromethane rinse.Then at N
2under atmosphere according to heating schedule processing: 50 ℃ of beginnings rise to 310 ℃ with 5 ℃/min and keep 3h.After handling, wait until and be coated with stain.
(2) painting stain capillaceous
Get appropriate PIL-C
18-NTf
2by the phase that fixes, with CH
2c
l2for solvent, the solution (g/ml) of the fixing phase concentration 0.3% of preparation, adopts static coating method to be coated with the aforesaid empty capillary column of stain.When 32 ℃ of the about 20mmHg of pressure, temperature, post internal solvent volatilizees completely about 48 hours.
(3) capillary column is aging
At N
2under atmosphere, adopt following temperature programming method to carry out aging to the chromatographic column being coated with after having steeped.40 ℃ keep 20 minutes, then with 1 ℃/min, rise to 150 ℃, keep 30min, then rise to 240 ℃ with 1 ℃/min, keep 1h, then rise to 320 ℃ of about 6h of maintenance with 0.6 ℃/min.
Detect PIL-C
18-NTf
2post effect and the polarity of capillary column:
(1) when 120 ℃ of column temperatures, the post effect of measuring with naphthalene is that 2800plates/m(k is 3.20).
(2) polarity of fixing phase
Take benzene, n-butanol, 2 pentanone, nitropropane and pyridine as probe, measured PIL-C
18-NTf
2average polarity (Maxwell constant), the results are shown in Table 1.Each probe molecule representative and a kind of special role power of fixing between phase, wherein benzene embodies dispersion interaction power (X '); N-butanol embodies proton and supplies with and proton acceptance effect and dipole active force (Y '); 2 pentanone embodies dipole active force and proton acceptance effect (Z '), but does not have proton to supply with active force; Nitropropane embodies dipole active force (U '); Pyridine embodies proton ability to accept (S ').
Table 1 ionic liquid is fixed phase PIL-C
18polarity
From table 1, proton supply power (Y ') and the proton capacity (S ') of this fixing phase are all very strong, and therefore, hydrogen bond action will be the fixing alternate Main Function power of various analytes and ionic liquid.
Claims (3)
1. the fixing phase of ionic liquid bonding polysiloxanes, is characterized in that the general structure of the fixing phase of this ionic liquid bonding polysiloxanes is:
2. the synthetic method of the fixing phase of ionic liquid bonding polysiloxanes as claimed in claim 1, is characterized in that comprising the following steps:
(1), γ-(1-imidazoles) propyl group methyldiethoxysilane and dimethyldiethoxysilane are added in alkaline solution according to the mol ratio of 1:2.3, be warming up to 80 ℃ of reaction 12h, remove the ethanol generating in course of reaction, then add HMDO, the mol ratio of the HMDO adding and γ-(1-imidazoles) propyl group methyldiethoxysilane is 0.0333:1; Be warming up to 100 ℃ and at this temperature, continue reaction 48h, react rear decompression and removed the compound 1 that makes thickness after micromolecular compound, compound 1 contains the polysiloxanes of imidazole group for side chain, and its structural formula is as follows:
(2), compound 1 is fully dissolved in chloroform, add enough halides (X-R), wherein R is C
8, Ph, i-C
5, C
18and the one in five kinds of groups of CN; Then back flow reaction reduced pressure and removes chloroform after 48 hours, then the product of back flow reaction is dissolved in acetonitrile, adopt n-hexane extraction to remove excessive halides, after finally acetonitrile is removed in decompression, make compound 2, compound 2 is ionic liquid bonding polysiloxanes (PIL-R-X), and its structural formula is as follows:
(3), compound 2 is dissolved in ethanol, adds after two fluoroform sulfimide lithiums and react 24h under normal temperature, react rear decompression and removed ethanolic solution, then by product with carrene dissolving and be washed till and can't detect halogen ion residues with distilled water; Decompression is removed after carrene and distilled water, and vacuum drying makes faint yellow thick compound 3, and compound 3 is the fixing phase (PIL-R-NTf of ionic liquid bonding polysiloxanes
2), its structural formula is:
3. according to ionic liquid bonding polysiloxanes Stationary phase preparation method claimed in claim 2, it is characterized in that X-R used in step (2), wherein X represents Cl or Br.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105146755A (en) * | 2015-07-10 | 2015-12-16 | 湖北中烟工业有限责任公司 | Method for preparing polysiloxane ionic liquid additives for cigarette filters |
| CN108164707A (en) * | 2018-01-08 | 2018-06-15 | 济南大学 | A kind of novel fluorescence polysiloxane group ionic liquid and its application |
| CN110746451A (en) * | 2019-10-28 | 2020-02-04 | 大连工业大学 | Dicationic liquid chromatographic stationary phase and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006021302A1 (en) * | 2004-08-24 | 2006-03-02 | Basf Aktiengesellschaft | Method for producing high-purity quaternary ammonium compounds |
| CN101182300A (en) * | 2007-12-12 | 2008-05-21 | 河北工业大学 | Quaternary ammonium ionic liquid as well as preparation and application method thereof |
-
2013
- 2013-12-19 CN CN201310704099.9A patent/CN103736469B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006021302A1 (en) * | 2004-08-24 | 2006-03-02 | Basf Aktiengesellschaft | Method for producing high-purity quaternary ammonium compounds |
| CN101182300A (en) * | 2007-12-12 | 2008-05-21 | 河北工业大学 | Quaternary ammonium ionic liquid as well as preparation and application method thereof |
Non-Patent Citations (2)
| Title |
|---|
| QINGQUAN WEI ET AL.: "Separation Characteristics of Ionic Liquids Grafted Polymethylsiloxanes Stationary Phases for Capillary GC", 《CHROMATOGRAPHIA》 * |
| XIAOJIE SUN ET AL.: "High temperature and highly selective stationary phases of ionic liquid bonded polysiloxanes for gas chromatography", 《JOURNAL OF CHROMATOGRAPHY A》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105146755A (en) * | 2015-07-10 | 2015-12-16 | 湖北中烟工业有限责任公司 | Method for preparing polysiloxane ionic liquid additives for cigarette filters |
| CN105146755B (en) * | 2015-07-10 | 2019-01-11 | 湖北中烟工业有限责任公司 | A kind of preparation method of polysiloxanes ionic liquid cigarette filter-tip additive agent |
| CN108164707A (en) * | 2018-01-08 | 2018-06-15 | 济南大学 | A kind of novel fluorescence polysiloxane group ionic liquid and its application |
| CN108164707B (en) * | 2018-01-08 | 2021-02-09 | 济南大学 | Polysiloxane-based ionic liquid and application thereof |
| CN110746451A (en) * | 2019-10-28 | 2020-02-04 | 大连工业大学 | Dicationic liquid chromatographic stationary phase and preparation method and application thereof |
| CN110746451B (en) * | 2019-10-28 | 2023-04-14 | 大连工业大学 | Dicationic liquid chromatographic stationary phase and preparation method and application thereof |
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