CN101234339A - Silica matrix chemically bonded phase packing - Google Patents
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- CN101234339A CN101234339A CNA2007101501727A CN200710150172A CN101234339A CN 101234339 A CN101234339 A CN 101234339A CN A2007101501727 A CNA2007101501727 A CN A2007101501727A CN 200710150172 A CN200710150172 A CN 200710150172A CN 101234339 A CN101234339 A CN 101234339A
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Abstract
The invention relates to a preparation method of silica matrix chemically bonded phase stuffing, which belongs to the technical field of high efficiency liquid phase chromatography. The method comprises the following procedures: firstly, the acidification pretreatment of silica matrix stuffing produces silica matrix particles rich in hydroxide radical; secondly, the bonding of silica matrix stuffing; thirdly, the deactivation processing of silica matrix chemically bonded phase stuffing. Compared with the traditional organic solvent method, the stuffing prepared by the method has higher surface functional group bond rate, thus raising the selectivity and the separating size of the compartment analysis of samples.
Description
Technical field
The present invention relates to the preparation method of silica matrix chemically bonded phase packing in the liquid chromatogram.
Background technology
High performance liquid chromatography (HPLC) is to utilize compound in the technology that the difference of distribution coefficient is separated multicomponent mixture between phase and the fixing phase that flows.Since last century, the seventies came out, the HPLC method is with its quick, efficient, as to be easy to realize operation automation and high flux sample treatment characteristics, obtaining extensive use in fields such as chemistry, pharmacy, clinical, biological, environment, quality inspections, is topmost means in the technical fields such as present trace analysis, process control, preparation separation and purification.Liquid chromatograph is made up of infusion pump, chromatographic column and detector.Wherein chromatographic column is the core component of liquid chromatogram, also is the attrition component that needs often replacing and safeguard.According to the scale of liquid chromatogram separation and the geometric parameter of chromatographic column, liquid-phase chromatographic column can be divided into preparative column, three types of analytical column and microbore columns.Preparative column is used for the preparation of milligram level to kilogram levels high-purity medical product, and column internal diameter does not wait from ten millimeters to tens centimetres, is the key equipment in the bio-pharmaceuticals industry.And column internal diameter is the chromatographic column of 4.6mm, is mainly used in production process monitoring and control of product quality in the fields such as biology, pharmacy, environment, chemical industry, occupied analytical instrument Related product market than great share.In recent years, along with the fast development of liquid chromatography/mass spectrometry GC-MS with popularize, market is the new army that present chromatographic column produce market emerges to the demand sharp increase of column internal diameter less than the microbore column of 4mm.Liquid-phase chromatographic column mainly is made up of with the porous prilled medium of filling wherein glass or stainless steel column jecket.Wherein the performance of porous media is the principal element of decision chromatographic isolation usefulness.According to the character of used host material, liquid chromatography stuffing can be divided into organic and inorganic matrix two big classes.At present, be that the inorganic matrix filler of representative is the main product on the liquid chromatogram consumptive material market with the Bio-sil.Bio-sil is owing to its intensity height, and surface area is big, and the aperture is controlled, and surface silanol group is abundant, good chemical stability, and obtained to use widely, its market share accounts for 90% of all matrix chromatogram packings.
