CN102101043A - Method for preparing polyvinyl imidazole type silica gel filler - Google Patents
Method for preparing polyvinyl imidazole type silica gel filler Download PDFInfo
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- CN102101043A CN102101043A CN2009101177510A CN200910117751A CN102101043A CN 102101043 A CN102101043 A CN 102101043A CN 2009101177510 A CN2009101177510 A CN 2009101177510A CN 200910117751 A CN200910117751 A CN 200910117751A CN 102101043 A CN102101043 A CN 102101043A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Abstract
The invention discloses a method for preparing a high-efficiency liquid-phase chromatogram filler, in particular to a method for preparing a polyvinyl imidazole type silica gel filler by an atom transfer free radical polymerization technique. The method comprises the following steps of: bromizing full porous spherical silica gel modified by an aminopropyl silanization reagent to prepare bromized silica gel; and performing atom transfer free radical polymerization on the bromized silica gel and N-vinylimidazole to generate polyN-vinylimidazole grafted silica gel. The filler has the advantages of uniform thickness of a polymerized layer, controllability, multiple action mechanism, capacity of separating many kinds of substances under the same chromatographic mode, separation under inverse phase, normal phase and ion chromatography modes, high selectivity and stability, symmetrical peak shape, high column efficiency, large column capacity, good application potential and the like.
Description
Technical field
The invention belongs to the preparation method of efficient liquid phase chromatographic stuffing, particularly adopt the ATRP technology, prepare the method for poly N-vinyl imidazoles grafting silica gel as efficient liquid phase chromatographic stuffing.Under different chromatographic isolation patterns, use this chromatographic material and carry out compartment analysis, with this filler respectively as anti-phase, positive, chromatography of ions applying filler in chromatographic isolation.
Background technology
The silica matrix efficient liquid phase chromatographic stuffing that traditional bonding method is prepared has that fixedly the phase molecule surface coverage is lower, remaining silicon hydroxyl effect, defective such as case carbon is lower, and column capacity is lower.For the fixedly phase coverage rate that improves the silica matrix surface with reduce problem such as remaining silicon hydroxyl effect, the silica gel surface grafting polymerization looks for the spectrum filler to be paid attention to by people, institute's polymers grafted molecule has long carbochain, have a plurality of monomer molecules can improve the filling surface coverage rate on each polymer molecule, and long steric hindrance and the screen effect of polymer molecule in separation process can reduce remaining silicon hydroxyl effect.Normally by free radical chain transfer polymerization method at silica gel surface preparation graft polymers filler because the limitation of this method, cause that polymer layer of thickness is inhomogeneous, polymerisation is uncontrollable, synthetic reappearance is lower.Transfer Radical Polymerization is a kind of novel polymerization technique, has the controlled advantage of reaction.This polymerization technique is that the polymerization process by a dynamic equilibrium carries out, and living radical can keep a metastable quantity under certain condition, makes polymerisation reach controlled.Utilize the ATRP technology that the poly N-vinyl imidazoles is grafted to full porous spherical silica gel surface, the filler of preparation has that silica gel surface aggregate layer thickness is all even adjustable, and polymerisation is controlled, preparation reappearance height, and post is imitated advantages of higher.
Same high-efficient liquid phase color spectral model separates detection compound of different nature down, and the chromatographic applications under the same chromatographic column multi-mode, all is the research contents that the chromatogram worker pays close attention to all the time.And traditional efficient liquid phase chromatographic stuffing has selectivity, and separating mechanism is comparatively single, is difficult to separate under same chromatogram mode form complicated sample, and can not realizes the chromatographic applications under the same chromatographic column multi-mode.The chromatograph packing material that preparation has the multiple mechanism of action is to realize complex separations and with the key of post multi-mode chromatographic applications.Fixedly phase molecule on the poly N-vinyl imidazoles grafting silica filler can provide the multiple mechanism of action, and for example: the carbochain that the carbon-carbon double bond polymerization forms has certain hydrophobicity, and the imidazole molecule that is connected on the carbochain has certain hydrophily; Imidazole ring has sub-conjugated system in Wuyuan and carbon-to-nitrogen double bon, and conjugated system has the pi-electron cloud, can have π-π effect with having between the molecule of phenyl ring, and have induced dipole-dipole, n-π effect between the same polarity compound; Unsubstituted nitrogen-atoms can also form the imidazole ring cation in conjunction with the hydrogen ion in flowing mutually, with there being ion exchange between the anion on the imidazole ring except that can sheltering remaining silicon hydroxyl; C-2 position hydrogen and sample room have hydrogen bond action etc. on the imidazole ring.
