CN103272574A - Core-shell ordered hybrid mesoporous chromatographic filling material and preparation method thereof - Google Patents
Core-shell ordered hybrid mesoporous chromatographic filling material and preparation method thereof Download PDFInfo
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- CN103272574A CN103272574A CN2013101560646A CN201310156064A CN103272574A CN 103272574 A CN103272574 A CN 103272574A CN 2013101560646 A CN2013101560646 A CN 2013101560646A CN 201310156064 A CN201310156064 A CN 201310156064A CN 103272574 A CN103272574 A CN 103272574A
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Abstract
The invention discloses a core-shell liquid chromatographic filling material. An inner layer of the filling material is a nonporous silica gel, an outer layer of the filling material is clad with an ordered hybrid mesoporous silica gel, and a framework of the ordered hybrid mesoporous silica gel is admixed with ethylene. At the same time, the invention also discloses a preparation method for the core-shell liquid chromatographic filling material. The existing core-shell filling material which has the advantages of high column efficiency and fast analyzing speed is combined with the hybrid mesoporous silica gel which has the advantages of high specific surface area, high permeability, good stability and uniform distribution of organic functional groups, so that the core-shell liquid chromatographic filling material becomes a novel chromatographic stationary phase filling material.
Description
Technical field
The present invention relates to porous material preparation and technical field of analytical chemistry, be specifically related to a kind of nucleocapsid liquid chromatography stuffing and preparation method thereof.
Background technology
Hybridization mesoporous material is an emerging in recent years class functional material, refers to adopt the estersil [(R of organic group bridging
2O)
3Si-R
1-Si (OR
2)
3] as one of silicon source, after hydrolytic-polymeric reaction, directly prepare the mesoporous silica gel that contains organic group in the skeleton.Compare with inorganic mesoporous silica gel, hybrid mesoporous silica gel not only has high-specific surface area, regularly arranged duct, narrow pore-size distribution equally, and have better hydrothermal stability, mechanical stability and chemical stability, become the hybrid material that a class has higher using value.By in preparation process, directly organo-functional group being incorporated into the hybrid material for preparing in the material skeleton, can effectively avoid loaded down with trivial details bonding process.Simultaneously, the introducing amount of organo-functional group and distributing homogeneity can be well controlled.Hybrid mesoporous silica gel is used for chromatographic isolation, has application promise in clinical practice.
The core-shell type material is to be nuclear with a size at the spheric granules of micron to nano grade, coats several layers of even polymer on its surface and a kind of compound heterogeneous structure that forms, interconnects by physics or chemical action between nuclear and the shell.Horv á t team has proposed since the concept of hud typed fixedly phase before 40 years, and the development of this kind filler is good, becomes the rising star in the chromatographic column filler.Hud typed filler is than the filler of full porous, has higher theoretical cam curve (the full loose structure post of the nucleocapsid of 3 μ m and inferior 2 μ m is imitated quite), mainly be because the operating path of solute in particle shortens, can overcome because the peak shape diffusion that resistance to mass tranfer causes.At present commercial hud typed chromatograph packing material is existing a lot, and the silica matrix core-shell material has obtained the most deep research, and they have chromatographic performance preferably, and such as pH stability, higher post is imitated, preferably separation selectivity etc.But because the particularity of hud typed filling-material structure, contained organo-functional group load capacity is few, and the back pressure height still can run into some problems in actual applications.And hybridization mesoporous material has high specific area, organo-functional group load capacity height; The duct of running through, the advantage of low back pressure can well solve the problem that hud typed filler brings, and therefore both is combined, and certainly will become the novel chromatographic stationary phase that is easy to popularize of a class.And the report relevant for the hud typed filler of hybrid mesoporous class is not seen in Literature Consult yet, so this problem has certain innovation and applied value.
Summary of the invention
Goal of the invention: the objective of the invention is at the deficiencies in the prior art, a kind of novel nucleocapsid liquid chromatography stuffing is provided.
