CN1958151A - Multiple structured bonding silica gel filling material in high pure chromatogram, and preparation method - Google Patents
Multiple structured bonding silica gel filling material in high pure chromatogram, and preparation method Download PDFInfo
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- CN1958151A CN1958151A CN 200610016153 CN200610016153A CN1958151A CN 1958151 A CN1958151 A CN 1958151A CN 200610016153 CN200610016153 CN 200610016153 CN 200610016153 A CN200610016153 A CN 200610016153A CN 1958151 A CN1958151 A CN 1958151A
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Abstract
A bonded high-purity silica gel with multi-layer structure and used as chromatographic filler for separating alkaline compound is prepared from high-purity silicon sol through coagulating, sintering to obtain high-purity spherical gel, treating its surface by acid and silicate, and bonding a series of silane fixing phases.
Description
Technical field
The invention belongs to the packing technique field, particularly a kind of multiple structured bonding silica gel filling material in high pure chromatogram and preparation method.
Background technology
(the porous spherical silica gel of metal impurities＜50ppm) is that the chromatograph packing material of matrix progressively replaces traditional main product that is become international chromatogram industry by the silica gel chromatograph filler of waterglass manufacturing with high-purity.Account for the whole world at present and analyze more than 80% of chromatographic column market.The preparation of high-purity porous spherical silica matrix has two big class methods usually: 1) prepare the high-purity silicasol aqueous solution by organosilan, realize under certain acidity that then controlled flocculation obtains the micron order uniform microsphere, through high temperature sintering and acid treatment, obtain can be used for high-purity porous spherical silica gel of further bonding again.2) prepare the high-purity organosilicon polymer by the organosilan partial hydrolysis; As prepolymer, a certain amount of pore-foaming agent carries out emulsion polymerization under certain condition in addition, obtains high-purity porous spherical silica gel; Aging through further heating up again, obtain the further chromatograph packing material matrix of bonding.
Two kinds of methods cut both ways.Utilize the silica gel of pore polymerization preparation, aging temperature relatively low (about 300-500 ℃), thereby surface-active is relatively low; But mechanical performance such as withstand voltage properties and anti-shear performance are relatively poor, and particle diameter distributes and the pore-size distribution broad, and chromatography column is imitated on the low side.The porous high-purity silica gel microball material of Nano silica sol preparation has good, the no dead hole of resistance to pressure, post effect height and long characteristics of life-span.But the required high temperature sintering (usually more than 800 ℃) of preparation of silica gel can cause the inhomogeneities and the high activity of hole surface.This part produces the part surface controlled micro crystallization because silica gel begins meeting at 600 ℃, thereby causes the inhomogeneous of surface.The inhomogeneities on this surface and high activity make and cause one of major reason that polar compound trails on silica gel behind the bonding.
People such as Kirkland have reported to adopt acid treatment have been carried out on the surface, can increase surface silanol group density, have reduced surface-active to a certain extent; But still can't solve the alkali compounds tailing problem that surperficial heterogeneity causes.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, high-purity Bio-sil of a kind of sandwich construction and preparation method are provided; And corresponding sandwich construction high-purity porous bonded chromatographic filler and preparation method are further provided on this basis.By cohesion, prepare high-purity porous spherical silica gel through high temperature sintering by high-purity silicasol again; By adopt surface acid handle and esters of silicon acis handle obtain one new, have low activity, the fresh surface of low acidity and excellent homogeneity.
The preparation method of high-purity low porous acid spherical silica gel of the present invention, concrete steps are:
(1) ortho-silicate hydrolysis under the pH=7-10 condition is prepared high-purity silicasol, reaction temperature is 10-40 ℃, hydrolysis 2-10 hour;
(2) above-mentioned Ludox is blended in rapidly in urea and the formalin, between 1: 5 to 2: 1, Ludox and formaldehyde mole ratio are usually between 1: 8 to 2: 1 usually for Ludox and urea mol ratio; Regulating pH with nitric acid is 0-4, static then, generates the microballoon precipitation gradually; Reaction temperature is 10-40 ℃;
(3) sintering is removed organic substance and is obtained the high-purity silica gel microball of higher mechanical strength under 700-1100 ℃ of high temperature.The preferred 800-1050 of sintering temperature ℃;
(4) with high-purity silica gel microball through hydrofluoric acid treatment, open because the Si-O-Si key that high temperature dehydration forms on the surface.Hydrofluoric acid concentration usually can be about the 0.1-2 molar concentration; The acid treatment time usually can be at 1-24 hour;
(5) again with ortho-silicate reaction, silica gel and ortho-silicate part by weight be at 100: 1 to 5: 1, immediately 0-100 ℃ of temperature hydrolysis 1-5 hour, drying obtains high-purity low porous acid spherical silica gel under 150 ℃ of conditions being no more than then; The preferred 10-60 of hydrolysis temperature ℃.