In view of the advantage of atom transition free radical polymerization reaction technology and the characteristics of poly N-vinyl imidazole molecule, the present invention passes through atom transfer radical polymerization method, the bromination silica gel reaction of N-vinyl imidazole monomer and modified silica-gel acquisition is generated poly N-vinyl imidazoles grafting silica gel, make a kind of efficient liquid phase chromatographic stuffing.This filler has that synthetic repeatability is high, the surface aggregate layer thickness all even adjustable, fixedly the phase molecule length controlled, shelter that remaining silicon hydroxyl effect, separating property are good, post imitate high, column capacity greatly, multiple action mechanism, with advantages such as post multi-mode chromatographic applications.By utilizing the chromatographic column of this filler, we are under the reverse-phase chromatography pattern, separation has detected neutral organic compound, acidic organic compound, alkaline organic compound etc. effectively, the immixture of effects such as the mechanism of action is hydrophobic for mainly comprising, π-π, static, hydrogen bond; Under the normal-phase chromatography pattern, also can separate effectively and detect neutral organic compound, acidic organic compound, alkaline organic compound etc., the mechanism of action is for mainly comprising the immixture of effects such as dipole-dipole, hydrogen bond, n-π, π-π; Under the chromatography of ions pattern, to separate effectively and detected inorganic anion, organic anion etc., the mechanism of action is for mainly comprising the immixture of static, π-π, effect such as hydrophobic.Poly N-vinyl imidazoles grafting silica gel chromatograph filler by the preparation of atom transition free radical polymerization reaction technology has good application prospects.
Summary of the invention
The purpose of this invention is to provide a kind of on full porous silicon ball surface, by the ATRP technology, the method for preparing a kind of performance liquid chromatographic column filler prepares that a kind of range of application is wide, column capacity is big, separate the efficient liquid phase chromatographic stuffing of using with the post multi-mode.Behind this chromatogram filler dress post, not only have multiple action mechanism, and can be used for, can be respectively applied for reverse-phase chromatography, normal-phase chromatography, ion chromatographic separation detection with post multi-mode chromatographic isolation.
The present invention realizes by following measure:
The full porous spherical silica gel of the present invention after with the modification of aminopropyl silylating reagent carries out bromination and makes bromination silica gel, then bromination silica gel and N-vinyl imidazole are passed through atom transition free radical polymerization reaction, generate poly N-vinyl imidazoles grafting silica gel, make efficient liquid phase chromatographic stuffing.
A kind of preparation method of polyvinyl imidazol type silica filler is characterized in that comprising successively two steps of following A, B:
A. bromination silica gel is synthetic
Aminopropyl silica gel is added in the reaction vessel, add toluene as reaction dissolvent, mechanical agitation is even, adds an amount of 2-bromine isobutyl acylbromide and triethylamine, reacts under the room temperature; Cooling after reaction finishes, vacuum filtration is used methyl alcohol, water, methanol wash successively, and vacuum drying obtains bromination silica gel;
B. poly N-vinyl imidazoles grafting silica gel is synthetic
Bromination silica gel is added in the reaction vessel, add N, N '-dimethyl formamide stirs as reaction dissolvent, adds 2, the N of the cuprous complex of 2 '-bipyridyl, and N '-dimethyl formamide solution adds the N-vinyl imidazole again, and the noble gas protection adds thermal response; Cooling after reaction finishes, suction filtration is used methyl alcohol, water, methanol wash successively, and drying obtains poly N-vinyl imidazoles grafting silica gel.
The present invention adopts the ATRP technology, and the N-vinyl imidazole is grafted on the full porous spherical silica gel at bromination silica gel surface aggregate.
The present invention is that the weight ratio between aminopropyl silica gel, 2-bromine isobutyl acylbromide, triethylamine, the toluene is 1: 0.15-0.35: 0.05-0.15: 8-12, the following reaction time of room temperature is 6-48h in bromination silica gel synthetic.