Another object of the present invention is to provide the preparation method of above-mentioned nucleocapsid liquid chromatography stuffing.
Technical scheme: in order to achieve the above object, the present invention specifically is achieved like this: a kind of nucleocapsid liquid chromatography stuffing, internal layer are atresia silica gel, the outer coating by doping-CH in the skeleton of 1,2-two (triethoxy is silica-based) ethane hydrolytie polycondensation one-tenth
2-CH
2The orderly hybridization mesoporous material of-group.
Wherein, the outer orderly hybrid mesoporous silica gel skeleton that coats of described filler is except mixing-CH
2-CH
2Outside-the group, also can mix-CH=CH--C
6H
4-group.
A kind of preparation method of nucleocapsid liquid chromatography stuffing may further comprise the steps:
(1) gets ammoniacal liquor, ethanol and deionized water be mixed and made into A liquid at 150～250: 40～80: 60～120 by volume, A liquid and ethyl orthosilicate under condition of ice bath are mixed stir 0.5h～2h by volume at 1～3: 1, the product that obtains is extremely neutral with deionized water and ethanol washing, 80～100 ℃ of drying 8～10h, the atresia silica gel that obtains having spherical morphology;
(2) the atresia silica gel that obtains is carried out acidification reaction, and product is washed till neutrality with deionized water, 80～100 ℃ of drying 10～12h;
(3) 1: 1 by volume～5 with ethanol and deionized water mixing, adds 0.1～0.8% (w/v) softex kw, 1～10% (w/v) P123 block copolymer, makes B liquid;
(4) 1: 1 by volume～5 with ethanol and deionized water mixing, the atresia silica gel of getting after the acidifying adds wherein, and every 100ml solution adds 1～8g atresia silica gel, and ultrasonic 10～30min, 28% ammoniacal liquor that adds above-mentioned cumulative volume 2～10%, stirring at room 15～20min;
(5) 1: 1 by volume～3 with B liquid adding step (4) gained, dropwise adds mixeding liquid volume 0.5～6% (v/v) 1,2-two (triethoxy is silica-based) ethane, and room temperature reaction 1～1.5h, the centrifugal product that gets obtains coating doping-CH in one deck skeleton
2-CH
2-the hud typed material of orderly hybrid mesoporous silica gel;
(6) with ethanol and deionized water that the hud typed material washing of step (5) gained is extremely neutral, 80～90 ℃ of oven dry 8～10h;
(7) 200: 1 by volume～8 get ethanol, concentrated hydrochloric acid is mixed into the stripper plate agent, every 1g step (6) product at room temperature stirs 12h with the agent of 200ml stripper plate at twice;
(8) step (7) products therefrom is spent deionised water to neutral, 80～90 ℃ of drying 8～10h namely obtain finished product nucleocapsid liquid chromatography stuffing.
Wherein, the diameter of atresia silica gel is 0.2 μ m～5 μ m in the described step (1).
Wherein, described step (2) acidification reaction is the atresia silica gel that adds its quality 1～6% in 10% hydrochloric acid, stirs 12h.
Wherein, skeleton mixes in the described step (5)-CH
2-CH
2-group can be by-CH=CH-,-C
6H
4-replace.
In order to make the outer multilayer order mesoporous silica gel that coats of filler, with the atresia silica gel after the acidifying in the centrifugal product replacement step of step (5) gained (4), repeating step (4) and (5) and other steps are constant, obtain coating the hud typed material of the hybrid mesoporous silica gel of multilayer order, coating the number of plies is 2～8 layers, and the thickness of coating is 50～500nm.
Beneficial effect: the present invention combines that hybrid mesoporous class silica gel has high-specific surface area, high-permeability, good stability, organo-functional group is evenly distributed and hud typed filled column imitate high, the advantage that analysis speed is fast and become the novel chromatograph stationary-phase stuffing of a class.