Also can repeat the ortho-silicate processing procedure of above-mentioned steps (5), obtain the silica gel of surperficial multilayer modification.
Described ortho-silicate is methyl orthosilicate, ethyl orthosilicate, orthosilicic acid propyl ester or orthosilicic acid phenyl ester or their mixing ortho-silicate.
The high-purity low porous acid spherical silica gel that preparation method of the present invention makes, aperture 5-100 nanometer, particle diameter 1-10 micron, silicon hydroxyl 5＜pH＜7.By using the processing of ortho-silicate to the silica gel surface, reduced the acidity of surface to hydroxyl, reduced surperficial activity, improved surface uniformity.
The present invention also is included on the above-mentioned silica matrix, further passes through fixedly phase of a series of silane of bonding, obtains possessing good chromatographic separation performance, particularly alkali compounds is had the chromatograph packing material of good separating property.
Resultant silica gel can be used for preparing fixedly phase of all kinds of liquid chromatograies.As C18, C8, CN, phenyl, aminopropyl etc.Concrete preparation method all has report in the literature.
In the present invention, in conjunction with the novel high-purity silica gel matrix and the following particular type silane group of foregoing description, the novel chromatograph packing material that obtains having special chromatographic performance.These specific silane comprise the octadecyl dimethylchlorosilane, octadecyl methyl dichlorosilane, octadecyl diisopropyl chlorosilane, octadecyl isopropyl dichlorosilane, octadecyl diisobutyl chlorosilane, octadecyl isobutyl group dichlorosilane.Reaction can, but be not limited to following routine condition: with silica gel, above-mentioned a certain silane and organic base be in reflux in toluene, about 110 ℃, 2-48 hour; Washing then, drying.Be good for and close coverage rate between 25-60%.Silica gel behind the bonding can be directly used in the filling liquid-phase chromatographic column.By octadecyl diisopropyl chlorosilane; octadecyl isopropyl dichlorosilane; octadecyl diisobutyl chlorosilane; the resulting reverse-phase chromatography filler of octadecyl isobutyl group dichlorosilane bonding; have of the protection of big steric group owing to used, have very high acid resistance the chemical bond of silane and the generation of silica gel surface.Owing to the silica gel that has used through the ortho-silicate processing, there is a large amount of but acid lower remaining silicon hydroxyl on the surface simultaneously, makes resulting bonding filler have the characteristic and symmetrical chromatographic peak profile that flows and be complementary mutually with 100% water.
With the octadecyl dimethylchlorosilane, the filler that octadecyl methyl dichlorosilane bonding obtains, available following silane further with remaining silicon hydroxyl reaction.Reaction condition and above-mentioned condition are similar.Silane commonly used has trim,ethylchlorosilane, dimethyldichlorosilane, methyl trichlorosilane etc.The bonding coverage rate can rise between the 40-65%.Thereby obtain in alkalescence flows mutually, more long-life bonded silica gel filler being arranged.Silica gel behind the bonding can be directly used in the filling liquid-phase chromatographic column.The bonding coverage rate refers to the percentage of surface silanol group and silane group.
Technology of the present invention, the Si-O-Si key that the part surface dehydration is formed is opened, and increases surface silanol group.Handle and hydrolysis with orthosilicic acid fat again.After vacuum drying, resulting material can carry out further bonding.Because the processing of orthosilicic acid fat has further improved surface silanol group quantity, has reduced surface-active and acidity, and has made the surface become even; Resulting reverse-phase chromatography carrier performance particularly to the separating property of alkali compounds, has tangible improvement.The present invention is further by adopting the bonding of isopropyl silane, has acid-resisting and the novel anti-phase C18 filler that flows and be complementary mutually with 100% water when developing, and has unique chromatographic characterization.Use contains the sample of 4 kinds of organic bases, respectively to carrying out the liquid phase separation test through the ortho-silicate surface-treated with without ortho-silicate surface-treated reverse phase filler; The result shows that resulting peak shape has clear improvement on the surface-treated filler of ortho-silicate.Employed organic base comprises that many thiophenes are flat, nortriptyline, the gentle amitriptyline of bent rice handkerchief.