The present invention is in poly N-vinyl imidazoles grafting silica gel synthetic, bromination silica gel, 2, and the cuprous complex of 2 '-bipyridyl, N-vinyl imidazole, N, the weight ratio of N '-dimethyl formamide is 1: 0.03-0.15: 0.5-2: 8-12.
The present invention is in poly N-vinyl imidazoles grafting silica gel synthetic, carries out the noble gas protection with high pure nitrogen or argon gas, and reaction temperature is 30-140 ℃, and the reaction time is 6-48h.
The present invention is in the clastotype of reverse-phase chromatography condition, with methanol-water, acetonitrile-water etc. as chromatogram flow phase, flow rate of mobile phase 0.5-2.0ml/min, ultraviolet detects wavelength 254nm, and the object of separation is phenol, phenyl amines, fused ring compound, purine and pyrimidine etc.
The present invention is in the clastotype of normal-phase chromatography condition, with n-hexane-isopropyl alcohol, n-hexane-ethanol etc. as chromatogram flow phase, flow rate of mobile phase 0.5-2.0ml/min, ultraviolet detects wavelength 254nm, and the object of separation is fused ring compound, phthalate esters, parabens, phenol, phenyl amines etc.
The present invention is in the clastotype of chromatography of ions condition, with the sodium chloride solution of 50-200mmol/L or sodium dihydrogen phosphate as chromatogram flow phase, the phase pH that flows is 3.5-7.0, flow rate of mobile phase 0.5-2.0ml/min, the ultraviolet that sodium chloride solution is made mobile phase detects wavelength 214nm, the ultraviolet that sodium dihydrogen phosphate is made mobile phase detects wavelength 200nm, and the object of separation is common inorganic anion (Cl
-, IO
3 -, BrO
3 -, Br
-, NO
3 -, I
-, SCN
-); Ultraviolet detects wavelength 254nm, and the object of separation is organic anion (phenol, neighbour// hydroquinones, benzoate anion class, benzene sulfonic acid root class, phthalate class) etc.
The present invention compares with existing chromatograph packing material and has the following advantages:
1. by the filler of this invention preparation, the polymer layer thickness on surface is even, controlled, synthetic favorable reproducibility, and chromatographic performance is stable.
2. poly N-vinyl imidazoles grafting silica gel chromatograph filler separates the chromatographic peak symmetry of alkali compounds, and fixedly phase molecule itself has good masking action to the remaining silicon hydroxyl on silica gel surface, the remaining silicon hydroxyl effect in the time of can reducing to separate alkali compounds.
3. poly N-vinyl imidazoles grafting silica gel is a kind of filler with multiple action mechanism, not only can separate acidity, neutrality and alkaline organic compound etc., can also separate that some are inorganic, organic anion etc.
4. poly N-vinyl imidazoles grafting silica gel chromatograph filler can be applied to the chromatographic isolation under the multi-mode, can realize the same chromatographic column chromatographic isolation under anti-phase, positive, chromatography of ions pattern respectively.
5. the chromatographic performance of new filler is superior, post is imitated height, column capacity is big.
The present invention adopts the ATRP technology, surface at the full porous silicon ball of micron-scale, grafting the poly N-vinyl imidazoles, prepared a kind of efficient liquid phase chromatographic stuffing, filling surface polymer layer thickness is even, controlled, post is imitated high, column capacity is big, and the separating mechanism with multiple immixture separates the special benefits of using with a post multi-mode, can be respectively at positive, separate acid under the reverse-phase chromatography pattern, neutral, alkali compounds etc., and separate inorganic under the chromatography of ions pattern, organic anions etc. are the chromatographic column fillers that a kind of extremely has application potential.
Description of drawings
Fig. 1 is the synthetic schematic diagram of poly N-vinyl imidazoles grafting silica gel chromatograph filler.
Fig. 2 is the separating effect schematic diagram of fused ring compound under the embodiment 5 reverse-phase chromatography patterns.Abscissa unit is min, and ordinate unit is mv.(1 benzene, 2 naphthalenes, 3 fluorenes, 4 anthracenes, 5 fluoranthene 6 are bent).