The specific embodiment
Embodiment 1:
Get ammoniacal liquor, ethanol and deionized water in 150: 40: 60 by volume and be mixed and made into A liquid, A liquid and ethyl orthosilicate were mixed stirring 0.5h in 1: 1 by volume under condition of ice bath, the product that obtains is extremely neutral with deionized water and ethanol washing, 80～100 ℃ of dry 8h, obtaining diameter is the atresia silica gel of 0.2 μ m; In 10% hydrochloric acid, add the atresia silica gel of its quality 1%, stir 12h, and product is washed till neutrality with deionized water, 80 ℃ of dry 10h; Ethanol and deionized water mixing were added 0.1g softex kw and 1gP123 block copolymer in every 100ml mixed liquor, make B liquid in 1: 5 by volume; Ethanol and deionized water mixed in 1: 5 by volume, the atresia silica gel of getting after the acidifying adds wherein, and every 100ml solution adds 1g atresia silica gel, and ultrasonic 10min, adds 28% ammoniacal liquor of above-mentioned cumulative volume 2%, stirring at room 15min; B liquid added the mixed liquor of above-mentioned atresia silica gel in 1: 3 by volume, dropwise add 1 of total mixeding liquid volume 0.5%, 2-two (triethoxy is silica-based) ethane, room temperature reaction 1h, the centrifugal product that gets obtains covering one deck 1, the hud typed material of 2-two (triethoxy is silica-based) ethane; With ethanol and ionized water that the hud typed material washing of gained is extremely neutral, 80～90 ℃ of oven dry 8h; Got ethanol in 200: 1 by volume, concentrated hydrochloric acid is mixed into the stripper plate agent, the hud typed material of every 1g at room temperature stirs 12h with the agent of 200ml stripper plate at twice, the washing of back deionized water is to neutral, 80 ℃ of dry 8h namely obtain finished product nucleocapsid liquid chromatography stuffing.
Embodiment 2:
Get ammoniacal liquor, ethanol and deionized water in 250: 80: 120 by volume and be mixed and made into A liquid, A liquid and ethyl orthosilicate were mixed stirring 2h in 3: 1 by volume under condition of ice bath, the product that obtains is extremely neutral with deionized water and ethanol washing, 80～100 ℃ of dry 10h, obtaining diameter is the atresia silica gel of 5 μ m; In 10% hydrochloric acid, add the atresia silica gel of its quality 6%, stir 12h, and product is washed till neutrality with deionized water, 80～100 ℃ of dry 12h; Ethanol and deionized water mixing were added 0.8g softex kw and 10gP123 block copolymer in every 100ml mixed liquor, make B liquid in 1: 1 by volume; Ethanol and deionized water mixed in 1: 1 by volume, the atresia silica gel of getting after the acidifying adds wherein, and every 100ml solution adds 8g atresia silica gel, and ultrasonic 30min, adds 28% ammoniacal liquor of above-mentioned cumulative volume 10%, stirring at room 20min; B liquid adding atresia silica gel mixed liquor was dropwise added 1 of total mixeding liquid volume 6%, 2-two (triethoxy is silica-based) ethane in 1: 1 by volume, room temperature reaction 1.5h, the centrifugal product that gets obtains covering one deck 1, the hud typed material of 2-two (triethoxy is silica-based) ethane; Ethanol and deionized water mixing were got centrifugal product and added wherein in 1: 1 by volume, every 100ml solution adds the centrifugal product of 8g, and ultrasonic 30min, adds 28% ammoniacal liquor of above-mentioned cumulative volume 10%, stirring at room 20min; B liquid added centrifugal product mixed liquor in 1: 1 by volume, dropwise add 1 of total mixeding liquid volume 6%, 2-two (triethoxy is silica-based) ethane, room temperature reaction 1.5h, centrifugal product, obtain covering two-layer 1, the hud typed material of 2-two (triethoxy is silica-based) ethane; With ethanol and ionized water that the hud typed material washing of gained is extremely neutral, 80～90 ℃ of oven dry 8h; Got ethanol in 200: 8 by volume, concentrated hydrochloric acid is mixed into the stripper plate agent, the hud typed material of every 1g at room temperature stirs 12h with the agent of 200ml stripper plate at twice, the washing of back deionized water is to neutral, 80～90 ℃ of dry 8h namely obtain finished product nucleocapsid liquid chromatography stuffing.
