CN102172519A - Silica gel bonded cellulose derivative chromatographic filler and preparation method and use thereof - Google Patents
Silica gel bonded cellulose derivative chromatographic filler and preparation method and use thereof Download PDFInfo
- Publication number
- CN102172519A CN102172519A CN 201110048690 CN201110048690A CN102172519A CN 102172519 A CN102172519 A CN 102172519A CN 201110048690 CN201110048690 CN 201110048690 CN 201110048690 A CN201110048690 A CN 201110048690A CN 102172519 A CN102172519 A CN 102172519A
- Authority
- CN
- China
- Prior art keywords
- silica gel
- cellulose
- volume
- reaction
- washing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a silica gel bonded cellulose derivative chromatographic filler and a preparation method and use thereof, which belong to the field of chromatographic fillers. The preparation method comprises the following steps: (1) activating silica gel; (2) modifying the surface of the silica gel by using KH-550 to obtain 3-aminosilylated silica gel; (3) preparing cellulose-2,3-bis(3,5-dimethylphenyl carbamate) by surface hydroxyl derivation of microcrystalline cellulose; and (4) bonding cellulose-2,3-bis(3,5-dimethylphenyl carbamate) on the surface of the 3-aminosilylated silica gel to obtain a bonded chiral filler. When the chiral filler is used, by using hexane-isopropyl alcohol serving as a flowing phase, DL-phenethyl alcohol, p-pentyloxy isophenethyl alcohol, (+/-)-3-p-chlorobenzyl-4-nitrosulfobutyl acetate and (+/-)-2-p-chlorobenzyl-3-nitrosulfopropyl acetate are better separated. The silica gel bonded cellulose derivative chromatographic filler has the characteristics of high column efficiency, short separation time and desirable chiral compound separation effect.
Description
Technical field
The present invention relates to the preparation of chiral chromatogram column packing, relate in particular to the preparation that is bonded to the efficient liquid phase chiral chromatogram of cellulose derivative chirality filler on the silica matrix.
Background technology
Chromatographic column is the core of chromatographic separation technology, and fixedly the research of phase then is the basis that various high performance liquid chromatographies are rely and set up and develop.In the face of in the research and production to the demand of high purity substance, new packing and the chipal compounds separating filler of developing more effective preparation isolation technics, preparative chromatography are vital.Fixing that research and development are good with separative efficiency height, selectivity that chipal compounds adapts, activity reclaims and mass recovery is good, the life-span is long is the target that people pursue all the time mutually.Why the HPLC-CSP method can split enantiomer, is because when the interaction of CSP and racemic modification, one of them enantiomer and CSP generate unsettled of short duration enantiomer compound, retention time difference when causing post drip washing, thus reach the purpose of fractionation.Oneself develops the chiral stationary phase that much is used for liquid chromatogram at present, mainly contains polysaccharide derivates, cyclodextrin and protein etc.Cellulose is as a kind of natural polysaccharide derivative, and it is cheap, nontoxic, bio-compatible, degradable and environmental friendliness etc. and be used widely.At present external existing many commercial cellulose family chiral columns are sold, and compare with other chiral stationary phase, and it has remarkable advantages such as applied widely, good stability and column capacity height.The seminar of external Okamoto is the most representative and contribution property in the research of polysaccharides chiral CSP, we follow the tracks of it in the fixing progress of phase of high performance liquid chromatography polysaccharides chiral, find that cellulose carbamate class chiral stationary phase shows the highest chiral Recognition ability, and the separation kind is extensive.Yet the cellulose chiral post of great majority sale at present is all application type, when using acetone, oxolane, chloroform etc., can cause the dissolving of fixing phase and swelling and run off as solvent, make it lose the chiral separation ability and influence the pillar life-span, so the synthesizing new bonded chiral is fixing particularly important mutually.Okamoto adopts the space to connect reagent 4,4'-diphenyl methyl two isocyanic acids have prepared the cellulose chiral post of bonding type, the use kind and the scope of mobile phase have been increased, yet its chiral separation ability is but low than application type, because cellulosic chiral Recognition ability and its spatially spiral structure are closely related.The present invention adopts the simple hexamethylene diisocyanate of space structure for connecting reagent, cellulose-two (3, the 5-dimethylphenyl isocyanate) is bonded to aminopropyl silica gel surface, thereby has prepared bonding type cellulose chiral post.Reagent is existing to be reported though hexamethylene diisocyanate is as connecting, yet is that it is directly linked to each other with the silica gel surface of unmodified, also will add the capping reagent trim,ethylchlorosilane at last for the remaining silicon hydroxyl in surface and shelter.This paper adopts the 3-aminopropyl triethoxysilane that silica gel is modified, and has sheltered the surface hydroxyl of silica gel on the one hand, provides the amino that can link to each other with isocyanates on the one hand, and need not end-blocking at last, makes reaction simpler.
Summary of the invention
The object of the invention provides the efficient liquid phase chiral chromatogram of bonding microcrystalline cellulose analog derivative filler and preparation method thereof on a kind of silica matrix.