Fig. 3 is the separating effect schematic diagram of amino benzenes compounds under the embodiment 6 normal-phase chromatography patterns.Abscissa unit is min, and ordinate unit is mAU.(1N, N '-4 pairs of methylanilines of dimethylaniline 2N-MEA 3 diphenylamines, 5 aniline, 6 ortho-nitranilines, 7 meta nitro anilines, 8 paranitroanilinum).
Fig. 4 is the separating effect schematic diagram of inorganic anion under the embodiment 5 chromatography of ions patterns.Abscissa unit is min, and ordinate unit is mv.(1IO
3 -?2Cl
-?3Br
-?4NO
3 -?5I
-?6SCN
-)。
The specific embodiment
In order to understand the present invention better, describe by example:
Embodiment 1: the preparation of poly N-vinyl imidazoles grafting silica gel
Comprise two steps of following A, B successively:
A. bromination silica gel is synthetic
5.0g aminopropyl silica gel adds in the reaction vessel, adds 50ml toluene, mechanical agitation is even, adds 0.8ml 2-bromine isobutyl acylbromide and 0.6ml triethylamine, reacts 24h under the room temperature.Then, vacuum filtration is used 200ml methyl alcohol, 300ml water, 200ml methanol wash successively, and 65 ℃ of following vacuum drying 12h obtain bromination silica gel then.
B. poly N-vinyl imidazoles grafting silica gel is synthetic
4.0g bromination silica gel adds in the reaction vessel; add 20ml N; N '-dimethyl formamide is done reaction dissolvent; mechanical agitation is even, adds to be dissolved with 150mg cuprous bromide and 180mg 2, the 20ml N of 2 '-bipyridyl; N '-dimethyl formamide solution; add 2ml N-vinyl imidazole again, high pure nitrogen protection adds thermal response 36h under 45 ℃.Be cooled to room temperature then, suction filtration is used 200ml methyl alcohol, 400ml water, 200ml methanol wash successively, and last 65 ℃ of following vacuum drying 12h obtain poly N-vinyl imidazoles grafting silica gel.
Embodiment 2: the preparation of poly N-vinyl imidazoles grafting silica gel
Comprise two steps of following A, B successively:
A. bromination silica gel is synthetic
5.0g aminopropyl silica gel adds in the reaction vessel, adds 60ml toluene, mechanical agitation is even, adds 1.2ml 2-bromine isobutyl acylbromide and 0.5ml triethylamine, reacts 12h under the room temperature.Then, vacuum filtration is used 300ml methyl alcohol, 400ml water, 200ml methanol wash successively, and 65 ℃ of following vacuum drying 8h obtain bromination silica gel then.
B. poly N-vinyl imidazoles grafting silica gel is synthetic
4.0g bromination silica gel adds in the reaction vessel; add 20ml N; N '-dimethyl formamide is done reaction dissolvent; mechanical agitation is even, adds to be dissolved with 120mg cuprous bromide and 150mg 2, the 20ml N of 2 '-bipyridyl; N '-dimethyl formamide solution; add 4ml N-vinyl imidazole again, high pure nitrogen protection adds thermal response 24h under 80 ℃.Be cooled to room temperature then, suction filtration is used 300ml methyl alcohol, 400ml water, 200ml methanol wash successively, and last 65 ℃ of following vacuum drying 12h obtain poly N-vinyl imidazoles grafting silica gel.
Embodiment 3: the preparation of poly N-vinyl imidazoles grafting silica gel
Comprise two steps of following A, B successively:
A. bromination silica gel is synthetic
5.0g aminopropyl silica gel adds in the reaction vessel, adds 50ml toluene, mechanical agitation is even, adds 0.7ml 2-bromine isobutyl acylbromide and 0.6ml triethylamine, reacts 36h under the room temperature.Then, vacuum filtration is used 200ml methyl alcohol, 400ml water, 200ml methanol wash successively, and 65 ℃ of following vacuum drying 8h obtain bromination silica gel then.
B. poly N-vinyl imidazoles grafting silica gel is synthetic
4.0g bromination silica gel adds in the reaction vessel; add 20ml N; N '-dimethyl formamide is done reaction dissolvent; mechanical agitation is even, adds to be dissolved with 160mg cuprous bromide and 200mg 2, the 20ml N of 2 '-bipyridyl; N '-dimethyl formamide solution; add 4ml N-vinyl imidazole again, argon shield adds thermal response 24h under 130 ℃.Be cooled to room temperature then, suction filtration is used 300ml methyl alcohol, 400ml water, 200ml methanol wash successively, and last 65 ℃ of following vacuum drying 12h obtain poly N-vinyl imidazoles grafting silica gel.