Embodiment 3:
Get ammoniacal liquor, ethanol and deionized water in 200: 60: 100 by volume and be mixed and made into A liquid, A liquid and ethyl orthosilicate were mixed stirring 1.5h in 2: 1 by volume under condition of ice bath, the product that obtains is extremely neutral with deionized water and ethanol washing, 80～100 ℃ of dry 9h, obtaining diameter is the atresia silica gel of 3 μ m; In 10% hydrochloric acid, add the atresia silica gel of its quality 4%, stir 12h, and product is washed till neutrality with deionized water, 80～100 ℃ of dry 10h; Ethanol and deionized water mixing were added 0.6g softex kw and 6gP123 block copolymer in every 100ml mixed liquor, make B liquid in 1: 2 by volume; Ethanol and deionized water mixed in 1: 2 by volume, the atresia silica gel of getting after the acidifying adds wherein, and every 100ml solution adds 6g atresia silica gel, and ultrasonic 20min, adds 28% ammoniacal liquor of above-mentioned cumulative volume 8%, stirring at room 15min; B liquid adding atresia silica gel mixed liquor was dropwise added 1 of total mixeding liquid volume 5%, 2-two (triethoxy is silica-based) ethane in 1: 2 by volume, room temperature reaction 1.5h, the centrifugal product that gets obtains covering one deck 1, the hud typed material of 2-two (triethoxy is silica-based) ethane; Ethanol and deionized water mixing were got centrifugal product and added wherein in 1: 2 by volume, every 100ml solution adds the centrifugal product of 6g, and ultrasonic 20min, adds 28% ammoniacal liquor of above-mentioned cumulative volume 8%, stirring at room 20min; B liquid added centrifugal product mixed liquor in 1: 2 by volume, dropwise add 1 of total mixeding liquid volume 5%, 2-two (triethoxy is silica-based) ethane, room temperature reaction 1.5h, the centrifugal product that gets obtains covering two-layer 1, the hud typed material of 2-two (triethoxy is silica-based) ethane, repeat this step once, obtain obtain three layers 1, the hud typed material of 2-two (triethoxy is silica-based) ethane; With ethanol and ionized water that the hud typed material washing of gained is extremely neutral, 80～90 ℃ of oven dry 8h; Got ethanol in 200: 8 by volume, concentrated hydrochloric acid is mixed into the stripper plate agent, the hud typed material of every 1g at room temperature stirs 12h with the agent of 200ml stripper plate at twice, the washing of back deionized water is to neutral, 80～90 ℃ of dry 8h namely obtain finished product nucleocapsid liquid chromatography stuffing.
