CN105435759A - Ferrocene bonding chromatographic stationary phase and preparing method thereof - Google Patents
Ferrocene bonding chromatographic stationary phase and preparing method thereof Download PDFInfo
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- CN105435759A CN105435759A CN201510884322.1A CN201510884322A CN105435759A CN 105435759 A CN105435759 A CN 105435759A CN 201510884322 A CN201510884322 A CN 201510884322A CN 105435759 A CN105435759 A CN 105435759A
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Abstract
The invention discloses a ferrocene bonding chromatographic stationary phase and a preparing method thereof. The ferrocene bonding chromatographic stationary phase is obtained in the way that under the protection of inert atmosphere in an organic solvent, azodiisobutyronitrile is added dropwise to 3-mercaptopropyl silanized inorganic matrix microspheres and vinylferrocene to serve as the initiator, reaction is conducted for 18-36 h at 80-120 DEG C, and then cooling, filtration, washing and drying are conducted. The preparing process is simple, cost is low, reaction materials are easy to obtain and have wide sources, and the ferrocene bonding chromatographic stationary phase can be directly used without any modification; the prepared ferrocene bonding chromatographic stationary phase is a universal hydrophobic interaction chromatographic stationary phase, has high separation selectivity for most compounds, and has high application value and potential.
Description
Technical field
The invention belongs to liquid chromatography technology field, be specifically related to a kind of ferrocene bonded chromatographic Stationary liquid and preparation method thereof.
Technical background
High performance liquid chromatography (HPLC) is the topmost part of contemporary chromatographic technique, be with fastest developing speed, the most widely used separate analytical technique of Modern Analytical Chemistry, it plays an increasingly important role in various fields such as chemistry, medicine, food, environmental protection, biochemistry and industry preparations.In highly effective liquid phase chromatographic system, Stationary liquid occupy critical role, and the development of New Stationary Phase is the most active research frontier of modern efficient liquid chromatogram always.
Ferrocene has another name called bicyclopentadiene and closes iron, is a kind of organo-transition metal compound with aromatic nature.Be orange-yellow powder under normal temperature, have camphor smell.Water insoluble, be soluble in the organic solvents such as benzene, ether, gasoline, diesel oil.Do not have an effect with acid, alkali, ultraviolet, stable chemical nature, does not decompose within 400 degrees Celsius.Its molecule presents polarity, has high heat stability, chemical stability and radiation resistance.Since Kealy and the Paulson synthesis of nineteen fifty-one Du Ken university obtains ferrocene, this metallo-organic compound just attract attention with the structure of its uniqueness and physical property, because it has good hydrophobicity, biological oxidability, armaticity, stability, hypotoxicity, biologically active etc., be widely used in the multiple fields such as biology, medicine, space flight, energy-saving and environmental protection, dyestuff, electrochemistry, liquid crystal material, photosensitive material and industry.
The chemical constitution special due to ferrocene and good hydrophobicity, armaticity, stability, make it also have a good application prospect in high performance liquid chromatography field, the preparation and application research about ferrocenyl Stationary Phase for HPLC progressively causes the extensive concern of people.As O.Bordelanne (Chromatographia, 52 (2000) 51-57) adopt ferrocene formyl chloride and Aminopropyl silica gel to react obtained ferrocene bonded silica gel chromatographic stationary phases with Huai (Chromatographia, 55 (2002) 59-553) etc.Ferrocene chlorobenzoyl chloride, N-ferrocenyl (benzoyl group)-phenyalanine methyl ester and Aminopropyl silica gel are reacted obtained two kinds of ferrocenyl bonded silica gel chromatographic stationary phases (CN201410021645.3 by Yu Ajuan etc.; JournalofChromatographyA1283 (2013) 75-81), and its corresponding chromatographic performance is evaluated.
Although reported the synthetic method of multiple ferrocenyl bonded silica gel chromatographic stationary phases at present, but be all carry out bonding gained by Aminopropyl silica gel and ferrocenyl ligands substantially, the synthesis in various degree of associated ligands needs, modification, process is comparatively complicated, and cost is higher.
Summary of the invention
The object of this invention is to provide a kind of ferrocene bonded chromatographic Stationary liquid and preparation method thereof.This Stationary phase preparation method has that raw material is easy to get, reaction condition is gentle, efficiency is high, simple operation and other advantages.
For achieving the above object, the ferrocene bonded chromatographic Stationary liquid that the technical solution used in the present invention provides has following feature structure:
Wherein Matrix is inorganic spherical matrix fill.
Described ferrocene bonded chromatographic Stationary liquid is adopted and is prepared with the following method: by under 3-mercapto propyl silane inorganic matrix microballoon and vinyl ferrocene in organic solvent inert atmosphere protection; dripping azodiisobutyronitrile (AIBN) is initator; react 18 ~ 36 hours under 80 ~ 120 DEG C of conditions, after cooling, filtration, washing, drying, obtain described bonded chromatographic Stationary liquid.