Silica matrix chemically bonded phase chromatography stuffing is by covalent bond some functional groups to be attached to the silica gel surface, has good chromatogram thermodynamics and kinetics performance.Silica matrix chemically bonded phase packing is used comparatively extensive, is mainly used in fields such as product compartment analysis, chipal compounds preparation, synthetic peptide purification, natural drug column chromatography, bio-separation.Wherein be most widely used, be mainly used in anti-phase, positive, chirality, ion-exchange and the steric exclusion chromatography in the high performance liquid chromatography field.According to statistics, bonded-phase chromatography accounts for about 80% in the whole application of high performance liquid chromatography.The chemical surface modification technique of silica gel is divided into three kinds substantially, i.e. liquid phase method, the gentle solid reaction process of self-assembly method.Liquid phase method is to be the silica gel bonded technology of reaction medium with the liquid phase solvent, according to reaction medium whether the existence of water is arranged, and can be divided into aqueous systems method and liquid phase organic solvent method again.The aqueous systems method, be that silica gel is to carry out in moisture medium when carrying out silanization, its reaction is halogen or the at first hydrolysis of alkoxyl in the silylating reagent, cover the silica gel surface after self condensation, hydroxyl that hydrolysis generates and silanol base form hydrogen bond, make the hydrogen bond dehydration promptly obtain alkyl linked phase under the condition of heating.This reaction exists the difficult control of process, the shortcoming of overburden cover poor repeatability.The liquid phase organic solvent method be with organic solvent as reaction medium, under heating condition, halogen in the silylating reagent or alkoxyl are directly and the silanol radical reaction.This method need consume a large amount of organic solvents and have contaminative, and reaction time consumption is long, and post processing is loaded down with trivial details, and batch between repeatability relatively poor.Self-assembly method is to utilize the Langmuir-Blodgett film technique, make the bigger molecule of some polarity on solvent immiscible surface, form the liquid film of one deck high-sequential with it, in substrate insertion or the immersion solvent, then the monolayer liquid film is adsorbed on the monomolecular film that forms one deck densification on the substrate automatically then.The filler that obtains with self-assembling method has good chromatographic performance, and stable under acid and alkali condition, if but the alkyl chain of introducing when oversize because phosphorus content is too high, can cause the chromatogram selectivity to descend, and this procedure is difficult to operate.The silica gel that tradition gas-solid phase reaction method is opposite in the ampere bottle heats, and utilizes the reaction of the silicon hydroxyl on silane reagent steam and silica gel surface, thereby makes silica matrix chemically bonded phase packing.The shortcoming of this method is operation inconvenience, is difficult to amplify.Owing in the ampere bottle, can not stir to reactant, cause surface reaction inhomogeneous, the surface functional group bonded amount is low.
We find in research gas-solid phase reaction method is applied to the process of silica matrix chemically bonded phase packing preparation, after acidifying silica matrix, silane reagent and triethylamine mixing, place autoclave, in inert atmosphere, reactant is carried out high-temperature process, can obtain silica matrix chemically bonded phase packing easily.Compare with above-mentioned conventional method, this method has simple and safe operation, and reaction time consumption is short, and functional group surface bond amount height is easy to amplify advantages such as production.What is more important, this method has been got rid of reaction mediums such as organic solvent or supercritical fluid fully, not only simplified the post processing of product, reduced the production cost of chromatograph packing material, and help reducing labour intensity, improve environmental quality, opened up one for the production of silica matrix chemically bonded phase packing and saved energy and reduce the cost eco-friendly green approach.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of novel silica matrix chemically bonded phase packing, to obtain the high silica matrix chemically bonded phase packing of surface bond amount and to have preparation repeatability between good batch, open up one for the production of silica matrix chemically bonded phase packing and save energy and reduce the cost eco-friendly green approach.
To achieve these goals, the present invention adopts following preparation route: at first silica matrix is carried out the acidifying preliminary treatment.Then dry acidifying silica gel is transferred in the autoclave of a constant volume, added a certain amount of silylating reagent, base catalyst, sealing autoclave charges into inert gas.Stoichiometric number hour under suitable temperature.After reaction finishes, take out and washing dry reaction product, finally obtain silica matrix chemically bonded phase packing.
Above-mentioned preparation method's concrete operations step is as follows:
The preliminary treatment of silica matrix: take by weighing a certain amount of sphere or amorphous silica gel, put into there-necked flask, condenser pipe is installed, add a certain amount of 10% hydrochloric acid, add hot reflux 12h under the mechanical agitation, be neutral with deionized water cyclic washing to filtrate, drying obtains the acidifying silica matrix that hydroxyl is rich on the surface.
The preparation of bonded phase silica filler: take by weighing a certain amount of dry acidifying silica gel, place the autoclave of a constant volume, add a certain amount of silane reagent and base catalyst, mix, sealing autoclave, logical people's dry inert gas.Under stirring reactor is warmed up between 100-350 ℃, the reaction that picks up counting, 0.5-10h is carried out in reaction.Stop heating, the question response system is cooled to room temperature, and the silica matrix chemically bonded phase packing of gained is taken out, use successively methanol-water (1: 1, v/v), the acetone washing, more than 60 ℃ of vacuum drying 12h.