Silica gel surface bond cellulose derivative chiral chromatogram filler, its structural formula is;
(1) silica gel activating: press hydrochloric acid and silica gel volume mass ratio 2-6ml/g, with percent by volume is that 20% hydrochloric acid and 30nm-300nm pore size silica gel are mixed with mixture, be heated to 90-100 ℃ of reaction backflow 2-6 hour, suction filtration, spend deionised water to neutral, 100-120 ℃ was dried by the fire 4-8 hour, and in 50 ℃ of vacuum drying 4-8 hours, it was standby to get activated silica gel;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel that has activated and pack in the there-necked flask, add the dry toluene of the 1/3-2/3 of reaction vessel volume, be 2-3:1-2 (ml/g) adding 3-aminopropyl triethoxysilane by KH-550 and silica gel volume/mass ratio, at 80-100 ℃ of following backflow 20-28 hour, whole process was at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 60 ℃ of vacuum drying 4-10 hours.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose is mixed by mass ratio 1-2:3-5 with triphenylchloromethane, add anhydrous pyridine again, the addition of anhydrous pyridine is the 1/3-2/3 of reaction vessel volume; At 80-100 ℃, mechanical agitation, logical N
2Reaction condition under after backflow 18-24 hour with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing 1-1.5g and 1. get 6-position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 1-4.5ml, with dry toluene and pyridine volume ratio is that the mixed liquor of 3-5:1-2 is a solvent, stirring and refluxing 18-24 hour, after finishing, reaction adds methyl alcohol and 0.6-1.5ml concentrated hydrochloric acid stirring at room reaction a period of time, after volatilizing with methyl alcohol suction filtration, washing, fume hood at last, 60-100 ℃ of vacuum drying obtains cellulose-2,3-two (3,5-3,5-dimethylphenyl carbamate);
Reaction equation:
(4) 3-aminopropyl silanized silica gel surface bond cellulose-2,3-two (3,5-3,5-dimethylphenyl carbamate) obtains the bonded chiral filler:
Take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl carbamate) and 3-aminopropyl silanized silica gel mix according to mass ratio 1-2:2-3, add pyridine and volume of toluene than for the mixing material of 1-2:2-3 as solvent, add the hexamethylene diisocyanate reaction again, hexamethylene diisocyanate volume and 3-aminopropyl silanized silica gel mass ratio are 1-2:2-4 (ml/g), 80-100 ℃, mechanical agitation, after backflow 24-48 hour, be cooled to room temperature, use earlier the dry toluene suction filtration, washing, again with methyl alcohol suction filtration repeatedly, washing, product dry 6-10h under 60-80 ℃ gets product.
The specific embodiment
Embodiment 1:
(1) silica gel activating: press hydrochloric acid and silica gel volume mass ratio 2ml/g, with percent by volume is that 20% hydrochloric acid and silica gel 30nm aperture are mixed with mixture, heating 90 ℃ of reactions refluxed 2 hours, suction filtration, spend deionised water to neutral, 100 ℃ were dried by the fire 4 hours, and 50 ℃ of vacuum drying 4 hours, activated silica gel is standby;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel 2.0g that has activated and pack in the 250ml there-necked flask, the dry toluene, the adding 3-aminopropyl triethoxysilane 2.0ml that add the 80ml of reaction vessel volume, refluxed 20 hours down at 80 ℃, whole process is at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 4 hours in 60 ℃ of vacuum drying.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose (1.5g) is mixed by mass ratio 1:3 with triphenylchloromethane (4.5g), add anhydrous pyridine 80ml again, be warming up to 80 ℃, mechanical agitation, logical N
2Reaction condition refluxed 18 hours down after with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing the above-mentioned 6-of 1.0g position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 1ml, with dry toluene and pyridine volume ratio is that the mixed liquor 60ml of 2:1 is a solvent, stirring and refluxing 18 hours, after finishing, reaction adds methyl alcohol and 0.6ml concentrated hydrochloric acid stirring at room reaction a period of time, use methyl alcohol suction filtration, washing at last, fume hood volatilizes, obtain cellulose-2 after changing 60 ℃ of vacuum drying over to, 3-two (3,5-3,5-dimethylphenyl carbamate);
(4) take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl carbamate) 1.0g and 3-aminopropyl silanized silica gel 2g mix, adding than the mixed solvent 40ml that is 1:3, adds the reaction of 0.5ml hexamethylene diisocyanate with pyridine and volume of toluene, and 80 ℃, mechanical agitation, backflow are after 24 hours, be cooled to room temperature, with dry toluene suction filtration, washing, again with methyl alcohol suction filtration, washing repeatedly, product is dry 6h under 80 ℃ earlier.
Embodiment 2:
(1) silica gel activating: press hydrochloric acid and silica gel volume mass ratio 2ml/g, with percent by volume is that 20% hydrochloric acid and silica gel 100nm aperture are mixed with mixture, heating 95 ℃ of reactions refluxed 4 hours, suction filtration, spend deionised water to neutral, 100 ℃ were dried by the fire 4 hours, and 50 ℃ of vacuum drying 6 hours, activated silica gel is standby;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel 2.0g that has activated and pack in the 250ml there-necked flask, the dry toluene, the adding 3-aminopropyl triethoxysilane 2.5ml that add the 100ml of reaction vessel volume, refluxed 22 hours down at 90 ℃, whole process is at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 8 hours in 60 ℃ of vacuum drying.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose (1.5g) is mixed by mass ratio 1:3 with triphenylchloromethane (4.5g), add anhydrous pyridine 100ml again, be warming up to 85 ℃, mechanical agitation, logical N
2Reaction condition refluxed 18 hours down after with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing the above-mentioned 6-of 1.0g position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 1ml, with dry toluene and pyridine volume ratio is that the mixed liquor 60ml of 2:1 is a solvent, stirring and refluxing 18 hours, after finishing, reaction adds methyl alcohol and 0.6ml concentrated hydrochloric acid stirring at room reaction a period of time, use methyl alcohol suction filtration, washing at last, fume hood volatilizes, obtain cellulose-2 after changing 60 ℃ of vacuum drying over to, 3-two (3,5-3,5-dimethylphenyl carbamate);
(4) take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl amino methyl) 1.0g and 3-aminopropyl silanized silica gel 3g mix, adding than the mixed solvent 60ml that is 1:3, adds the reaction of 1.0ml hexamethylene diisocyanate with pyridine and volume of toluene, and 90 ℃, mechanical agitation, backflow are after 28 hours, be cooled to room temperature, with dry toluene suction filtration, washing, again with methyl alcohol suction filtration, washing repeatedly, product is dry 6h under 80 ℃ earlier.