Reaction equation is as follows:
Described 3-mercapto propyl silane inorganic matrix microballoon adopts known method, uses the activated inorganic matrix microspheres of 3-mercapto propyl silane reagent and particle diameter 5 ~ 10 μm through triethylamine catalysis, at toluene and N
2the lower back flow reaction of protection obtains.
In such scheme, described 3-mercapto propyl silane reagent is 3-mercaptopropyltriethoxysilane or 3-mercaptopropyl trimethoxysilane.
In such scheme, described inorganic spherical matrix fill includes but not limited to silica gel microball, zirconium oxide microballoons, titania microsphere, aluminum oxide micro-sphere.
In such scheme, vinyl ferrocene and described 3-mercapto propyl silane inorganic matrix microspheres quality are than being 1:3 ~ 3:1.
Tool of the present invention has the following advantages:
1. preparation process is simple, with low cost.Raw material required for the present invention is easy to get, wide material sources, and directly uses without the need to any modification, and manufacturing cycle is short, with low cost; Reaction condition is gentle, efficient, and preparation process is simple, operates very easy.
2. applied range.Ferrocene bonded chromatographic Stationary liquid provided by the invention is a kind of general type hydrophobic interaction chromatography Stationary liquid, all has good separation selectivity, have higher using value and potentiality to most compound.
Accompanying drawing explanation
Fig. 1 is benzene and four kinds of homologue (a: benzene thereof; B: toluene; C: ethylbenzene; D: propyl benzene; E: butylbenzene) chromatographic fractionation figure.
Fig. 2 is four kinds of condensed-nuclei aromatics compound (a: benzene; B: naphthalene; C: biphenyl; D: anthracene; E: pyrene) chromatographic fractionation figure.
Fig. 3 is four kinds of phenolic compound (a: resorcinol; B: paranitrophenol; C: phenol; D: naphthols) chromatographic fractionation figure.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.Embodiment is only limitted to the present invention is described, but not limitation of the invention.
Embodiment 1:
Get 5.0g activated silica gel (particle diameter 5um), in 250mL three-necked round bottom flask, add new steaming dry toluene 150mL; logical nitrogen 30min, under stirring, adds 5mL3-mercaptopropyl trimethoxysilane; drip 3 triethylamines; under nitrogen protection, be warming up to 110 ~ 120 DEG C, stirring and refluxing reaction 24h; be filtered dry after being cooled to room temperature; wash 2 ~ 3 times respectively with toluene, ether, acetone, methyl alcohol, acetone successively, 60 DEG C of vacuum drying 18h, obtain 3-mercapto propyl silica gel.
Getting 4.5g3-mercapto propylated silica gel joins in 150mL dry toluene; under stirring condition; add vinyl ferrocene 6.0g respectively; 0.3gAIBN, under nitrogen protection, oil bath is heated to 110 DEG C; back flow reaction 24h; products therefrom is successively with toluene, ethanol, acetone washing, and 80 DEG C of vacuum drying, obtain ferrocene bonded silica gel chromatographic stationary phases.This Stationary liquid structure is:
Embodiment 2:
By the method for synthesizing 3-mercapto propyl silica gel in embodiment 1, get 5g active oxidation titanium microballoon (particle diameter 7.5um) as matrix fill, 3-mercapto propyl group titania microsphere can be obtained.
Getting 4.5g3-mercapto propylated titania microsphere joins in 150mL dry toluene; under stirring condition; add vinyl ferrocene 9.0g respectively; 0.3gAIBN, under nitrogen protection, oil bath is heated to 80 DEG C; reaction 36h; products therefrom is successively with toluene, ethanol, acetone washing, and 80 DEG C of vacuum drying, obtain ferrocene bonding titanium oxide chromatographic stationary phases.This Stationary liquid structure is:
Embodiment 3:
By the method for synthesizing 3-mercapto propyl silica gel in embodiment 1, get 5g active oxidation zirconium microballoon (particle diameter 10.0um) as matrix fill, 3-mercaptopropyl trimethoxysilane replaces with 3-mercaptopropyltriethoxysilane, can obtain 3-mercapto propyl group zirconium oxide microballoons.
Getting 4.5g3-mercapto propylated zirconium oxide microballoons joins in 150mL dry toluene; under stirring condition; add vinyl ferrocene 13.5g respectively; 0.3gAIBN, under nitrogen protection, oil bath is heated to 120 DEG C; backflow 12h; products therefrom is successively with toluene, ethanol, acetone washing, and 80 DEG C of vacuum drying, obtain ferrocene bonding zirconia chromatographic stationary phases.This Stationary liquid structure is:
Embodiment 4:
By the method for synthesizing 3-mercapto propyl silica gel in embodiment 1, get 5g activated alumina microballoon (particle diameter 5.0um) as matrix fill, 3-mercaptopropyl trimethoxysilane replaces with 3-mercaptopropyltriethoxysilane, can obtain 3-mercapto propyl group aluminum oxide micro-sphere.