The termination process of bonded phase silica filler: take by weighing a certain amount of bonded phase silica filler, place the autoclave of a constant volume, add a certain amount of little molecule silane reagent, mix, sealing autoclave feeds dry inert gas.Under stirring reactor is warmed up between 100-350 ℃, the reaction that picks up counting, 0.5-10h is carried out in reaction.Stop heating, the question response system is cooled to room temperature, and the bonded phase silica filler that termination process is crossed takes out, and (1: 1, v/v), the acetone washing, 60 ℃ in vacuum is dry 12h down to use methanol-water successively.
The used silica matrix of the present invention is the porous that has hydroxyl, withstand voltage, particle that epigranular distributes, can be unbodied, spherical silica gel, and its surface area is at 50-500m
2/ g, particle diameter is at 2-50 μ m.It can be all Silanization reaction reagent that chemical bonding reacts used silane modifier, as carbon chain lengths in the alkyl silane reagent at C
1-C
40Between all silylating reagents, trim,ethylchlorosilane, HMDS, hexamethyl cyclotrisiloxane, 3-mercaptopropyltriethoxysilane, gamma-aminopropyl-triethoxy-silane, VTES, γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, MTMS, phenyltrimethoxysila,e etc.The functional group of silylating reagent and silicon hydroxyl reaction is chlorine or alkoxyl, and reactive functionality can change to 3 from 1, and alkoxyl can be a methoxy or ethoxy.Used inert gas can be nitrogen, hydrogen, argon gas, neon, argon gas, krypton gas, xenon, radon gas etc.The volume of reactor can change to 10000ml from 10ml, and temperature controlling range is a room temperature to 350 ℃.It is little molecule low boiling silylating reagent that used capping reagent is handled in the deactivation of bonded phase silica filler, as trim,ethylchlorosilane (TMCS), HMDS (HMDS), hexamethyl cyclotrisiloxane (D3), dimethyldichlorosilane (DMDCS), monomethyl trichlorosilane (MTCS), octamethylcy-clotetrasiloxane (D4), decamethylcyclopentaandoxane (D5) etc.Used base catalyst can be pyridine, triethylamine, diethylamine, imidazoles, 2,6-lutidines, 2,4-lutidines etc.
Preparation route by the invention described above, at first silica matrix is carried out acidifying, adopt the autoclave reaction unit then, at a certain temperature, with the silylating reagent itself that gasified as the chemical bonding reaction reagent, by the gas-solid phase reaction course of diffusion-surface absorption-surface chemistry bonding reaction-desorption process, with the silicon hydroxyl generation chemical combination on acidifying silica gel surface, thereby Direct Bonding has the functional group of separation selectivity, with the preparation silica matrix chemically bonded phase packing.By further termination process, prepare the bonded phase silica filler that has suitable selectivity function group, alkali compounds is had inertia.According to the present invention, the gas-solid phase reaction method has the reaction time consumption weak point in the autoclave, the organic solvent that does not need to consume a large amount of costlinesses and have contaminative, and treating capacity is big, and handling safety is reliable, and post processing work is simple, prepares advantages such as good reproducibility between batch.What is more important, the prepared bonded phase silica filler of this method is rolled into a ball bonding rate height than conventional organic solvents method function of surface, thereby has improved selectivity and separating degree that sample separation is analyzed.
Description of drawings
Fig. 1 is data analysis figure among the embodiment 4; 3.0g the acidifying chromatographic silica gel, fixedly γ-mercaptopropyl trimethoxysilane reagent dosage is 1.5ml, triethylamine 0.3ml, and reaction time 6h, reaction temperature is to the influence of silica gel surface bond amount; Abscissa for reaction temperature unit is ℃; Ordinate is the surface bond amount, and unit is mmol/g.
Fig. 2 is the data analysis figure among the embodiment 5; 3.0g the acidifying chromatographic silica gel, 150 ℃ of fixation reaction temperature, triethylamine 0.3ml, reaction time 6h, used γ-mercaptopropyl trimethoxysilane reagent is to the influence of silica gel surface bond amount; Abscissa is the hydrosulphonyl silane reagent dosage, and unit is: mL; Ordinate is the surface bond amount, and unit is: mmol/g.