Embodiment 4: the separation under the poly N-vinyl imidazoles grafting silica filler post reverse-phase chromatography
The poly N-vinyl imidazoles grafting silica gel of embodiment 1 is adorned post, column length 250mm, column internal diameter 4.6mm.With methanol-water (75: 25) as mobile phase, flow velocity 1ml/min, ultraviolet detects wavelength 254nm, separates fused ring compound (benzene, naphthalene, fluorenes, anthracene, fluoranthene, bend); With n-hexane-ethanol (90: 10) as mobile phase, flow velocity 1.0ml/min, ultraviolet detects wavelength 254nm, Separation of Benzene aminated compounds (N, N '-dimethylaniline, N-ethylaniline, diphenylamines, para-totuidine, aniline, ortho-nitraniline, meta nitro aniline, paranitroanilinum); With 100mM NaCl solution (pH=7) as mobile phase, flow velocity 1.0ml/min, ultraviolet detects wavelength 214nm, separates inorganic anion (IO
3 -, Cl
-, Br
-, NO
3 -, I
-, SCN
-).
Embodiment 5: the separation under the poly N-vinyl imidazoles grafting silica filler post normal-phase chromatography
The poly N-vinyl imidazoles grafting silica gel of embodiment 2 is adorned post, column length 200mm, column internal diameter 4.6mm.With methanol-water (75: 25) as mobile phase, flow velocity 1.0ml/min, ultraviolet detects wavelength 254nm, separates fused ring compound (benzene, naphthalene, fluorenes, anthracene, fluoranthene, bend); With n-hexane-ethanol (80: 20) as mobile phase, flow velocity 1.0ml/min, ultraviolet detects wavelength 254nm, Separation of Benzene aminated compounds (N, N '-dimethylaniline, N-ethylaniline, diphenylamines, to methylaniline, aniline, ortho-nitraniline, meta nitro aniline, paranitroanilinum); With 150mmol/L NaH
2PO
4The mobile phase of solution (pH=5.0) conduct, flow velocity 2.0ml/min, ultraviolet detects wavelength 200nm, separates inorganic anion (IO
3 -, Cl
-, Br
-, NO
3 -, I
-, SCN
-).
Embodiment 6: the separation under the poly N-vinyl imidazoles grafting silica filler post chromatography of ions
The poly N-vinyl imidazoles grafting silica gel of embodiment 3 is adorned post, column length 150mm, column internal diameter 4.6mm.With methanol-water (80: 20) as mobile phase, flow velocity 1.0ml/min, ultraviolet detects wavelength 254nm, separates fused ring compound (benzene, naphthalene, fluorenes, anthracene, fluoranthene, bend); With n-hexane-ethanol (85: 15) as mobile phase, flow velocity 1.0ml/min, ultraviolet detects wavelength 254nm, Separation of Benzene aminated compounds (N, N '-dimethylaniline, N-ethylaniline, diphenylamines, to methylaniline, aniline, ortho-nitraniline, meta nitro aniline, paranitroanilinum); With 100mmol/LNaCl solution (pH=7.0) as mobile phase, flow velocity 1.0ml/min, ultraviolet detects wavelength 214nm, separates inorganic anion (IO
3 -, Cl
-, Br
-, NO
3 -, I
-, SCN
-).
Claims (4)
1. the preparation method of a polyvinyl imidazol type silica filler is characterized in that comprising successively two steps of following A, B:
A. bromination silica gel is synthetic
Aminopropyl silica gel is added in the reaction vessel, add toluene as reaction dissolvent, mechanical agitation is even, adds an amount of 2-bromine isobutyl acylbromide and triethylamine, reacts under the room temperature; Cooling after reaction finishes, vacuum filtration is used methyl alcohol, water, methanol wash successively, and vacuum drying obtains bromination silica gel;
B. poly N-vinyl imidazoles grafting silica gel is synthetic
Bromination silica gel is added in the reaction vessel, add N, N '-dimethyl formamide stirs as reaction dissolvent, adds 2, the N of the cuprous complex of 2 '-bipyridyl, and N '-dimethyl formamide solution adds the N-vinyl imidazole again, and the noble gas protection adds thermal response; Cooling after reaction finishes, suction filtration is used methyl alcohol, water, methanol wash successively, and drying obtains poly N-vinyl imidazoles grafting silica gel.
