CN1220055C - Alkyl silica gel bonded chromatographic fixed phase and its prepn process - Google Patents
Alkyl silica gel bonded chromatographic fixed phase and its prepn process Download PDFInfo
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- CN1220055C CN1220055C CN 02128061 CN02128061A CN1220055C CN 1220055 C CN1220055 C CN 1220055C CN 02128061 CN02128061 CN 02128061 CN 02128061 A CN02128061 A CN 02128061A CN 1220055 C CN1220055 C CN 1220055C
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Abstract
The present invention provides an alkyl silica gel bonded chromatographic stationary phase and a preparing method thereof. A bonding chain is embedded in an amide polar radical, and the structural formula of the stationary phase with a bidentate structure is disclosed in the specification, wherein SG represents silica gel particles, and R represents normal-chain alkyl. The present invention also provides the preparing method of the stationary phase, which comprises the following steps: a. silica gel particles react with a silane coupling agent in an organic solvent for 4 to 10 hours at 70 to 130 DEG C; b. then the resulting product reacts with acyl chloride at 20 to 130 DEG C for 8 to 48 hours to prepare the stationary phase. The external part of the stationary phase has a hydrophobic property, and the internal part of the stationary phase has a hydrophilic property. Internal amide radicals and silanol radicals remained on particulate silicon gel can form hydrogen bonds or ion pairs to better shield the activity of the silanol radicals and eliminate the influence of the residual silanol radicals. The stationary phase can be used as a filling material of liquid phase chromatographs to effectively separate and analyze most of organic compounds, particularly alkaline organic compounds under the condition of a relatively-simple moving phase, and can effectively improve the chromatographic peak symmetry of alkaline compounds.
Description
Technical field
The present invention relates to a kind of chromatographic stationary phase and preparation method thereof, specifically, the present invention relates to alkyl silica gel bonded stationary phase that a kind of high performance liquid chromatography compartment analysis uses and preparation method thereof.
Background technology
In the high performance liquid chromatography practice, the application that surpasses half is to adopt reversed-phase liquid chromatography method (Ronald E.Majors, LC-GC Asia Pacific, 1998,1 (4), 33) to realize.Alkyl linked silica stationary is the main stuffing that the reversed-phase liquid chromatography analytical approach is used mutually, wherein uses C
18And C
8The compartment analysis work of bonded silica gel stationary phase accounts for 80% of reversed-phase liquid chromatography method.But, because the existence of silica gel remained on surface silanol base, when the separating polar compound, chromatographic peak distortion hangover.Because factors such as steric restrictions, closed-end technology can not be eliminated the influence of silanol base fully.In recent years, chromatogram worker is the chromatographic resolution analysis that improves alkali compounds, has prepared various alkyl silica gel bonded stationary phase.Kirkland etc. adopt silane reagent, have prepared bidentate silane group stationary phase (Anal.Chem.1998,70,4344), but this one type of silane reagent preparation difficulty is big, the price height.(J.Chromatogr.A such as Buszewski; 1994,763,11), (chromatogram such as Huang Xiaojia; 2001; 19,293), (SCI, 2002 such as scape Yuqin; 23; 210) prepare acid amide type electron screening bonded stationary phase, obtained good chromatographic peak profile and result preferably, be used for the separation of alkali compounds.The deficiencies in the prior art part is: 1, the preparation difficulty is big, the price height; Hangover appears when 2, separating alkali compounds.
Summary of the invention
At above-mentioned defective, the invention provides a kind of novel alkyl silica gel bonded stationary phase and preparation method thereof, to satisfy under better simply chromatographic condition, realization comprises the compartment analysis of most of organic compounds of alkali compounds.
This bonded stationary phase novel structure has the design feature of bidentate silane group stationary phase and amide linkage stationary phase concurrently, and promptly the bonding chain has embedded the acid amides polar group, and has the bidentate structure.The stationary phase outside has hydrophobicity, inner possess hydrophilic property.Silanol base residual on inner amide group and the silica particles forms hydrogen bond or ion pair, can shield silanol base activity better, eliminates the influence of residual silicon alcohol radical.
The present invention is achieved by the following technical solutions:
Chromatographic stationary phase of the present invention is characterized in that the bonding chain embeds the acid amides polar group, and has the bidentate structure, and its structural formula is as follows:
Wherein SG is an aerosil particles, and R is the normal chain alkyl.
The preparation method of stationary phase of the present invention comprises the steps:
The pre-service of a, silica particles: add hydrochloric acid or salpeter solution in the silica particles, ultrasonic Treatment refluxed 1～8 hour, filtered, and was washed till neutrality with redistilled water, in 110～200 ℃ of dryings, made the aerosil particles that the surface has even distribution hydroxyl;
Synthesizing of the amino silica gel of b, two (3-propyl group): in pretreated aerosil particles, add organic solvent, silane coupling agent, ultrasonic or vacuumize processing after, in 70～130 ℃ of reactions 4～10 hours, filter with glass sand hourglass while hot, use toluene and methanol wash successively, be placed on drying in the vacuum dryer then, get the amino silica gel of two (3-propyl group);
The preparation of c, amide linkage stationary phase: in the above-mentioned amino aerosil particles of two (3-propyl group) that makes, add organic solvent and acyl chlorides, wherein said organic solvent comprises triethylamine, in room temperature to 130 ℃ reaction 8～48 hours, filter, solids is used toluene, methanol-water (volume ratio 1: 1), methyl alcohol, ether washing for several times successively, obtains bonded stationary phase of the present invention after the drying.
