CN103736469B - A kind of ionic liquid bonding polysiloxane stationary phase and preparation method thereof - Google Patents
A kind of ionic liquid bonding polysiloxane stationary phase and preparation method thereof Download PDFInfo
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- CN103736469B CN103736469B CN201310704099.9A CN201310704099A CN103736469B CN 103736469 B CN103736469 B CN 103736469B CN 201310704099 A CN201310704099 A CN 201310704099A CN 103736469 B CN103736469 B CN 103736469B
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Abstract
The invention discloses a kind of ionic liquid bonding polysiloxanes chromatographic stationary phases, its general structure is
wherein R is C
8, Ph, i-C
5, C
18and the one in CN five kinds of groups, the present invention additionally provides the preparation method of above-mentioned ionic liquid bonding polysiloxanes chromatographic stationary phases simultaneously, first the polysiloxanes of side chain containing imidazole group is synthesized, then react with halides, obtain the polysiloxanes of side chain containing ionic liquid group, finally, halide anion is exchanged for two (fluoroform sulphonyl) imines anion.This Solid-phase synthesis method is simple, favorable reproducibility; There is good painting stain performance, Heat stability is good, and there is good separation selectivity.
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, side chain contains the chromatographic stationary phases of different imidazole type ion liquid group.
Background technology
Ionic liquid (ionicliquids), also known as organic molten salt, ionic liquid at room temperature etc., be the ionic compound that one (is less than 100 DEG C) at normal temperatures in liquid, be generally made up of the larger organic cation of volume and the relatively little inorganic anion of volume or organic anion.Although PaulWalden etc. have just synthesized this liquid ionic compound as far back as 1914, but, because its heat endurance is not good, fail to obtain deep research in chromatographic stationary phases field always.Until 1992, Wilkes etc. synthesized with 1-ethyl-3-methylimidazole be cation, the novel ion liquid of stable in properties, the research of ionic liquid aspect just really attracts attention.After this, constantly occur containing cationic various ionic liquids such as imidazoles, pyridine, quaternary alkylphosphonium salts, the kind of anion is also increasing, has effectively shifted the application study of ionic liquid in fields such as synthesis, 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 traditional Stationary liquid unexistent " two property " Dualnature) " feature; namely same fixing relative non-polarity, polar compound all have good separation selectivity, and this feature discloses the great potential of ionic liquid in complex sample is separated.This achievement, impels ionic liquid to become rapidly a focus of GC stationary phase research in nearly ten years.
Up to the present, the ionic liquid Stationary liquid reported is broadly divided into three classes, i.e. 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 the mixture (ChineseJ.Anal.Chem.2007 of small molecular ion liquid and traditional polymer Stationary liquid, 35:511-514 and J.ChineseU.2007,28:1260-1262) etc. two types.Supelco company in 2008, takes the lead in being proposed commercial ion liquid chromatography post for Stationary liquid with dication small molecular ion liquid, up to the present, only has 7 kinds of models to select for users.Although the research of polymer ions stationary liquid phase is relatively less, from having been reported, this Stationary liquid is coated with tool advantage in stain performance and modification convenience etc. in raising heat endurance, improvement.From synthetic method, be two classes, a class is that ionic liquid is positioned at main polymer chain (Anaylcalmethods, 2010,2,455-457); Another kind of is that ion liquid based cumularsharolith is in the side chain of polymer with polysiloxanes or polyethylene (Anal.Chem.2005,77,6453-6462) for skeleton.Wherein side chain is containing the polysiloxane stationary phase of ionic liquid, the synthetic method reported at present has two kinds, a kind of method being us and proposing, namely first synthesize the chloride polysiloxanes of side chain, then utilize quaterisation directly to synthesize method (J.Sep.Sci.2010,3 of ionic liquid group at polysiloxanes side chain, 3159-3167 and J.Chromatogr.A, 2011,1218,833-841); Another kind method (Chromatographia, 2011,74,717-724) take containing hydrogen silicone oil as raw material, and by the hydrosilylation with vinyl iminazole ionic liquid, induce one ionic liquid group polysiloxanes.
Summary of the invention
The invention provides a kind of ionic liquid bonding polysiloxane stationary phase, the general structure of this ionic liquid bonding polysiloxane stationary phase is:
wherein R is C
8, Ph, i-C
5, C
18and the one in CN five kinds of groups.