Embodiment 3:
⑴ silica gel activating: press hydrochloric acid and silica gel volume mass ratio 3ml/g, with percent by volume is that 20% hydrochloric acid and silica gel aperture 200nm are mixed with mixture, heating 90 ℃ of reactions refluxed 4 hours, suction filtration, spend deionised water to neutral, 110 ℃ were dried by the fire 5 hours, and 50 ℃ of vacuum drying 6 hours, activated silica gel is standby;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel 2.0g that has activated and pack in the 250ml there-necked flask, the dry toluene, the adding 3-aminopropyl triethoxysilane 3.0ml that add the 100ml of reaction vessel volume, refluxed 24 hours down at 90 ℃, whole process is at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 6 hours in 60 ℃ of vacuum drying.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose (1.5g) with after triphenylchloromethane (5.0g) mixes, is added anhydrous pyridine 100ml again, be warming up to 80 ℃, mechanical agitation, logical N
2Reaction condition refluxed 18 hours down after with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing the above-mentioned 6-of 1.0g position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 2ml, with dry toluene and pyridine volume ratio is that the mixed liquor 90ml of 2:1 is a solvent, stirring and refluxing 20 hours, after finishing, reaction adds methyl alcohol and 0.8ml concentrated hydrochloric acid stirring at room reaction a period of time, use methyl alcohol suction filtration, washing at last, fume hood volatilizes naturally, obtain cellulose-2 after 70 ℃ of vacuum drying, 3-two (3,5-3,5-dimethylphenyl carbamate);
(4) take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl amino methyl) 1.0g and 3-aminopropyl silanized silica gel 3g mix, adding than the mixed solvent 80ml that is 1:3, adds the reaction of 1.0ml hexamethylene diisocyanate with pyridine and volume of toluene, and 90 ℃, mechanical agitation, backflow are after 36 hours, be cooled to room temperature, with dry toluene suction filtration, washing, again with methyl alcohol suction filtration, washing repeatedly, product is dry 6h under 90 ℃ earlier.
Embodiment 4:
(1) silica gel activating: press hydrochloric acid and silica gel volume mass ratio 3ml/g, with percent by volume is that 20% hydrochloric acid and silica gel 200nm, aperture are mixed with mixture, heating 95 ℃ of reactions refluxed 6 hours, suction filtration, spend deionised water to neutral, 100 ℃ were dried by the fire 6 hours, and 50 ℃ of vacuum drying 8 hours, activated silica gel is standby;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel 2.0g that has activated and pack in the 250ml there-necked flask, the dry toluene, the adding 3-aminopropyl triethoxysilane 3.0ml that add the 120ml of reaction vessel volume, refluxed 28 hours down at 100 ℃, whole process is at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 6 hours in 60 ℃ of vacuum drying.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose (1.5g) with after triphenylchloromethane (5.0g) mixes, is added anhydrous pyridine 100ml again, be warming up to 85 ℃, mechanical agitation, logical N
2Reaction condition refluxed 20 hours down after with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing the above-mentioned 6-of 1.0g position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 3ml, with dry toluene and pyridine volume ratio is that the mixed liquor 80ml of 3:1 is a solvent, stirring and refluxing 24 hours, after finishing, reaction adds methyl alcohol and 1ml concentrated hydrochloric acid stirring at room reaction a period of time, use methyl alcohol suction filtration, washing at last, fume hood volatilizes naturally, obtain cellulose-2 after 80 ℃ of vacuum drying, 3-two (3,5-3,5-dimethylphenyl carbamate);
(4) take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl amino methyl) 1.0g and 3-aminopropyl silanized silica gel 4g mix, adding than the mixed solvent 100ml that is 1:3, adds the reaction of 1.0ml hexamethylene diisocyanate with pyridine and volume of toluene, and 90 ℃, mechanical agitation, backflow are after 28 hours, be cooled to room temperature, with dry toluene suction filtration, washing, again with methyl alcohol suction filtration, washing repeatedly, product is dry 8h under 90 ℃ earlier.
Embodiment 5:
(1) silica gel activating: press hydrochloric acid and silica gel volume mass ratio 4ml/g, with percent by volume is that 20% hydrochloric acid and silica gel 300nm aperture are mixed with mixture, heating 95 ℃ of reactions refluxed 2 hours, suction filtration, spend deionised water to neutral, 105 ℃ were dried by the fire 4 hours, and 50 ℃ of vacuum drying 4 hours, activated silica gel is standby;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel 2.0g that has activated and pack in the 250ml there-necked flask, the dry toluene, the adding 3-aminopropyl triethoxysilane 4.0ml that add the 120ml of reaction vessel volume, refluxed 24 hours down at 80 ℃, whole process is at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 8 hours in 60 ℃ of vacuum drying.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose (1.5g) with after triphenylchloromethane (5.0g) mixes, is added anhydrous pyridine 100ml again, be warming up to 90 ℃, mechanical agitation, logical N
2Reaction condition refluxed 24 hours down after with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing the above-mentioned 6-of 1.0g position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 4ml, with dry toluene and pyridine volume ratio is that the mixed liquor 100ml of 4:1 is a solvent, stirring and refluxing 24 hours, after finishing, reaction adds methyl alcohol and 1.2ml concentrated hydrochloric acid stirring at room reaction a period of time, use methyl alcohol suction filtration, washing at last, fume hood volatilizes naturally, obtain cellulose-2 after 90 ℃ of vacuum drying, 3-two (3,5-3,5-dimethylphenyl carbamate);
(4) take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl amino methyl) 1.0g and 3-aminopropyl silanized silica gel 4g mix, adding than the mixed solvent 100ml that is 1:3, adds the reaction of 2.0ml hexamethylene diisocyanate with pyridine and volume of toluene, and 95 ℃, mechanical agitation, backflow are after 28 hours, be cooled to room temperature, with dry toluene suction filtration, washing, again with methyl alcohol suction filtration, washing repeatedly, product is dry 10h under 80 ℃ earlier.