2. the method for claim 1, it is characterized in that: in bromination silica gel synthetic, weight ratio between aminopropyl silica gel, 2-bromine isobutyl acylbromide, triethylamine, the toluene is 1: 0.15-0.35: 0.05-0.15: 8-12, the following reaction time of room temperature is 6-48h.
3. the method for claim 1, it is characterized in that: in poly N-vinyl imidazoles grafting silica gel synthetic, bromination silica gel, 2, the cuprous complex of 2 '-bipyridyl, N-vinyl imidazole, N, the weight ratio of N '-dimethyl formamide is 1: 0.03-0.15: 0.5-2: 8-12.
4. the method for claim 1 is characterized in that: in poly N-vinyl imidazoles grafting silica gel synthetic, carry out the noble gas protection with high pure nitrogen or argon gas, reaction temperature is 30-140 ℃, and the reaction time is 6-48h.
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|---|---|---|---|
| CN2009101177510A CN102101043B (en) | 2009-12-18 | 2009-12-18 | Method for preparing polyvinyl imidazole type silica gel filler |
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|---|---|---|---|
| CN2009101177510A CN102101043B (en) | 2009-12-18 | 2009-12-18 | Method for preparing polyvinyl imidazole type silica gel filler |
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| CN102101043B CN102101043B (en) | 2012-12-12 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103028383A (en) * | 2012-12-31 | 2013-04-10 | 浙江月旭材料科技有限公司 | Silica gel chromatography packing and preparation method thereof |
| CN104415740A (en) * | 2013-09-04 | 2015-03-18 | 北京蛋白质组研究中心 | Hydrophilic chromatographic packing as well as preparation method and application thereof |
| CN106268715A (en) * | 2016-09-12 | 2017-01-04 | 中国科学院兰州化学物理研究所 | A kind of green synthesis method of carbon quantum dot bonded silica gel chromatograph packing material |
| CN109926034A (en) * | 2019-04-04 | 2019-06-25 | 中国科学院兰州化学物理研究所 | A kind of preparation and application of the silica gel chromatographic column filling material of amphipathic Ionic Liquid Modified |
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| CN101045201A (en) * | 2006-03-30 | 2007-10-03 | 中国科学院兰州化学物理研究所 | Method for preparing liquid phase chromatographic filling of imidazole bond linking silica gel |
| CN101234339A (en) * | 2007-11-14 | 2008-08-06 | 天津大学 | Silica matrix chemically bonded phase packing |
| CN101468307A (en) * | 2007-12-25 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Method for preparing N-methylimidazole based liquid phase chromatography stuffing |
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| CN103028383A (en) * | 2012-12-31 | 2013-04-10 | 浙江月旭材料科技有限公司 | Silica gel chromatography packing and preparation method thereof |
| CN103028383B (en) * | 2012-12-31 | 2014-12-10 | 浙江月旭材料科技有限公司 | Silica gel chromatography packing and preparation method thereof |
| CN104415740A (en) * | 2013-09-04 | 2015-03-18 | 北京蛋白质组研究中心 | Hydrophilic chromatographic packing as well as preparation method and application thereof |
| CN106268715A (en) * | 2016-09-12 | 2017-01-04 | 中国科学院兰州化学物理研究所 | A kind of green synthesis method of carbon quantum dot bonded silica gel chromatograph packing material |
| CN109926034A (en) * | 2019-04-04 | 2019-06-25 | 中国科学院兰州化学物理研究所 | A kind of preparation and application of the silica gel chromatographic column filling material of amphipathic Ionic Liquid Modified |
| CN109926034B (en) * | 2019-04-04 | 2021-08-03 | 中国科学院兰州化学物理研究所 | Preparation and application of silica gel chromatographic packing modified by amphiphilic ionic liquid |
| CN113247863A (en) * | 2021-06-11 | 2021-08-13 | 浙江陶特容器科技股份有限公司 | Preparation method of electronic grade hydrogen bromide gas and application of electronic grade hydrogen bromide gas in etching of polycrystalline silicon grid |
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