The synthetic method additionally providing above-mentioned ionic liquid bonding polysiloxane stationary phase in the present invention comprises the following steps:
(1), γ-(1-imidazoles) hydroxypropyl methyl diethoxy silane and dimethyldiethoxysilane are added in alkaline solution according to the mol ratio of 1:2.3, be warming up to 80 DEG C of reaction 12h, the ethanol generated in removing course of reaction, then add HMDO, the mol ratio of the HMDO added and γ-(1-imidazoles) hydroxypropyl methyl diethoxy silane is 0.0333:1; Be warming up to 100 DEG C and also continue reaction 48h at this temperature, namely obtain the compound 1 of thickness after having reacted rear decompression removing micromolecular compound, compound 1 is for side chain is containing the polysiloxanes of imidazole group, and its structural formula is as follows:
(2), by compound 1 be fully dissolved in chloroform, add enough halides (X-R), wherein R is C
8, Ph, i-C
5, C
18and the one in CN five kinds of groups; Then back flow reaction chloroform removed under pressure after 48 hours, then the product of back flow reaction is dissolved in acetonitrile, n-hexane extraction is adopted to remove excessive halides, namely compound 2 is obtained after finally decompression removing acetonitrile, compound 2 is ionic liquid bonding polysiloxanes (PIL-R-X), and its structural formula is as follows:
(3), compound 2 is dissolved in ethanol, after adding two trifluoromethanesulfonimide lithium, under normal temperature, reacts 24h, react rear decompression and removed ethanolic solution, then the dissolving of product carrene is washed till with distilled water and can't detect halogen ion residues; After decompression removes carrene and distilled water, vacuum drying obtains faint yellow thick compound 3, and compound 3 is ionic liquid bonding polysiloxane stationary phase (PIL-R-NTf
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) contain the polysiloxanes of imidazoles with side chain for synthesis platform, by the quaterisation with halides, not only can synthesize the polysiloxanes of side chain containing ionic liquid group, and special groups contained in halides be introduced this polymer simultaneously.(3) if the polysiloxanes halides different from two kinds making side chain contain imidazoles is reacted, then two kinds of different ionic liquid groups can be introduced on same main chain.(4), time for Stationary liquid, painting stain performance is good, post effect is high, and maximum operation (service) temperature is not less than 300 DEG C.(5) introducing opposed polarity group can the polarity of Effective Regulation Stationary liquid and separation selectivity.
Detailed description of the invention
Below in conjunction with specific embodiment, detailed specific description is done to the present invention, but content that the present invention protects is not limited to following examples.
Embodiment 1
In the present embodiment, in obtained ionic liquid bonding polysiloxane stationary phase, R is C
18, its structural formula is:
its preparation method is as follows:
1, the synthesis of PSOIm
In reaction bulb, add γ-(1-imidazoles) hydroxypropyl methyl diethoxy silane 4.84g and dimethyldiethoxysilane and 3.6g water, the mol ratio of γ-(1-imidazoles) hydroxypropyl methyl diethoxy silane and dimethyldiethoxysilane is 1:2.3.Add 0.004gKOH again, be warming up to about 80 DEG C of reaction 12h.The most of ethanol of decompression removing, then HMDO is added, the mol ratio of the HMDO added and γ-(1-imidazoles) hydroxypropyl methyl diethoxy silane is 0.0333:1, reaction 48h is continued at 100 DEG C, the product Compound 1 of thickness is obtained after decompression removing Small molecular, compound 1 is for side chain is containing the polysiloxanes (PSOIm) of imidazole group, and its structural formula is as follows:
2, PIL-C
18the synthesis of-Br
3.1g compound 1 is dissolved in 10ml chloroform, adds 4gBr (CH
2)
17cH
3rear backflow 48 hours, removal of solvent under reduced pressure.Then add 20ml acetonitrile to dissolve, remove excessive bromoalkane with n-hexane extraction three times (each 6ml), removal of solvent under reduced pressure obtains compound 2(PIL-C
18-Br), its structural formula is as follows:
3, PIL-C
18-NTf
2synthesis
By 2.9gPIL-C
18-Br is dissolved in 25ml ethanol and dissolves, and adds LiNTf
2about 2.0g, normal-temperature reaction 24h.After removing 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 is checked), 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
18outward, can also be C
8, Ph, i-C
5or CN group, preparation method is identical with the method in embodiment 1.
By the PIL-C obtained in upper step
18-NTf
2prepare capillary chromatographic column, be specially:
(1) pretreatment of capillary column
New void column (12m × 0.25mmI.D.) uses 5mL × 2 methyl alcohol and 5mL × 2 dichloromethane rinse respectively.Then at N
2according to heating schedule process under atmosphere: 50 DEG C start to rise to 310 DEG C with 5 DEG C/min and keep 3h.Painting stain is waited until after processing.