Embodiment 6:
(1) silica gel activating: press hydrochloric acid and silica gel volume mass ratio 4ml/g, with percent by volume is that 20% hydrochloric acid and silica gel 300nm aperture are mixed with mixture, heating 100 ℃ of reactions refluxed 4 hours, suction filtration, spend deionised water to neutral, 110 ℃ were dried by the fire 8 hours, and 50 ℃ of vacuum drying 6 hours, activated silica gel is standby;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel 2.0g that has activated and pack in the 250ml there-necked flask, the dry toluene, the adding 3-aminopropyl triethoxysilane 4.0ml that add the 140ml of reaction vessel volume, refluxed 24 hours down at 95 ℃, whole process is at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 6 hours in 60 ℃ of vacuum drying.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose (1.5g) with after triphenylchloromethane (5.5g) mixes, is added anhydrous pyridine 120ml again, be warming up to 90 ℃, mechanical agitation, logical N
2Reaction condition refluxed 18 hours down after with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing the above-mentioned 6-of 1.2g position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 3ml, with dry toluene and pyridine volume ratio is that the mixed liquor 100ml of 4:1 is a solvent, stirring and refluxing 20 hours, after finishing, reaction adds methyl alcohol and 1.0ml concentrated hydrochloric acid stirring at room reaction a period of time, use methyl alcohol suction filtration, washing at last, fume hood volatilizes naturally, obtain cellulose-2 after 80 ℃ of vacuum drying, 3-two (3,5-3,5-dimethylphenyl carbamate);
(4) take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl amino methyl) 1.0g and 3-aminopropyl silanized silica gel 4g mix, adding than the mixed solvent 100ml that is 1:3, adds the reaction of 3.0ml hexamethylene diisocyanate with pyridine and volume of toluene, and 100 ℃, mechanical agitation, backflow are after 36 hours, be cooled to room temperature, with dry toluene suction filtration, washing, again with methyl alcohol suction filtration, washing repeatedly, product is dry 6h under 90 ℃ earlier.
Embodiment 7:
(1) silica gel activating: press hydrochloric acid and silica gel volume mass ratio 5ml/g, with percent by volume is that 20% hydrochloric acid and silica gel 300nm aperture are mixed with mixture, heating 90 ℃ of reactions refluxed 4 hours, suction filtration, spend deionised water to neutral, 110 ℃ were dried by the fire 2 hours, and 50 ℃ of vacuum drying 6 hours, activated silica gel is standby;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel 2.0g that has activated and pack in the 250ml there-necked flask, the dry toluene, the adding 3-aminopropyl triethoxysilane 5.0ml that add the 140ml of reaction vessel volume, refluxed 24 hours down at 90 ℃, whole process is at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 8 hours in 60 ℃ of vacuum drying.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose (1.5g) with after triphenylchloromethane (6.0g) mixes by mass ratio 1:4, is added anhydrous pyridine 120ml again, be warming up to 95 ℃, mechanical agitation, logical N
2Reaction condition refluxed 20 hours down after with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing the above-mentioned 6-of 1.2g position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 4ml, with dry toluene and pyridine volume ratio is that the mixed liquor 100ml of 4:1 is a solvent, stirring and refluxing 22 hours, after finishing, reaction adds methyl alcohol and 1.2ml concentrated hydrochloric acid stirring at room reaction a period of time, use methyl alcohol suction filtration, washing at last, fume hood volatilizes naturally, obtain cellulose-2 after 100 ℃ of vacuum drying, 3-two (3,5-3,5-dimethylphenyl carbamate);
(4) take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl amino methyl) 1.5g and 3-aminopropyl silanized silica gel 4g mix, adding than the mixed solvent 140ml that is 1:3, adds the reaction of 4.0ml hexamethylene diisocyanate with pyridine and volume of toluene, and 100 ℃, mechanical agitation, backflow are after 48 hours, be cooled to room temperature, with dry toluene suction filtration, washing, again with methyl alcohol suction filtration, washing repeatedly, product is dry 8h under 90 ℃ earlier.
Embodiment 8:
(1) silica gel activating: press hydrochloric acid and silica gel volume mass ratio 5ml/g, with percent by volume is that 20% hydrochloric acid and silica gel 300nm aperture are mixed with mixture, heating 100 ℃ of reactions refluxed 4 hours, suction filtration, spend deionised water to neutral, 120 ℃ were dried by the fire 2 hours, and 50 ℃ of vacuum drying 8 hours, activated silica gel is standby;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel 2.0g that has activated and pack in the 250ml there-necked flask, the dry toluene, the adding 3-aminopropyl triethoxysilane 5.0ml that add the 160ml of reaction vessel volume, refluxed 28 hours down at 100 ℃, whole process is at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 10 hours in 60 ℃ of vacuum drying.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose (1.5g) with after triphenylchloromethane (6.0g) mixes by mass ratio 1:4, is added anhydrous pyridine 120ml again, be warming up to 95 ℃, mechanical agitation, logical N
2Reaction condition refluxed 20 hours down after with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing the above-mentioned 6-of 1.2g position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 4ml, with dry toluene and pyridine volume ratio is that the mixed liquor 100ml of 4:1 is a solvent, stirring and refluxing 22 hours, after finishing, reaction adds methyl alcohol and 1.2ml concentrated hydrochloric acid stirring at room reaction a period of time, use methyl alcohol suction filtration, washing at last, fume hood volatilizes naturally, obtain cellulose-2 after 100 ℃ of vacuum drying, 3-two (3,5-3,5-dimethylphenyl carbamate);
(4) take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl amino methyl) 1.0g and 3-aminopropyl silanized silica gel 5g mix, adding than the mixed solvent 140ml that is 1:3, adds the reaction of 2.5ml hexamethylene diisocyanate with pyridine and volume of toluene, and 90 ℃, mechanical agitation, backflow are after 36 hours, be cooled to room temperature, with dry toluene suction filtration, washing, again with methyl alcohol suction filtration, washing repeatedly, product is dry 10h under 80 ℃ earlier.