Description of drawings
Fig. 1: the chromatographic peak profile symmetry relatively.
The specific embodiment
Embodiment 1:
Tetraethoxysilane 208g is dissolved in the glass container of mixed solution that 5L is equipped with 2500ml ethanol and 1000ml deionized water.Add 30% ammonia spirit 60ml (mixture pH is about about 9-10), the rotating speed with 600rpm under 35 ℃ carried out mechanical agitation 30 seconds, and mixture at room temperature slowly stirs with magnetic force nano silicon spheres is generated then.Mixture heats on electromagnetic oven removing most of ethanol, and the volume of volatilization back mixture reduces to 800ml, through filtering, obtains colourlessly, and the silicon sol solution that contains high-purity nm silica gel bead of clarification adds less ammonia pH is transferred to about 7-8.Solid content=6.6%, particle diameter=107nm.
Embodiment 2:
Tetraethoxysilane 150g and being dissolved in the glass container of mixed solution that 5L is equipped with 2000ml ethanol and 500ml deionized water.Add 30% ammonia spirit 1ml (mixture pH is about about 8-9), the rotating speed with 600rpm under about 18 ℃ of room temperatures carried out mechanical agitation 30 seconds, and mixture at room temperature slowly stirs with magnetic force nano silicon spheres is generated then.Mixture heats on electromagnetic oven removing most of ethanol, and the volume of volatilization back mixture reduces to 600ml, through filtering, obtains colourlessly, and the silicon sol solution that contains high-purity nm silica gel bead of clarification adds less ammonia pH is transferred to about 8-9.Solid content=7.1%, particle diameter=12nm.
1240ml pure water, 26g red fuming nitric acid (RFNA), 840g are added in the 6000ml beaker successively according to the Ludox and the 37g urea of embodiment 2 preparations, be stirred to the urea dissolving.
Under stirring fast, add 100g formaldehyde, continued to stir soon 25 ℃ of room temperatures 15 seconds
Leave standstill.10-15min separates out white precipitate.
Placed 5-8 hour, and skimmed liquid, add pure water and stir, left standstill 30 minutes, skim liquid.
With the acetone washing, 3 times, filter.100 ℃ in vacuum, oven dry in 12 hours.Microscopy is 4--5 μ m, sphere, evenly.
Under 800 ℃ of high temperature, fire 10h.
Get white solid 53 grams after the burning-out; 400 milliliters of 0.5M HF heated in water solution to 90 ℃ 4 hours; Filter, 200 ml pure waters washing 2 times, 200 milliliters of acetone wash 3 times; Vacuum drying 8 hours.Microscopy is 5 μ m spheries.Aperture 8nm, specific surface: 198m
2/ g,
Get silica gel 50 grams that prepare, add tetraethoxysilane 5 grams, triethylamine 1 gram, 200 milliliters of toluene; Electronic stirring added hot reflux 4 hours for following 110 ℃; Filter, use 100 milliliters of toluene wash 3 times respectively; 100 ml methanol washing 3 times; 40 ℃ of 100 ml methanol/water (1: 1) add thermal agitation 4 hours, washing 3 times; 100 ml methanol washing 3 times; 100 ℃, vacuum drying 12 hours; Get white spherical solid powder 52 grams.C%=0.2, the acid pH=5.6 of silicon hydroxyl.
Embodiment 4:
1240ml pure water, 10g red fuming nitric acid (RFNA), 840g are added in the 6000ml beaker successively according to the Ludox and the 37g urea of embodiment 2 preparations, be stirred to the urea dissolving.
Under stirring fast, add 40g formaldehyde, in 35 ℃ of water-baths, continued to stir soon 15 seconds,
Leave standstill.10-15min separates out white precipitate.
Placed 5-8 hour, and skimmed liquid, add pure water and stir, left standstill 30 minutes, skim liquid.
With the acetone washing, 3 times, filter.100 ℃ in vacuum, oven dry in 12 hours.Microscopy is 4-5 μ m, sphere, evenly.
High-temperature firing, 1000 ℃, 2h.