The stationary phase outside has hydrophobicity, inner possess hydrophilic property.Silanol base residual on inner amide group and the silica particles forms hydrogen bond or ion pair, can shield silanol base activity better, eliminates the influence of residual silicon alcohol radical.Can be under better simply chromatographic condition, realization comprises the compartment analysis of most of organic compounds of alkali compounds.
Description of drawings
Fig. 1 is the comparison of the FT-IR collection of illustrative plates of stationary phase of the present invention and silica gel: last figure is silica gel SILICA,
Figure below is bidentate bonding phase BBP (Bidenate Bonded Phase).
Results of elemental analyses: C 15.25%, H 2.89%, and N 0.99%
Embodiment
Chromatographic stationary phase of the present invention is characterized in that the bonding chain embeds the acid amides polar group, and has the bidentate structure, and its structural formula is as follows:
Wherein SG is an aerosil particles, and R is the normal chain alkyl.
The concrete synthesis step of stationary phase of the present invention is as follows:
1, the pre-service of silica particles: add a certain amount of hydrochloric acid or salpeter solution in the silica particles, ultrasonic Treatment refluxed 1～8 hour, filtered, and was washed till neutrality with redistilled water, in 110～200 ℃ of dryings, made the aerosil particles that the surface has even distribution hydroxyl.
2, the amino silica gel of two (3-propyl group) is synthetic: add organic solvent, silane coupling agent in pretreated aerosil particles, ultrasonic or vacuumize processing after, in 70～130 ℃ of reactions 4～10 hours, filter with glass sand hourglass while hot, use toluene and methanol wash successively, be placed on drying in the vacuum dryer then, get the amino silica gel of two (3-propyl group).This reaction is:
In the formula, X is methoxyl, ethoxy, chlorine atom, and Y and Z are methoxyl, ethoxy, chlorine atom, methyl, isopropyl.
3, the preparation of bidentate amide bonded stationary phase: in the above-mentioned amino aerosil particles of two (3-propyl group) that makes, add organic solvent and acyl chlorides, wherein said organic solvent comprises triethylamine, in room temperature to 130 ℃ reaction 8～48 hours, filter, solids is used toluene, methanol-water (volume ratio 1: 1), methyl alcohol, ether washing for several times successively, obtains bonded stationary phase of the present invention after the drying.React as follows:
The used aerosil particles carrier of the present invention is a kind of porous, and is withstand voltage, and even-grained particulate can be the aerosil particles of unformed or ball-type.Used coupling agent is the silylating reagent that contains two (3-propyl group) amino group, can be two (3-propyl trimethoxy silicon) amine, two (3-propyl-triethoxysilicane) amine, two (3-propyl group dimethoxy-methyl silicon) amine, two (3-propyl group methoxyl dimethyl-silicon) amine, two (3-propyl group methoxyl diisopropyl silicon) amine, two (3-propyl-trichlorosilicane) amine, two (3-propyl-dimethyl chlorine silicon) amine, two (3-propyl group diisopropyl chlorine silicon) amine.The carbon number of used acyl chlorides is from 2 to 30, wherein with chain alkyl the bests of 8 carbon to 18 carbon.
Stationary phase of the present invention can be used for the liquid chromatography of organic compound effectively and separate, and particularly to the separation of alkaline organic compound, the ratio of methyl alcohol and water in the moving phase of only needing usually to regulate just can satisfy the compartment analysis requirement of sample.
Below in conjunction with embodiment and accompanying drawing, the present invention is described further.Embodiment only limits to the present invention is described and is not limitation of the invention.
Embodiment 1:
Get 3.10 gram 7 microns unformed silica gel of pretreated YWG (Haiyang Chemical Plant, Qingdao) in reactor, add 2 milliliter of two (3-propyl trimethoxy silicon) amine and 70 milliliters of toluene, stir, oil bath calorifies under the reflux temperature reacted 6 hours, filter, solids is used toluene and methanol wash successively, drying under reduced pressure then, dried solids adds 70 milliliters of toluene in reactor, 3 milliliters of n-octadecanoyl chlorides, 3 milliliters of triethylamines, reflux 12 hours is filtered, and solids is used toluene successively, methanol-water (volume ratio 1: 1), methyl alcohol, after the ether washing for several times, dry, get 3.62 gram stationary phase, results of elemental analyses: C 15.25%, H 2.89%, N 0.99%, and accompanying drawing 1 is the comparison diagram of the infrared spectrum of prepared stationary phase and silica gel.