Embodiment 9:
(1) silica gel activating: press hydrochloric acid and silica gel volume mass ratio 6ml/g, with percent by volume is that 20% hydrochloric acid and silica gel 300nm aperture are mixed with mixture, heating 95 ℃ of reactions refluxed 4 hours, suction filtration, spend deionised water to neutral, 100 ℃ were dried by the fire 6 hours, and 50 ℃ of vacuum drying 6 hours, activated silica gel is standby;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel 2.0g that has activated and pack in the 250ml there-necked flask, the dry toluene, the adding 3-aminopropyl triethoxysilane 6.0ml that add the 160ml of reaction vessel volume, refluxed 24 hours down at 90 ℃, whole process is at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 6 hours in 60 ℃ of vacuum drying.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose (1.5g) with after triphenylchloromethane (7.0g) mixes, is added anhydrous pyridine 120ml again, be warming up to 90 ℃, mechanical agitation, logical N
2Reaction condition refluxed 20 hours down after with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing the above-mentioned 6-of 1.2g position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 3.5ml, with dry toluene and pyridine volume ratio is that the mixed liquor 100ml of 4:1 is a solvent, stirring and refluxing 24 hours, after finishing, reaction adds methyl alcohol and 1.2ml concentrated hydrochloric acid stirring at room reaction a period of time, use methyl alcohol suction filtration, washing at last, fume hood volatilizes naturally, obtain cellulose-2 after 100 ℃ of vacuum drying, 3-two (3,5-3,5-dimethylphenyl carbamate);
(4) take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl amino methyl) 1.0g and 3-aminopropyl silanized silica gel 5g mix, adding than the mixed solvent 140ml that is 1:3, adds the reaction of 3.5ml hexamethylene diisocyanate with pyridine and volume of toluene, and 100 ℃, mechanical agitation, backflow are after 42 hours, be cooled to room temperature, with dry toluene suction filtration, washing, again with methyl alcohol suction filtration, washing repeatedly, product is dry 8h under 90 ℃ earlier.
Embodiment 10:
(1) silica gel activating: press hydrochloric acid and silica gel volume mass ratio 6ml/g, with percent by volume is that 20% hydrochloric acid and silica gel 300nm aperture are mixed with mixture, heating 100 ℃ of reactions refluxed 6 hours, suction filtration, spend deionised water to neutral, 110 ℃ were dried by the fire 2 hours, and 50 ℃ of vacuum drying 8 hours, activated silica gel is standby;
(2) KH-550 is to the modification of silica gel: take by weighing the above-mentioned spherical silica gel 2.0g that has activated and pack in the 250ml there-necked flask, the dry toluene, the adding 3-aminopropyl triethoxysilane 6.0ml that add the 160ml of reaction vessel volume, refluxed 28 hours down at 100 ℃, whole process is at N
2Carry out under the following protection.Cool off, filter the back with methyl alcohol, acetone and n-hexane washing, got white solid 3-aminopropyl silanized silica gel in 8 hours in 60 ℃ of vacuum drying.
(3) cellulose-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose (1.5g) with after triphenylchloromethane (6.0g) mixes by mass ratio 1:4, is added anhydrous pyridine 150ml again, be warming up to 100 ℃, mechanical agitation, logical N
2Reaction condition refluxed 24 hours down after with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing the above-mentioned 6-of 1.2g position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 4ml, with dry toluene and pyridine volume ratio is that the mixed liquor 120ml of 5:1 is a solvent, stirring and refluxing 24 hours, after finishing, reaction adds methyl alcohol and 1.5ml concentrated hydrochloric acid stirring at room reaction a period of time, use methyl alcohol suction filtration, washing at last, fume hood volatilizes naturally, obtain cellulose-2 after 90 ℃ of vacuum drying, 3-two (3,5-3,5-dimethylphenyl carbamate);
(4) take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl amino methyl) 2.0g and 3-aminopropyl silanized silica gel 5g mix, adding than the mixed solvent 140ml that is 1:3, adds the reaction of 5.0ml hexamethylene diisocyanate with pyridine and volume of toluene, and 100 ℃, mechanical agitation, backflow are after 48 hours, be cooled to room temperature, with dry toluene suction filtration, washing, again with methyl alcohol suction filtration, washing repeatedly, product is dry 6h under 100 ℃ earlier.
The evaluation of chromatograph packing material
The chromatograph packing material of Application Example 1 preparation, as mobile phase, flow velocity 1.5ml/min separates the DL-benzyl carbinol, obtains chromatogram shown in the drawings with n-hexane-isopropyl alcohol.As can be seen from the figure, realized baseline separation, the peak shape symmetry does not have hangover, and analysis speed is fast.
With examples of implementation 2-10 synthesized silicon rubber bonding cellulose derivative chromatograph packing material dress post, carry out chromatographic evaluation, these 9 kinds of fillers all can be to the DL-benzyl carbinol, the different benzyl carbinol of amoxy, (±)-3-rubigan-4-nitro thioacetic acid butyl ester, (±)-2-rubigan-3-nitro propyl thioacetate are separated, and the little separating effect in silica gel aperture is better.Liquid chromatograph: Agilent-LC2000; Chromatographic column: the silica gel bonded filler of 150x4.6mm i.d., phase: A flows: hexane solution, B: aqueous isopropanol, flow velocity: 1.5ml/min, UV-254nm.
Claims (3)
1. silica gel bonded cellulose derivative class chiral chromatogram filler, its structural formula is.