Get white solid 50 grams after the burning-out; 400 milliliters of 1.5M HF heated in water solution to 90 ℃ 2 hours; Filter, 200 ml pure waters washing 2 times, 200 milliliters of acetone wash 3 times; Vacuum drying 8 hours.Microscopy is 3 μ m spheries.Aperture 8nm, specific surface: 212m
2/ g
Silica gel 50 grams of obtaining add tetraethoxysilane 1 gram, MTES 0.2 gram, triethylamine 1 gram, 200 milliliters of toluene; Electronic stirring added hot reflux 16 hours for following 110 ℃; Filter, use 100 milliliters of toluene wash 3 times respectively; 100 ml methanol washing 3 times; 80 ℃ of 100 ml methanol/water (1: 1) add thermal agitation 16 hours, washing 3 times; 100 ml methanol washing 3 times; 100 ℃, vacuum drying 12 hours; Get white spherical solid powder 51 grams.C%=1.1, the acid pH=5.8 of silicon hydroxyl.
Embodiment 5
840ml pure water, 46g red fuming nitric acid (RFNA), 980g are added in the 6000ml beaker successively according to the Ludox and the 30g urea of embodiment 1 preparation, be stirred to the urea dissolving.
Under stirring fast, add 70g formaldehyde, continued to stir soon 25 ℃ of room temperatures 15 seconds.
Leave standstill.10-15min separates out white precipitate.
Placed 5-8 hour, and skimmed liquid, add pure water and stir, left standstill 30 minutes, skim liquid.
With the acetone washing, 3 times, filter.100 ℃ in vacuum, oven dry in 12 hours.Microscopy is 4-5 μ m, sphere, evenly.
High-temperature firing, 1000 ℃, 6h.
Get white solid 49 grams after the burning-out; 400 milliliters of 0.2M HF heated in water solution to 90 ℃ 4 hours; Filter, 200 ml pure waters washing 2 times, 200 milliliters of acetone wash 3 times; Vacuum drying 8 hours.Microscopy is 8 μ m spheries.Aperture 80nm, specific surface: 5m
2/ g
Get silica gel 49 grams that prepare, add tetramethoxy-silicane 0.2 gram, triethylamine 1 gram, 200 milliliters of toluene; Electronic stirring added hot reflux 8 hours for following 110 ℃; Filter, use 100 milliliters of toluene wash 3 times respectively; 100 ml methanol washing 3 times; 30 ℃ of 100 ml methanol/water (1: 1) add thermal agitation 2 hours, washing 3 times; 100 ml methanol washing 3 times; 100 ℃, vacuum drying 12 hours; Get white spherical solid powder 48 grams.C%=0.1, the acid pH=5.4 of silicon hydroxyl.
Embodiment 6
Silica gel 10 grams that obtain among the embodiment 3, octadecyl dimethylchlorosilane 10 grams, triethylamine 4 grams, 50 milliliters of toluene, about 110 ℃ were refluxed 6 hours.The gained solid filtering is used toluene wash 3 times, each 50 milliliters; Methanol wash 6 times, each 50 milliliters; 100 ℃ of vacuum drying, 8 hours.Silica gel behind the above-mentioned bonding, trim,ethylchlorosilane 5 grams, triethylamine 2 grams, 50 milliliters of toluene, about 110 ℃ were refluxed 2 hours.The gained solid filtering is used toluene wash 3 times, each 50 milliliters; Methanol wash 6 times, each 50 milliliters; 100 ℃ of vacuum drying, 8 hours.Get solid 11 grams.C%=14.2.; Bonding coverage rate 48%, silica gel behind the above-mentioned bonding, trim,ethylchlorosilane 5 grams, triethylamine 2 grams, 50 milliliters of toluene, about 110 ℃ were refluxed 2 hours.The gained solid filtering is used toluene wash 3 times, each 50 milliliters; Methanol wash 6 times, each 50 milliliters; 100 ℃ of vacuum drying, 8 hours.Get solid 11.2 grams.C%=14.6; Total bonding coverage rate 52%
Embodiment 7
Silica gel 10 grams that obtain among the embodiment 4, octadecyl methyl dichlorosilane 6 grams, triethylamine 4 grams, 50 milliliters of toluene, about 110 ℃ were refluxed 16 hours.The gained solid filtering is used toluene wash 3 times, each 50 milliliters; Methanol wash 6 times, each 50 milliliters; 100 ℃ of vacuum drying, 8 hours.C%=15.1%, bonding coverage rate 52%.Silica gel behind the above-mentioned bonding, dimethyldichlorosilane 5 grams, triethylamine 2 grams, 50 milliliters of toluene, about 110 ℃ were refluxed 2 hours.The gained solid filtering is used toluene wash 3 times, each 50 milliliters; Methanol wash 6 times, each 50 milliliters; 100 ℃ of vacuum drying, 8 hours.Get solid 12 grams.C%=16.4.; Total bonding coverage rate 65%