Getting 4.5g mercapto propylated aluminum oxide micro-sphere joins in 150mL dry toluene; under stirring condition; add vinyl ferrocene 1.5g respectively; 0.3gAIBN, under nitrogen protection, oil bath is heated to 110 DEG C; back flow reaction 24h; products therefrom is successively with toluene, ethanol, acetone washing, and 80 DEG C of vacuum drying, obtain ferrocene bonding aluminium oxide chromatographic stationary phases.This Stationary liquid structure is:
Accompanying drawings provide the ferrocene bonded silica gel chromatographic stationary phases actual separation design sketch of preparation in the embodiment of the present invention 1, wherein Fig. 1 is benzene and four kinds of homologue (a: benzene thereof; B: toluene; C: ethylbenzene; D: propyl benzene; E: butylbenzene) chromatographic fractionation figure, Fig. 2 is four kinds of condensed-nuclei aromatics compound (a: benzene; B: naphthalene; C: biphenyl; D: anthracene; E: pyrene) chromatographic fractionation figure.Fig. 3 is four kinds of phenolic compound (a: resorcinol; B: paranitrophenol; C: phenol; D: naphthols) chromatographic fractionation figure.Can find out that from spectrogram ferrocene bonded silica gel chromatographic stationary phases has good separating effect to target separator.
Claims (8)
1. a ferrocene bonded chromatographic Stationary liquid, is characterized in that: this ferrocene bonded chromatographic Stationary liquid has following feature structure:
Wherein Matrix is inorganic spherical matrix fill.
2. ferrocene bonded chromatographic Stationary liquid according to claim 1, is characterized in that:
Described inorganic spherical matrix fill is silica gel microball, zirconium oxide microballoons, titania microsphere, aluminum oxide micro-sphere.
3. the preparation method of ferrocene bonded chromatographic Stationary liquid according to claim 1, is characterized in that:
Described ferrocene bonded chromatographic Stationary liquid is by under 3-mercapto propyl silane inorganic matrix microballoon and vinyl ferrocene in organic solvent inert atmosphere protection; dropping azodiisobutyronitrile is initator; react 18 ~ 36 hours under 80 ~ 120 DEG C of conditions, obtain after cooling, filtration, washing, drying.
4. the preparation method of ferrocene bonded chromatographic Stationary liquid according to claim 3, is characterized in that:
Described 3-mercapto propyl silane inorganic matrix microballoon adopts following methods to prepare: use the activated inorganic matrix microspheres of 3-mercapto propyl silane reagent and particle diameter 5 ~ 10 μm through triethylamine catalysis, at toluene and N
2the lower back flow reaction of protection obtains.
5. the preparation method of ferrocene bonded chromatographic Stationary liquid according to claim 4, is characterized in that:
Described 3-mercapto propyl silane reagent is 3-mercaptopropyltriethoxysilane or 3-mercaptopropyl trimethoxysilane.
6. the preparation method of ferrocene bonded chromatographic Stationary liquid according to claim 3, is characterized in that:
Described organic solvent is toluene.
7. the preparation method of ferrocene bonded chromatographic Stationary liquid according to claim 3, is characterized in that:
Described inorganic spherical matrix fill is silica gel microball, zirconium oxide microballoons, titania microsphere, aluminum oxide micro-sphere.
8. the preparation method of the ferrocene bonded chromatographic Stationary liquid according to any one of claim 3 ~ 7, is characterized in that:
Described vinyl ferrocene and described 3-mercapto propyl silane inorganic matrix microspheres quality are than being 1:3 ~ 3:1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050064446A1 (en) * | 2001-11-01 | 2005-03-24 | Minerva Biotechnologies Corporation | Detection of binding species with colloidal and non-colloidal structures |
| CN103721690A (en) * | 2014-01-17 | 2014-04-16 | 郑州大学 | N-ferrocenyl (benzoyl)-phenylalanine methyl ester bonded silica gel stationary phase as well as preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050064446A1 (en) * | 2001-11-01 | 2005-03-24 | Minerva Biotechnologies Corporation | Detection of binding species with colloidal and non-colloidal structures |
| CN103721690A (en) * | 2014-01-17 | 2014-04-16 | 郑州大学 | N-ferrocenyl (benzoyl)-phenylalanine methyl ester bonded silica gel stationary phase as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| IGNACIO MARTÍNEZ-MONTERO ET AL: ""Thiol−Ene Chemistry of Vinylferrocene: A Simple and Versatile Access Route to Novel Electroactive Sulfur- and Ferrocene- Containing Model Compounds and Polysiloxanes"", 《MACROMOLECULES》 * |
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Application publication date: 20160330 |