The gained stationary phase, filling is in long 300mm, and in the stainless steel column of internal diameter 3.9mm, the chromatographic column that makes is used for the sample separation potpourri.The chromatographic condition that is used for Separation of Benzene, naphthalene, biphenyl, phenanthrene, anthracene is as follows: mobile phase methanol is 80 to 20 with the volume ratio of water, flow velocity 0.5ml/min, and 30 ℃ of column temperatures, the detection wavelength is 254nm.
Embodiment 2:
Embodiment 1 gained stationary phase, filling is in long 300mm, and in the stainless steel column of internal diameter 3.9mm, the chromatographic column that makes also is used for separating neutrality, acidity and alkaline organic compound potpourri.Be used to separate pyridine, aniline, o-toluidine, phenol, benzene and N, the condition of accelerine is as follows: mobile phase methanol is 55 to 45 with the volume ratio of water, flow velocity 0.4ml/min, and 30 ℃ of column temperatures, the detection wavelength is 254nm.
Embodiment 3:
Replace n-octadecanoyl chloride with positive caprylyl chloride, undertaken, get the chromatographic column of 3.51 gram stationary phase and this stationary phase filling by the step of embodiment 1.
Claims (6)
1, a kind of alkyl silica gel bonded chromatographic stationary phase is characterized in that the bonding chain embeds the acid amides polar group, and has the bidentate structure, and its structural formula is as follows:
Wherein SG is an aerosil particles, and R is the normal chain alkyl.
2, the preparation method of the described stationary phase of claim 1 is characterized in that comprising the steps:
The pre-service of a, silica particles: add hydrochloric acid or salpeter solution in the silica particles, ultrasonic Treatment refluxed 1～8 hour, filtered, and was washed till neutrality with redistilled water, in 110～200 ℃ of dryings, made the aerosil particles that the surface has even distribution hydroxyl;
Synthesizing of the amino silica gel of b, two (3-propyl group): in pretreated aerosil particles, add organic solvent, silane coupling agent, ultrasonic or vacuumize processing after, in 70～130 ℃ of reactions 4～10 hours, filter with glass sand hourglass while hot, use toluene and methanol wash successively, be placed on drying in the vacuum dryer then, get the amino silica gel of two (3-propyl group);
The preparation of c, amide linkage stationary phase: in the above-mentioned amino aerosil particles of two (3-propyl group) that makes, add organic solvent, acyl chlorides, wherein said organic solvent comprises triethylamine; In room temperature to 130 ℃ reaction 8～48 hours, filter, solids obtains bonded stationary phase after using toluene, 1: 1 methanol-water of volume ratio, methyl alcohol, ether washing for several times successively after the drying.
3,, it is characterized in that the used aerosil particles carrier of step a is a kind of porous, even-grained unformed or spheric grain according to the described preparation method of claim 2.
4, preparation method according to claim 2 is characterized in that the used silane coupling agent of step b has following chemical structural formula:
In the formula, X is methoxyl, ethoxy, chlorine atom, and Y and Z are methoxyl, ethoxy, chlorine atom, methyl, isopropyl.
5, preparation method according to claim 2 is characterized in that the used acyl chlorides of step c has following chemical structural formula:
R-CO-Cl
In the formula, R is the normal chain alkyl, and carbon number is 2～30.
6,, it is characterized in that the used acyl chlorides of step c has following chemical structural formula according to claim 2 or 5 described preparation methods:
R-CO-Cl
In the formula, R is the normal chain alkyl, and carbon number is 8～18.
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| CN100429512C (en) * | 2006-05-29 | 2008-10-29 | 济南大学 | Coated column for capillary electrophoresis |
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| CN101829551B (en) * | 2010-05-12 | 2013-04-24 | 武汉大学 | Silica gel fixed phase of mixed model as well as preparation method and application thereof |
| CN103566912A (en) * | 2013-11-09 | 2014-02-12 | 四川师范大学 | Liquid chromatographic stationary phase filler and preparation and application thereof |
| CN105618016A (en) * | 2014-11-03 | 2016-06-01 | 中国科学院兰州化学物理研究所 | Preparation method of high-performance liquid chromatographic packing |
| CN105618013B (en) * | 2014-11-24 | 2017-12-15 | 中国科学院大连化学物理研究所 | A kind of preparation method using silica gel as the agglutinin high-effective affinity chromatography material of matrix |
| CN105597715A (en) * | 2016-01-12 | 2016-05-25 | 江苏汉邦科技有限公司 | Preparing method for amide-embedded alkyl bonding liquid chromatogram filler |
| CN106823461A (en) * | 2017-02-28 | 2017-06-13 | 甘肃政法学院 | A kind of preparation method of functionalization graphene coating probe and SPME handle |
| CN110013836B (en) * | 2019-03-27 | 2021-11-05 | 天津大学 | Reversed phase/ion exchange mixed mode chromatographic stationary phase, preparation method and application |
| CN113717548B (en) * | 2020-05-25 | 2022-10-11 | 中国石油化工股份有限公司 | Surface-modified silica gel and preparation method and application thereof |
| CN114748894B (en) * | 2021-11-08 | 2024-07-16 | 天津中科博蕴生物技术有限公司 | Method for separating salidroside by silica gel bonding filler |
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