Fig. 3 is the data analysis figure among the embodiment 6; 3.0g the acidifying chromatographic silica gel, 150 ℃ of fixation reaction temperature, triethylamine 0.3ml, γ-mercaptopropyl trimethoxysilane reagent dosage is 1.5ml, the reaction time is to the influence of silica gel surface bond amount; Abscissa is the reaction time, and unit is: h; Ordinate is the surface bond amount, and unit is: mmol/g.
Fig. 4 is the data analysis figure among the embodiment 7; The gentle solid phase of conventional organic solvents method is sent out the comparison of answering method to prepare chemical bonding silica filler silica gel surface bond amount under the peak optimization reaction condition; Ordinate is the surface bond amount, and unit is: mmol/g.
The specific embodiment
Give further instruction below by embodiment to technology of the present invention.
Adopt traditional liquid phase organic solvent reaction method synthesized silicon rubber matrix chemically bonded phase packing.
Take by weighing 20.0g column chromatography silica gel (subsidiary factory of Haiyang Chemical Plant, Qingdao, granularity: the 200-300 order), put in the there-necked flask, condenser pipe is installed, is added 200ml 10% aqueous hydrochloric acid solution, 105 ℃ of mechanical agitation backflow 12h, be neutral with deionized water cyclic washing to filtrate, 90 ℃ of vacuum drying 12h.
Take by weighing the pretreated silica gel of 6.0g acidifying, 90 ℃ of vacuum drying 12h insert after the cooling in the there-necked flask, and condenser pipe and drying tube are installed.Add dehydrated toluene 60ml (activated molecular sieve is handled more than the 12h), triethylamine 0.6ml, γ-mercaptopropyl trimethoxysilane 3ml.Mechanical agitation feeds drying nitrogen and is heated to refluxing toluene.110 ℃ of isothermal reaction 12h.Stop reaction, silica obtained matrix chemically bonded phase packing use successively toluene, methyl alcohol, methanol-water (1: 1, v/v), methyl alcohol, acetone washing.More than 60 ℃ of vacuum drying 12h.
Adopt gas-solid phase reaction method synthesized silicon rubber matrix chemically bonded phase packing.
Take by weighing the pretreated column chromatography silica gel of dry acidifying of 3.0g, insert in the autoclave of 250ml, the triethylamine that adds 1.5ml γ-mercaptopropyl trimethoxysilane and 0.3ml then, stir, sealing autoclave, logical people's dry inert gas is warmed up to reactor 250 ℃ then, and 3h is carried out in reaction.Stop heating, the question response system is cooled to room temperature, and silica obtained matrix chemically bonded phase packing is used methanol-water successively, acetone washing, 60 ℃ of following dry 12h of vacuum.
Take by weighing the dry sulfydryl chemically bonded phase packing of 3.0g, insert in the autoclave of 250ml, add 3.0ml HMDS (HMDS), stir, sealing autoclave feeds inert gas, reactor is warmed up to 250 ℃, reaction 3h stops heating, is cooled to room temperature, use methanol-water successively, the acetone washing, 60 ℃ of vacuum drying 12h obtain the sulfydryl chemically bonded phase packing that termination process is crossed.
The mensuration of sulfydryl silica filler surface bond rate
1, the silica filler of sulfydryl that accurately weighed 0.1g left and right sides bonding
2, accurately prepare the H of 1mol/L
2SO
4Standard liquid: the dense H of accurately measuring 14.21ml
2SO
4, be dissolved in the deionized water 250ml volumetric flask constant volume
3, accurately prepare 0.2mol/L KMnO
4-1mol/L H
2SO
4Standard liquid: accurately weigh 8.3158g KMnO
4, accurately measure the dense H of 14.21ml
2SO
4Be dissolved in the deionized water 250ml volumetric flask constant volume
The silica filler of the 0.1g left and right sides bonding sulfydryl that 4, will accurately weigh is dispersed in the H of 20ml 1mol/L
2SO
4In the standard liquid, ultrasonic 1-5min is with the 0.2mol/L KMnO that accurately prepares
4-1mol/L H
2SO
4Standard liquid carries out titration, and titration to solution is the pink terminal point that is, and accurately measures used 0.2mol/LKMnO
4-1mol/L H
2SO
4The amount of standard liquid
5, calculate:
5Si-SH+9H
2SO
4+6KMnO
4→5Si-SO
3H+3K
2SO
4+6MnSO
4+9H
2O
Calculate silica gel surface sulfydryl functional group bonded amount by quantitative relation, the each parallel determination of each sample 3 times is averaged.