2. according to the described silica gel bonded cellulose derivative chiral chromatogram filler of preparation claim 1, it is characterized in that may further comprise the steps:
1 silica gel activating: press hydrochloric acid and silica gel volume mass ratio 2-6ml/g, with percent by volume is that 20% hydrochloric acid and 30nm-300nm pore size silica gel are mixed with mixture, be heated to 90-100 ℃ of reaction backflow 2-6 hour, suction filtration, spend deionised water to neutral, 100-120 ℃ was dried by the fire 4-8 hour, and in 50 ℃ of vacuum drying 4-8 hours, it was standby to get activated silica gel;
2 KH-550 are to the modification of silica gel: take by weighing the above-mentioned spherical silica gel that has activated and pack in the there-necked flask, add the dry toluene of the 1/3-2/3 of reaction vessel volume, be 2-3:1-2 (ml/g) adding 3-aminopropyl triethoxysilane by KH-550 and silica gel volume/mass ratio, at 80-100 ℃ of following backflow 20-28 hour, whole process was at N
2Carry out under the following protection, cool off, filter the back, got white solid 3-aminopropyl silanized silica gel in 60 ℃ of vacuum drying 4-10 hours with methyl alcohol, acetone and n-hexane washing;
3 celluloses-2, the preparation of 3-two (3,5-3,5-dimethylphenyl carbamate):
1. microcrystalline cellulose 6-position hydroxyl protection: microcrystalline cellulose is mixed by mass ratio 1-2:3-5 with triphenylchloromethane, add anhydrous pyridine again, the addition of anhydrous pyridine is the 1/3-2/3 of reaction vessel volume; At 80-100 ℃, mechanical agitation, logical N
2Reaction condition under after backflow 18-24 hour with methyl alcohol suction filtration, washing, 6-position hydroxyl protection microcrystalline cellulose;
2. cellulose 2,3-position hydroxyl derivatization and 6-position hydroxyl go protection: take by weighing 1-1.5g and 1. get 6-position hydroxyl protection microcrystalline cellulose, add 3,5-dimethylphenyl isocyanate 1-4.5ml, with dry toluene and pyridine volume ratio is that the mixed liquor of 3-5:1-2 is a solvent, stirring and refluxing 18-24 hour, after finishing, reaction adds methyl alcohol and 0.6-1.5ml concentrated hydrochloric acid stirring at room reaction a period of time, after volatilizing with methyl alcohol suction filtration, washing, fume hood at last, 60-100 ℃ of vacuum drying obtains cellulose-2,3-two (3,5-3,5-dimethylphenyl carbamate);
4 3-aminopropyl silanized silica gel surface bond celluloses-2,3-two (3,5-3,5-dimethylphenyl carbamate) obtains fixedly phase of bonded chiral:
Take by weighing the cellulose-2 that above-mentioned reaction obtains, 3-two (3,5-3,5-dimethylphenyl carbamate) and 3-aminopropyl silanized silica gel silica gel mix according to mass ratio 1-2:2-3, add pyridine and volume of toluene than for the mixing material of 1-2:2-3 as solvent, add the hexamethylene diisocyanate reaction again, hexamethylene diisocyanate volume and 3-aminopropyl silanized silica gel mass ratio are 1-2:2-4 (ml/g), 80-100 ℃, mechanical agitation, after backflow 24-48 hour, be cooled to room temperature, use earlier the dry toluene suction filtration, washing, again with methyl alcohol suction filtration repeatedly, washing, product dry 6-10h under 60-80 ℃ gets product.
3. the application of silica gel bonded cellulose derivative chiral chromatogram filler according to claim 1, it is characterized in that, with n-hexane-isopropyl alcohol as mobile phase, to the DL-benzyl carbinol, the different benzyl carbinol of amoxy, (±)-3-rubigan-4-nitro thioacetic acid butyl ester, (±)-2-rubigan-3-nitro propyl thioacetate are better separated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100486904A CN102172519B (en) | 2011-03-01 | 2011-03-01 | Silica gel bonded cellulose derivative chromatographic filler and preparation method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100486904A CN102172519B (en) | 2011-03-01 | 2011-03-01 | Silica gel bonded cellulose derivative chromatographic filler and preparation method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102172519A true CN102172519A (en) | 2011-09-07 |
| CN102172519B CN102172519B (en) | 2012-11-14 |
Family
ID=44515875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100486904A Expired - Fee Related CN102172519B (en) | 2011-03-01 | 2011-03-01 | Silica gel bonded cellulose derivative chromatographic filler and preparation method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102172519B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055832A (en) * | 2012-12-31 | 2013-04-24 | 浙江月旭材料科技有限公司 | Chromatographic packing for separating water soluble polymer and protein and preparation method of same |
| CN103113480A (en) * | 2013-02-25 | 2013-05-22 | 广州研创生物技术发展有限公司 | Amylose derivative and preparation method and application thereof |
| CN103212386A (en) * | 2012-12-20 | 2013-07-24 | 北京化工大学 | High purity full porous silica gel-bonded chromatography immobile phase preparation method |
| CN103752293A (en) * | 2014-01-10 | 2014-04-30 | 常州南京大学高新技术研究院 | Bis-(ureido)/ureido-carbamate liquid chromatography stationary phase and preparation method thereof |
| CN104262496A (en) * | 2014-10-24 | 2015-01-07 | 南通裕弘分析仪器有限公司 | Chiral stationary phase of bonding amylose derivative and preparing method thereof |
| CN104607163A (en) * | 2015-01-26 | 2015-05-13 | 北京迪马欧泰科技发展中心 | Micro-chiral adjusting cellulose chromatography stationary phase, as well as preparation method and application thereof |