Embodiment 8
Silica gel 10 grams that obtain among the embodiment 3, octadecyl diisopropyl chlorosilane 10 grams, triethylamine 4 grams, 50 milliliters of toluene, about 110 ℃ were refluxed 48 hours.The gained solid filtering is used toluene wash 3 times, each 50 milliliters; Methanol wash 6 times, each 50 milliliters; 100 ℃ of vacuum drying, 12 hours.Get solid 11 grams.C%=10.2; Bonding coverage rate 28%
Embodiment 9
Get in the example 3 and restrain octadecyl diisopropyl chlorosilane 10 grams, triethylamine 4 grams, 50 milliliters of toluene, about 110 ℃ of backflows 48 hours without ortho-silicate surface-treated silica gel 10.The gained solid filtering is used toluene wash 3 times, each 50 milliliters; Methanol wash 6 times, each 50 milliliters; 100 ℃ of vacuum drying, 12 hours.Get solid 9.5 grams.C%=9.7 bonding coverage rate 26%
Embodiment 10
Silica gel 10 grams that obtain among the embodiment 5, octadecyl diisopropyl chlorosilane 5 grams, triethylamine 1 gram, 50 milliliters of toluene, about 110 ℃ were refluxed 48 hours.The gained solid filtering is used toluene wash 3 times, each 50 milliliters; Methanol wash 6 times, each 50 milliliters; 100 ℃ of vacuum drying, 12 hours.Get solid 9 grams.C%=1.6; Bonding coverage rate 42%
Embodiment 11
Get each 2 gram of bonded silica gel filler of example 6 and example 7 gained respectively, with the homogenate method fill out 4.6mm internal diameter * 150mm column length, chromatographic column is chromatographic column 6 and chromatographic column 7 respectively.Use is by each 5 milligrams of many thiophene of mixture in 100 ml methanol 85% and water 15% flat 1 of following four kinds of strongly alkaline compounds, nortriptyline 2, bent rice handkerchief flat 3, amitriptyline 4 is as specimen, with 0.01 molar concentration sodium phosphate of 70% acetonitrile and 30%, pH=6 is the phase that flows, at 30oC, under 1 milliliter of flow velocity of per minute two are detected on the 10A liquid chromatograph of Tianjin, island respectively.The detection wavelength is 254nm.The gained spectrogram is seen accompanying drawing 1.Its middle and upper part is chromatographic column 6 test results through the silica gel bonded gained of ortho-silicate processing, and the bottom is chromatographic column 7 test results without the silica gel bonded gained of ortho-silicate processing.The peak shape of chromatographic column 6 resulting each components all obviously is better than chromatographic column 7 resulting accordingly results.
Claims (9)
1. the preparation method of a high-purity low porous acid spherical silica gel is characterized in that:
(1) with ortho-silicate under the pH=7-10 condition, reaction temperature is 10-40 ℃, hydrolysis 2-10 hour;
(2) above-mentioned Ludox is blended in rapidly in urea and the formalin, between 1: 5 to 2: 1, Ludox and formaldehyde mole ratio are usually between 1: 8 to 2: 1 usually for Ludox and urea mol ratio; Regulating pH with nitric acid is 0-4, static then, generates the microballoon precipitation gradually; Reaction temperature is 10-40 ℃;
(3) sintering is removed organic substance and is obtained the high-purity silica gel microball of higher mechanical strength under 700-1100 ℃ of high temperature;
(4) high-purity silica gel microball that sintering is obtained is through hydrofluoric acid treatment, and hydrofluoric acid concentration is the 0.1-2 molar concentration; The acid treatment time is 1-24 hour;
(5) again with ortho-silicate reaction, silica gel and ortho-silicate part by weight be at 100: 1 to 5: 1, immediately 0-100 ℃ of temperature hydrolysis 1-5 hour, drying obtains high-purity low porous acid spherical silica gel under 150 ℃ of conditions being no more than then.
2. the preparation method of high-purity low porous acid spherical silica gel as claimed in claim 1 is characterized in that described ortho-silicate is methyl orthosilicate, ethyl orthosilicate, orthosilicic acid propyl ester or orthosilicic acid phenyl ester or their mixing ortho-silicate.