Embodiment 4:
Get ammoniacal liquor, ethanol and deionized water in 180: 50: 80 by volume and be mixed and made into A liquid, A liquid and ethyl orthosilicate were mixed stirring 2h in 3: 1 by volume under condition of ice bath, the product that obtains is extremely neutral with deionized water and ethanol washing, 80～100 ℃ of dry 10h, obtaining diameter is the atresia silica gel of 4 μ m; In 10% hydrochloric acid, add the atresia silica gel of its quality 5%, stir 12h, and product is washed till neutrality with deionized water, 80～100 ℃ of dry 9h; Ethanol and deionized water mixing were added 0.4g softex kw and 4g P123 block copolymer in every 100ml mixed liquor, make B liquid in 1: 3 by volume; Ethanol and deionized water mixed in 1: 3 by volume, the atresia silica gel of getting after the acidifying adds wherein, and every 100ml solution adds 5g atresia silica gel, and ultrasonic 20min, adds 28% ammoniacal liquor of above-mentioned cumulative volume 6%, stirring at room 15min; B liquid added atresia silica gel mixed liquor in 1: 3 by volume, dropwise add the aminopropyl triethoxysilane of total mixeding liquid volume 4%, room temperature reaction 1.5h, centrifugal product obtains covering the hud typed material of one deck aminopropyl; Ethanol and deionized water mixing were got centrifugal product and added wherein in 1: 3 by volume, every 100ml solution adds the centrifugal product of 5g, and ultrasonic 20min, adds 28% ammoniacal liquor of above-mentioned cumulative volume 6%, stirring at room 20min; B liquid added centrifugal product mixed liquor in 1: 3 by volume, dropwise add the aminopropyl of total mixeding liquid volume 4%, room temperature reaction 1.5h, the centrifugal product that gets, obtain covering the hud typed material of two-layer aminopropyl, repeat this step twice, obtain covering the hud typed material of 4 layers of aminopropyl; With ethanol and ionized water that the hud typed material washing of gained is extremely neutral, 80～90 ℃ of oven dry 10h; Got ethanol in 200: 4 by volume, concentrated hydrochloric acid is mixed into the stripper plate agent, the hud typed material of every 1g at room temperature stirs 12h with the agent of 200ml stripper plate at twice, the washing of back deionized water is to neutral, 80～90 ℃ of dry 10h namely obtain finished product nucleocapsid liquid chromatography stuffing.
Embodiment 5
Fig. 1 is the ESEM picture of atresia silica gel of the present invention
Fig. 2 is that outer the coating in the skeleton of atresia silica gel of the present invention contained-CH
2-CH
2The sem photograph of the hud typed filler of-orderly hybrid mesoporous silica gel
Fig. 3 is hud typed hybrid mesoporous silica gel of the present invention chromatographic fractionation figure to toluene, naphthalene and nitrobenzene under different in flow rate.
Claims (8)
1. a nucleocapsid liquid chromatography stuffing is characterized in that, internal layer is atresia silica gel, the outer orderly hybridization mesoporous material that coats by 1,2-two (triethoxy is silica-based) ethane hydrolytie polycondensation one-tenth.
2. the preparation method of nucleocapsid liquid chromatography stuffing is characterized in that, may further comprise the steps:
(1) gets ammoniacal liquor, ethanol and deionized water be mixed and made into A liquid at 150～250: 40～80: 60～120 by volume, A liquid and ethyl orthosilicate under condition of ice bath are mixed stir 0.5h～2h by volume at 1～3: 1, the product that obtains is extremely neutral with deionized water and ethanol washing, 80～100 ℃ of drying 8～10h, the atresia silica gel that obtains having spherical morphology;
(2) the atresia silica gel that obtains is carried out acidification reaction, and product is washed till neutrality with deionized water, 80～100 ℃ of drying 10～12h;
(3) 1: 1 by volume～5 with ethanol and deionized water mixing, adds 0.1～0.8% (w/v) softex kw, 1～10% (w/v) P123 block copolymer, makes B liquid;
(4) 1: 1 by volume～5 with ethanol and deionized water mixing, the atresia silica gel of getting after the acidifying adds wherein, and every 100ml solution adds 1～8g atresia silica gel, and ultrasonic 10～30min, 28% ammoniacal liquor that adds above-mentioned cumulative volume 2～10%, stirring at room 15～20min;
(5) 1: 1 by volume～3 with B liquid adding step (4) gained, dropwise adds mixeding liquid volume 0.5～6% (v/v) 1,2-two (triethoxy is silica-based) ethane, and room temperature reaction 1～1.5h, the centrifugal product that gets obtains coating doping-CH in one deck skeleton
2-CH
2-the hud typed material of orderly hybrid mesoporous silica gel;
(6) with ethanol and deionized water that the hud typed material washing of step (5) gained is extremely neutral, 80～90 ℃ of oven dry 8～10h;
(7) 200: 1 by volume～8 get ethanol, concentrated hydrochloric acid is mixed into the stripper plate agent, every 1g step (6) product at room temperature stirs 12h with the agent of 200ml stripper plate at twice;
(8) step (7) products therefrom is spent deionised water to neutral, 80～90 ℃ of drying 8～10h namely obtain finished product nucleocapsid liquid chromatography stuffing.