| CN105080518A (en) * | 2014-05-13 | 2015-11-25 | 中科院大连化学物理研究所淮安化工新材料研究中心 | Chemically-bonded cellulose-type chiral stationary phase and preparation method thereof |
| CN106188316A (en) * | 2015-05-08 | 2016-12-07 | 中国科学院化学研究所 | A kind of binding affinity Polysaccharides Type Chiral Stationary Phases and preparation method thereof |
| CN108752643A (en) * | 2018-04-10 | 2018-11-06 | 哈尔滨工程大学 | Preparation method based on cellulose derivative nano silicon dioxide hybridization material |
| CN110813266A (en) * | 2018-08-07 | 2020-02-21 | 中国科学院大连化学物理研究所 | Graphitized carbon chromatographic stationary phase and preparation method thereof |
| CN111229186A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Chromatographic stationary phase material and preparation method and application thereof |
| CN111534241A (en) * | 2020-05-08 | 2020-08-14 | 安徽格林开思茂光电科技股份有限公司 | Antistatic silica gel protection film |
| CN112375226A (en) * | 2020-10-12 | 2021-02-19 | 苏州纳微科技股份有限公司 | Bonded amylose derivative and preparation method and application thereof |
| CN112516976A (en) * | 2019-09-18 | 2021-03-19 | 有研工程技术研究院有限公司 | Method for preparing functional column chromatography silica gel |
| CN113651968A (en) * | 2021-07-21 | 2021-11-16 | 华南理工大学 | Lactide-derived chiral stationary phase and preparation method and application thereof |
| CN115569643A (en) * | 2022-10-20 | 2023-01-06 | 宁波大学 | Method for preparing chiral separation material by vacuum-assisted solid-phase reaction bonding |
| CN115999522A (en) * | 2023-01-05 | 2023-04-25 | 昆明医科大学 | Silica gel @ polyaniline @ polysaccharide derivative CSP filler and preparation method and application thereof |
| CN116351399A (en) * | 2022-12-30 | 2023-06-30 | 厦门色谱分析仪器有限公司 | Bonding cellulose derivative chiral liquid chromatographic column and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1578527A1 (en) * | 2002-09-13 | 2005-09-28 | Ciphergen Biosystems, Inc. | Preparation and use of mixed mode solid substrates for chromatography adsorbents and biochip arrays |
| CN101417227A (en) * | 2008-10-31 | 2009-04-29 | 北京化工大学 | Silica gel bonded double-chirality active center chromatogram filler, preparation method and use thereof |
| US20090216006A1 (en) * | 2008-02-21 | 2009-08-27 | Hui Xu | Covalently bound polysaccharide-based chiral stationary phases and method for their preparation |
| CN101811034A (en) * | 2010-03-25 | 2010-08-25 | 王荣 | Synthesis and application of large-grain diameter chiral stationary phase |
-
2011
- 2011-03-01 CN CN2011100486904A patent/CN102172519B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1578527A1 (en) * | 2002-09-13 | 2005-09-28 | Ciphergen Biosystems, Inc. | Preparation and use of mixed mode solid substrates for chromatography adsorbents and biochip arrays |
| US20090216006A1 (en) * | 2008-02-21 | 2009-08-27 | Hui Xu | Covalently bound polysaccharide-based chiral stationary phases and method for their preparation |
| CN101417227A (en) * | 2008-10-31 | 2009-04-29 | 北京化工大学 | Silica gel bonded double-chirality active center chromatogram filler, preparation method and use thereof |
| CN101811034A (en) * | 2010-03-25 | 2010-08-25 | 王荣 | Synthesis and application of large-grain diameter chiral stationary phase |
Non-Patent Citations (2)
| Title |
|---|
| 《河南科学》 20050630 孟磊等 "纤维素-三(3,5-二甲基苯基氨基甲酸酯)手性柱" 第23卷, 第3期 * |
| 《湖北民族学院学报(自然科学版)》 20080630 李国祥等 纤维素-三(苯基氨基甲酸酯)手性固定相的制备 第26卷, 第2期 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103212386A (en) * | 2012-12-20 | 2013-07-24 | 北京化工大学 | High purity full porous silica gel-bonded chromatography immobile phase preparation method |
| CN103212386B (en) * | 2012-12-20 | 2014-12-03 | 北京化工大学 | High purity full porous silica gel-bonded chromatography immobile phase preparation method |
| CN103055832B (en) * | 2012-12-31 | 2015-04-01 | 浙江月旭材料科技有限公司 | Chromatographic packing for separating water soluble polymer and protein and preparation method of same |
| CN103055832A (en) * | 2012-12-31 | 2013-04-24 | 浙江月旭材料科技有限公司 | Chromatographic packing for separating water soluble polymer and protein and preparation method of same |
| CN103113480A (en) * | 2013-02-25 | 2013-05-22 | 广州研创生物技术发展有限公司 | Amylose derivative and preparation method and application thereof |
| CN103752293A (en) * | 2014-01-10 | 2014-04-30 | 常州南京大学高新技术研究院 | Bis-(ureido)/ureido-carbamate liquid chromatography stationary phase and preparation method thereof |
| CN103752293B (en) * | 2014-01-10 | 2016-03-23 | 常州南京大学高新技术研究院 | Allophanamide base/urea groups-Carbamic acid ester type liquid phase chromatogram stationary phase and preparation method thereof |
| CN105080518A (en) * | 2014-05-13 | 2015-11-25 | 中科院大连化学物理研究所淮安化工新材料研究中心 | Chemically-bonded cellulose-type chiral stationary phase and preparation method thereof |
| CN104262496B (en) * | 2014-10-24 | 2016-09-07 | 南通裕弘分析仪器有限公司 | A kind of chiral stationary phase being bonded straight chain starch derivative and preparation method thereof |
| CN104262496A (en) * | 2014-10-24 | 2015-01-07 | 南通裕弘分析仪器有限公司 | Chiral stationary phase of bonding amylose derivative and preparing method thereof |
| CN104607163B (en) * | 2015-01-26 | 2018-05-15 | 北京迪马欧泰科技发展中心 | A kind of micro- chiral adjusting cellulose chromatography stationary phase, preparation method and applications |
| CN104607163A (en) * | 2015-01-26 | 2015-05-13 | 北京迪马欧泰科技发展中心 | Micro-chiral adjusting cellulose chromatography stationary phase, as well as preparation method and application thereof |