(2) the painting stain of capillary
Get appropriate PIL-C
18-NTf
2as Stationary liquid, with CH
2c
l2for solvent, the solution (g/ml) of preparation Stationary liquid concentration 0.3%, adopts static coating method to be coated with the aforesaid empty capillary column of stain.When pressure is about 20mmHg, temperature 32 DEG C, post internal solvent in 48 hours volatilizations completely.
(3) capillary column is aging
At N
2under atmosphere, adopt following temperature programming method to be coated with stain complete after chromatographic column carry out aging.40 DEG C keep 20 minutes, then rise to 150 DEG C with 1 DEG C/min, keep 30min, then rise to 240 DEG C with 1 DEG C/min, keep 1h, then rise to 320 DEG C with 0.6 DEG C/min and keep about 6h.
Detect PIL-C
18-NTf
2the post effect of capillary column and polarity:
(1) when column temperature 120 DEG C, the post effect measured with naphthalene is 2800plates/m(k is 3.20).
(2) polarity of Stationary liquid
With benzene, n-butanol, 2 pentanone, nitropropane and pyridine for probe, determine PIL-C
18-NTf
2average polarity (Maxwell constant), the results are shown in Table 1.A kind of special role power between the representative of each probe molecule and Stationary liquid, wherein benzene embodies dispersion interaction power (X '); N-butanol embodies proton supply 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 active force; Nitropropane embodies dipole active force (U '); Pyridine embodies proton ability to accept (S ').
Table 1 ionic liquid Stationary liquid PIL-C
18polarity
From table 1, the proton feed force (Y ') of this Stationary liquid and proton capacity (S ') are all very strong, and therefore, hydrogen bond action will be the predominant intermolecular forces between various analysis thing and ionic liquid Stationary liquid.
Claims (2)
1. a synthetic method for ionic liquid bonding polysiloxane stationary phase, the general structure of this ionic liquid bonding polysiloxane stationary phase is:
wherein R is i-C
5, C
18and the one in CN tri-kinds of groups; It is characterized in that described synthetic method comprises the following steps:
(1), γ-(1-imidazoles) hydroxypropyl methyl diethoxy silane and dimethyldiethoxysilane are added in alkaline solution according to the mol ratio of 1:2.3, be warming up to 80 DEG C of reaction 12h, the ethanol generated in removing course of reaction, then add HMDO, the mol ratio of the HMDO added and γ-(1-imidazoles) hydroxypropyl methyl diethoxy silane is 0.0333:1; Be warming up to 100 DEG C and also continue reaction 48h at this temperature, namely obtain the compound 1 of thickness after having reacted rear decompression removing micromolecular compound, compound 1 is for side chain is containing the polysiloxanes of imidazole group, and its structural formula is as follows:
(2), by compound 1 be fully dissolved in chloroform, add enough halides X-R, wherein R is i-C
5, C
18and the one in CN tri-kinds of groups; Then back flow reaction chloroform removed under pressure after 48 hours, then the product of back flow reaction is dissolved in acetonitrile, n-hexane extraction is adopted to remove excessive halides, namely compound 2 is obtained after finally decompression removing acetonitrile, compound 2 is ionic liquid bonding polysiloxanes PIL-R-X, and its structural formula is as follows:
(3), compound 2 is dissolved in ethanol, 24h is reacted under normal temperature after adding two trifluoromethanesulfonimide lithium, react rear decompression removing ethanolic solution, then product carrene dissolved and be washed till with distilled water and can't detect halogen ion residues; After decompression removes carrene and distilled water, vacuum drying obtains faint yellow thick compound 3, and compound 3 is ionic liquid bonding polysiloxane stationary phase PIL-R-NTf
2, its structural formula is:
2., according to the synthetic method of ionic liquid bonding polysiloxane stationary phase according to claim 1, it is characterized in that X-R used in step (2), wherein X represents Cl or Br.
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| Title |
|---|
| High temperature and highly selective stationary phases of ionic liquid bonded polysiloxanes for gas chromatography;Xiaojie Sun et al.;《Journal of Chromatography A》;20101221;第1218卷;第833-841页 * |
| Separation Characteristics of Ionic Liquids Grafted Polymethylsiloxanes Stationary Phases for Capillary GC;Qingquan Wei et al.;《Chromatographia》;20110727;第74卷;第717–724页 * |
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