3. the preparation method of high-purity low porous acid spherical silica gel as claimed in claim 1 is characterized in that described step (5) repetitive operation.
4. the preparation method of high-purity low porous acid spherical silica gel as claimed in claim 1 is characterized in that described hydrolysis temperature is 10-60 ℃.
5. the high-purity low porous acid spherical silica gel that the preparation method of high-purity low porous acid spherical silica gel as claimed in claim 1 makes is characterized in that described high-purity low porous acid spherical silica gel aperture 5-100 nanometer, particle diameter 1-10 micron, silicon hydroxyl 5＜pH＜7.
6. prepare the high-purity porous bonded chromatographic of sandwich construction filler by the described high-purity low porous acid spherical silica gel of claim 5, it is characterized in that and the organosilan bonding.
7. prepare the high-purity porous bonded chromatographic of sandwich construction filler by the described high-purity low porous acid spherical silica gel of claim 6, it is characterized in that described machine silane is one or more in octadecyl diisopropyl chlorosilane, octadecyl isopropyl dichlorosilane, octadecyl diisobutyl chlorosilane or the octadecyl isobutyl group dichlorosilane; The bonding coverage rate reaches 25%-60%.
8. prepare the high-purity porous bonded chromatographic of sandwich construction filler by the described high-purity low porous acid spherical silica gel of claim 6, it is characterized in that described machine silane is octadecyl dimethylchlorosilane or octadecyl methyl dichlorosilane, the bonding coverage rate reaches 25%-60%.
9. prepare the high-purity porous bonded chromatographic of sandwich construction filler by the described high-purity low porous acid spherical silica gel of claim 8, it is characterized in that the high-purity porous bonded chromatographic of the sandwich construction filler of the end-blocking that described sandwich construction high-purity porous bonded chromatographic filler and the further bonding of trim,ethylchlorosilane, dimethyldichlorosilane or methyl trichlorosilane obtain; Total bonding coverage rate reaches 40-65%.
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| CN101927154A (en) * | 2010-06-24 | 2010-12-29 | 常州嘉众新材料科技有限公司 | Preparation method of three-functional-group n-octadecyl bonded phase |
| CN101962361A (en) * | 2010-09-06 | 2011-02-02 | 海南美大制药有限公司 | Maleic acid Trimipramine compound and new preparation method thereof |
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| CN101927154A (en) * | 2010-06-24 | 2010-12-29 | 常州嘉众新材料科技有限公司 | Preparation method of three-functional-group n-octadecyl bonded phase |
| CN101927154B (en) * | 2010-06-24 | 2013-09-11 | 常州嘉众新材料科技有限公司 | Preparation method of three-functional-group n-octadecyl bonded phase |
| CN101962361A (en) * | 2010-09-06 | 2011-02-02 | 海南美大制药有限公司 | Maleic acid Trimipramine compound and new preparation method thereof |
| CN102030816A (en) * | 2010-12-22 | 2011-04-27 | 复旦大学 | Manufacture method and application of novel incomplete protein micro catcher |
| CN102091607A (en) * | 2010-12-27 | 2011-06-15 | 天津博纳艾杰尔科技有限公司 | Multi-layer structure high-purity bonded silica gel chromatographic filler and preparation method thereof |
| CN102160994A (en) * | 2011-03-01 | 2011-08-24 | 北京化工大学 | Silica gel bonded brush-type chiral stationary phase, synthesizing method and application |
| CN102160994B (en) * | 2011-03-01 | 2012-10-17 | 北京化工大学 | Silica gel bonded brush-type chiral stationary phase, synthesizing method and application |
| CN102389781A (en) * | 2011-08-12 | 2012-03-28 | 天津博纳艾杰尔科技有限公司 | Porous shell silica gel chromatograph filling material and preparation method thereof |
| CN102389781B (en) * | 2011-08-12 | 2014-11-05 | 天津博纳艾杰尔科技有限公司 | Porous shell silica gel chromatograph filling material and preparation method thereof |
| CN107304213A (en) * | 2016-04-20 | 2017-10-31 | 中国医药工业有限公司 | A kind of opium poppy extract-treated method and apparatus |
| CN107304213B (en) * | 2016-04-20 | 2021-08-20 | 李显林 | Method and equipment for processing poppy extract |
| CN115634675A (en) * | 2022-10-27 | 2023-01-24 | 青岛邦凯高新技术材料有限公司 | Electronic-grade industrial silicon dioxide base material chromatographic filler, and preparation method and application thereof |
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