| CN106188316A (en) * | 2015-05-08 | 2016-12-07 | 中国科学院化学研究所 | A kind of binding affinity Polysaccharides Type Chiral Stationary Phases and preparation method thereof |
| CN108752643A (en) * | 2018-04-10 | 2018-11-06 | 哈尔滨工程大学 | Preparation method based on cellulose derivative nano silicon dioxide hybridization material |
| CN110813266A (en) * | 2018-08-07 | 2020-02-21 | 中国科学院大连化学物理研究所 | Graphitized carbon chromatographic stationary phase and preparation method thereof |
| CN111229186A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Chromatographic stationary phase material and preparation method and application thereof |
| CN112516976B (en) * | 2019-09-18 | 2023-10-10 | 有研工程技术研究院有限公司 | Method for preparing functional column chromatography silica gel |
| CN112516976A (en) * | 2019-09-18 | 2021-03-19 | 有研工程技术研究院有限公司 | Method for preparing functional column chromatography silica gel |
| CN111534241A (en) * | 2020-05-08 | 2020-08-14 | 安徽格林开思茂光电科技股份有限公司 | Antistatic silica gel protection film |
| CN112375226A (en) * | 2020-10-12 | 2021-02-19 | 苏州纳微科技股份有限公司 | Bonded amylose derivative and preparation method and application thereof |
| WO2022077606A1 (en) * | 2020-10-12 | 2022-04-21 | 苏州纳微科技股份有限公司 | Bonded amylose derivative, and preparation method therefor and application thereof |
| CN113651968A (en) * | 2021-07-21 | 2021-11-16 | 华南理工大学 | Lactide-derived chiral stationary phase and preparation method and application thereof |
| CN115569643A (en) * | 2022-10-20 | 2023-01-06 | 宁波大学 | Method for preparing chiral separation material by vacuum-assisted solid-phase reaction bonding |
| CN115569643B (en) * | 2022-10-20 | 2023-10-03 | 宁波大学 | Method for preparing chiral separation material by vacuum-assisted solid phase reaction bonding |
| CN116351399A (en) * | 2022-12-30 | 2023-06-30 | 厦门色谱分析仪器有限公司 | Bonding cellulose derivative chiral liquid chromatographic column and preparation method and application thereof |
| CN115999522A (en) * | 2023-01-05 | 2023-04-25 | 昆明医科大学 | Silica gel @ polyaniline @ polysaccharide derivative CSP filler and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102172519B (en) | 2012-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102172519B (en) | Silica gel bonded cellulose derivative chromatographic filler and preparation method and use thereof | |
| CN101417227B (en) | Silica gel bonded double-chirality active center chromatogram filler and use thereof | |
| CN102921193B (en) | Preparation method of capillary electro-chromatography column taking beta-cyclodextrin as bonded stationary phase and application in chiral drug separation | |
| CN104262496B (en) | A kind of chiral stationary phase being bonded straight chain starch derivative and preparation method thereof | |
| US20070215549A1 (en) | Separating agent for enantiomeric isomers | |
| CN103601823A (en) | Preparation method for beta-cyclodextrin chiral stationary phase | |
| CN103551118B (en) | Column [5] aromatic bonding silica gel stationary phase as well as preparation method and application thereof | |
| CN103406113A (en) | Preparation method of immobilized beta-cyclodextrin derivative type chiral stationary phase | |
| CN102527357A (en) | SCX/HIC (Strong Cation Exchange/Hydrophobic) mixed-mode chromatograph stationary phase and preparation method thereof | |
| CN105080518A (en) | Chemically-bonded cellulose-type chiral stationary phase and preparation method thereof | |
| CN103951665B (en) | The method of the preparation of novel tropine alcohols amino acid anionic chiral ionic liquid, immobilization and fractionation DL-phenylalanine and DL-Trp | |
| CN103193898A (en) | Synthesis and application of L-phenylalanine derived Beta-cyclodextrin bonded silica gel for separating alanine enantiomer | |
| Shen et al. | Synthesis and immobilization of amylose derivatives bearing a 4-tert-butylbenzoate group at the 2-position and 3, 5-dichlorophenylcarbamate/3-(triethoxysilyl) propylcarbamate groups at 3-and 6-positions as chiral packing material for HPLC | |
| CN102160994B (en) | Silica gel bonded brush-type chiral stationary phase, synthesizing method and application | |
| CN105688858B (en) | A kind of Amylose Chiral Stationary Phase and preparation method thereof | |
| CN102059105B (en) | Oligopeptide-simulated CSP (Chiral Stationary Phase) and preparation method thereof | |
| JPS63156538A (en) | Separating agent | |
| CN104028253B (en) | A kind of gold nano grain-polysaccharide bonded silica gel stationary phase and preparation method thereof | |
| CN103182298B (en) | Synthesis of L-tryptophan derived beta-cyclodextrin bonded silica gel and application thereof for separating alanine enantiomers | |
| CN104117346A (en) | Bonded cellulose 3,5-dimethylphenyl carbamate stationary phase and preparation method thereof | |
| CN108745315B (en) | Cellulose-modified chloromethylated polystyrene hypercrosslinked resin and adsorption separation method | |
| CN104628892A (en) | Preparation method and use of 6-benzyl phenylethylamine derivative beta-cyclodextrin bonded SBA-15 | |
| CN101628225B (en) | 1-vinyl iminazole ionic liquid chromatography packing as well as preparation method and use method thereof | |
| CN105944701A (en) | Preparation method of bonded nanocellulose chiral stationary phase | |
| CN105601940A (en) | Chitosan derivatization calix [4] arene bonded silica gel stationary phase and preparing method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121114 Termination date: 20150301 |
|
| EXPY | Termination of patent right or utility model |