3. the preparation method of nucleocapsid liquid chromatography stuffing according to claim 2 is characterized in that, the diameter of atresia silica gel is 0.2 μ m～5 μ m in the described step (1).
4. the preparation method of nucleocapsid liquid chromatography stuffing according to claim 2 is characterized in that, described step (2) acidification reaction is the atresia silica gel that adds its quality 1～6% (w/v) in 10% hydrochloric acid, stirs 12h.
5. the preparation method of nucleocapsid liquid chromatography stuffing according to claim 2, it is characterized in that, with the atresia silica gel after the acidifying in the centrifugal product replacement step of step (5) gained (4), repeating step (4) and (5) and other steps are constant, obtain coating the hud typed material of the hybrid mesoporous silica gel of multilayer order.
6. the preparation method of nucleocapsid liquid chromatography stuffing according to claim 5 is characterized in that, the number of plies that described orderly hybridization mesoporous material coats is 2～8 layers.
7. according to the preparation method of the arbitrary described nucleocapsid liquid chromatography stuffing of claim 2～6, it is characterized in that skeleton mixes-CH in the step (5)
2-CH
2-group can be by-CH=CH-,-C
6H
4-replace.
8. the preparation method of nucleocapsid liquid chromatography stuffing according to claim 2 is characterized in that, in the described step (5), the thickness of hybridization mesoporous material coating is 50～500nm in order.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727909A (en) * | 2014-12-09 | 2016-07-06 | 中国科学院大连化学物理研究所 | Silica gel microsphere with core-shell structure and preparation and application thereof |
| CN113150280A (en) * | 2021-03-15 | 2021-07-23 | 苏州纳微科技股份有限公司 | Chromatographic packing and preparation method and application thereof |
| CN113680338A (en) * | 2021-08-26 | 2021-11-23 | 天津津颐生物科技有限公司 | Novel chromatographic material and preparation method thereof |
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| CN102276840A (en) * | 2011-05-06 | 2011-12-14 | 中国药科大学 | Camphor sulfonamide doped ethane bridge bond spherical mesoporous silica gel |
-
2013
- 2013-04-28 CN CN2013101560646A patent/CN103272574A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276840A (en) * | 2011-05-06 | 2011-12-14 | 中国药科大学 | Camphor sulfonamide doped ethane bridge bond spherical mesoporous silica gel |
Non-Patent Citations (1)
| Title |
|---|
| QI HONG: "Preparation of composite microporous silica membranes using TEOS and 1,2-bis(triethoxysilyl)ethane as precursors for gas separation", 《CHINESE JOURNAL OF CHEMICAL ENGINEERING》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727909A (en) * | 2014-12-09 | 2016-07-06 | 中国科学院大连化学物理研究所 | Silica gel microsphere with core-shell structure and preparation and application thereof |
| CN113150280A (en) * | 2021-03-15 | 2021-07-23 | 苏州纳微科技股份有限公司 | Chromatographic packing and preparation method and application thereof |
| CN113680338A (en) * | 2021-08-26 | 2021-11-23 | 天津津颐生物科技有限公司 | Novel chromatographic material and preparation method thereof |
| CN113680338B (en) * | 2021-08-26 | 2024-06-04 | 天津博蕴纯化装备材料科技有限公司 | Novel chromatographic material and preparation method thereof |
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Application publication date: 20130904 |