Embodiment 4
With 3.0g acidifying column layer chromatography silicone rubber filler is the response matrix material, fixing-mercaptopropyl trimethoxysilane reagent dosage 1.5ml, the 0.3ml triethylamine, the reaction time is 6h, investigate the influence of reaction temperature: select a temperature for 25 ℃ from 100 ℃ of-250 ℃ of intervals to silica gel surface bond amount silica gel surface sulfydryl bonded amount, 100 ℃, 125 ℃, 150 ℃, 175 ℃, 200 ℃, 225 ℃, 250 ℃.Fig. 1 is the change curve of the amount of silica gel surface bond mercapto propyl group functional group with reaction temperature.
With 3.0g acidifying column layer chromatography silicone rubber is the response matrix material, 150 ℃ of fixation reaction temperature, 0.3ml triethylamine, reaction time is 6h, and investigation-mercaptopropyl trimethoxysilane reagent dosage is to the influence of silica gel surface bond rate: 0.5ml, 1.0ml, 1.5ml, 2.0ml, 2.5ml.Fig. 2 is the variation relation curve of the amount of silica gel surface bond mercapto propyl group functional group with the silane reagent consumption.
With 3.0g acidifying column layer chromatography silicone rubber is the response matrix material, 150 ℃ of fixation reaction temperature, and-mercaptopropyl trimethoxysilane reagent dosage is 1.5ml, 0.3ml triethylamine is investigated 1h, 3h, 5h, 6h, different reaction time such as 8h is to the influence of silica gel surface bond rate.Fig. 3 is the variation relation curve of the amount of silica gel surface bond mercapto propyl group functional group with the reaction time.
The organic solvent method of embodiment 1 is prepared the chemical bonding reaction triplicate of sulfydryl functional group silica filler, and each silica obtained matrix chemically bonded phase packing carries out the mensuration of surface bond amount respectively, averages, and is 1.0mmol/g.Carry out the gas-solid phase chemistry bonding reaction of three embodiment 2 under the following conditions: 3.0g acidifying silica gel, γ-mercaptopropyl trimethoxysilane 1.5ml, 0.3ml triethylamine, 150 ℃ of reaction 3h.Measure each silica obtained matrix chemically bonded phase packing respectively, average, be 1.34mmol/g.Two kinds of preparation methods' bonded amount as shown in Figure 4.
The obtained sulfydryl bonded phase of embodiment 2 methods silica filler can adsorb some metal ion quantitatively from weak solution, demonstrating excellent performance aspect compartment analysis, enrichment and the recovery trace metal ion, so be with a wide range of applications in fields such as analysis, metallurgy, water treatment and marine resources utilizations.
Adopt the preparation of embodiment 2 methods with ball-type silica gel (BaseLine
Sil, ball-type silica gel, particle diameter 5 μ m, specific area 250m
2/ g, aperture 100 ) the sulfydryl bonded phase silica filler of crossing for the matrix termination process, and the sulfydryl bonded phase silica filler that adopts embodiment 3 methods that termination process is crossed carries out oxidation processes, thereby make the surface for sulfonic bonded phase silica filler, can be used for the analysis of strong cation exchange chromatographic isolation.
Claims (14)
1, a kind of preparation method of silica matrix chemically bonded phase packing is characterized in that, comprises following process:
Step 1: the acidifying preliminary treatment of silica matrix filler obtains being rich in the silica matrix particle of hydroxyl;
Step 2: the bonding of silica matrix filler, the dry silica matrix transfer of granules that has hydroxyl in the autoclave of a constant volume, is added a certain amount of silylating reagent, base catalyst, sealing autoclave charges into inert gas; Stoichiometric number hour under suitable temperature after reaction finishes, takes out also washing dry reaction product, obtains the chemically bonded phase packing of silica matrix;
Step 3: the deactivation of silica matrix chemically bonded phase packing is handled, dry silica matrix chemically bonded phase packing is transferred in the autoclave of a constant volume, add a certain amount of capping reagent, mix, sealing autoclave feeds dry inert gas, stoichiometric number hour under suitable temperature, after reaction finishes, take out and washing dry reaction product, obtain the silica matrix chemically bonded phase packing of deactivation.
2, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1 is characterized in that, described silica matrix particle can be the silica gel of unformed and ball-type.
3, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1 is characterized in that, the particle diameter of described silica matrix can change to 50 μ m from 2 μ m.
4, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1 is characterized in that, the specific area of described silica matrix can be from 50m
2/ g changes to 500m
2/ g.
5. the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1 and 2, it is characterized in that, described particle carries out the acidifying preliminary treatment, it is the hydrochloric acid solution that to add a certain amount of 10% in the matrix granule, 105 ℃ of mechanical agitation backflow 12h in there-necked flask, be neutral with deionized water cyclic washing to filtrate, obtain the equally distributed high-purity silica gel filler of surface hydroxyl.
6, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1 is characterized in that, described silylating reagent is the compound that contains the single, double or trifunctional of alkyl chain.
7, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1 is characterized in that, the functional group of described silylating reagent and silicon hydroxyl reaction is chlorine or alkoxyl, and alkoxyl can be a methoxy or ethoxy.
8. the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1, it is characterized in that, described autoclave is for having temperature controlled autoclave, and the volume of reactor can change to 10000mL from 10mL, and temperature controlling range is a room temperature to 350 ℃.
9, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1, it is characterized in that, the silica matrix chemically bonded phase packing preparation feedback is to carry out in inert gas, and inert gas is a kind of in the following gas at least: nitrogen, hydrogen, argon gas, neon, argon gas, krypton gas, xenon, radon gas.
10, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1 is characterized in that, places the silica matrix chemically bonded phase packing preparation feedback of autoclave to carry out under stirring condition.
11, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1 is characterized in that, described silane modifier can be that carbon chain lengths is at C
1-C
40Between all silylating reagents; For example: trim,ethylchlorosilane, HMDS, hexamethyl cyclotrisiloxane, 3-mercaptopropyltriethoxysilane, gamma-aminopropyl-triethoxy-silane, VTES, γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, MTMS, phenyltrimethoxysila,e.
12, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1 is characterized in that, used silica gel matrix chemically bonded phase packing preparation feedback is the reaction of gas-solid phase chemistry.
13, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1, it is characterized in that, used base catalyst is following a kind of at least: pyridine, triethylamine, diethylamine, imidazoles, 2,6-lutidines, 2,4-lutidines.
14, the preparation method of a kind of silica matrix chemically bonded phase packing according to claim 1, it is characterized in that it is following a kind of at least that used capping reagent is handled in the deactivation of bonded phase silica filler: trim,ethylchlorosilane (TMCS), HMDS (HMDS), hexamethyl cyclotrisiloxane (D3), dimethyldichlorosilane (DMDCS), monomethyl trichlorosilane (MTCS), octamethylcy-clotetrasiloxane (D4), decamethylcyclopentaandoxane (D5).
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| CN104475049A (en) * | 2014-11-07 | 2015-04-01 | 安徽瑞研新材料技术研究院有限公司 | Alkene-silica gel bonded new material and processing method thereof |
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| CN105618017B (en) * | 2016-02-29 | 2017-12-29 | 郑州英诺生物科技有限公司 | The preparation method and applications of controllable hydridization coating bonded silica stationary phase |
| CN109092275A (en) * | 2017-09-27 | 2018-12-28 | 江苏汉邦科技有限公司 | A kind of preparation method of the alkyl linked silica filler of novel hydrophilic |
| CN107970900A (en) * | 2017-11-28 | 2018-05-01 | 中国科学院青岛生物能源与过程研究所 | A kind of MT-PDMS bonded silica gels reversed-phase high performance liquid chromatography stationary phase and its preparation and application |
| CN110013836A (en) * | 2019-03-27 | 2019-07-16 | 天津大学 | Reverse phase/ion exchange mixed mode chromatographic stationary phases, preparation method and application |
| 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 |
| CN111122740A (en) * | 2019-12-31 | 2020-05-08 | 辰欣药业股份有限公司 | Method for separating and determining related substances of oxaliplatin based on C18 bonded phase chromatographic column |
| CN112919480A (en) * | 2021-02-01 | 2021-06-08 | 中国石油天然气股份有限公司 | Dihydroxy silica gel, preparation method thereof and detection system for concentration of functional polymer in produced liquid |
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