CN101717513B - Hybrid ordered mesoporous silica gel chromatograph stationary-phase stuffing and preparation method thereof - Google Patents
Hybrid ordered mesoporous silica gel chromatograph stationary-phase stuffing and preparation method thereof Download PDFInfo
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- CN101717513B CN101717513B CN2009102130189A CN200910213018A CN101717513B CN 101717513 B CN101717513 B CN 101717513B CN 2009102130189 A CN2009102130189 A CN 2009102130189A CN 200910213018 A CN200910213018 A CN 200910213018A CN 101717513 B CN101717513 B CN 101717513B
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Abstract
The invention relates to the chemical technical field of mesoporous material preparation and analysis, in particular to a hybrid ordered mesoporous silica gel chromatograph stationary-phase stuffing and a preparation method thereof. The hybrid ordered mesoporous silica gel chromatograph stationary-phase stuffing is characterized in that: hydroxyl connected with silicon atoms on the original hybrid ordered mesoporous silica gel is substituted by aminopropyl. The stuffing has regular and smooth spherical appearance; frameworks of the silicon gel are doped with ethylene radical which has weak hydrophobicity, therefore, the stuffing can not generate silicon gel dissolution phenomenon when being used in flow phase with high aqueous phase proportion and can bear larger pH range (1-11); furthermore, mesoporous pore paths are distributed sequentially, therefore, the mass transfer can be accelerated, and the column pressure is reduced; and the invention is suitable for fast segregation analysis under high aqueous phase proportion.
Description
Technical field
The present invention relates to porous material preparation and technical field of analytical chemistry, be specifically related to a kind of hybrid ordered mesoporous silica gel, this silica gel can be used as chromatograph stationary-phase stuffing.
Background technology
Hybrid ordered mesoporous silica gel be meant adopt the organic group bridging estersil [(OR)
3SiR ' Si (OR)
3] as one of silicon source, after hydrolytic-polymeric reaction, directly prepare the ordered mesoporous silica gel that contains organic group in the skeleton.Compare with ordered mesoporous silica gel, hybridisation 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 a chemical stability, and the preparation method is simple, controllable degree is big, shows superior prospect in the application of chromatographic separation.
The commercialization chromatographic column filler adopts grafting substantially, and soon organo-functional group is bonded to the silicon hydroxyl on the spherical silica gel carrier and makes.This method complex operation is time-consuming, and needs to guarantee that the bonding environment is anhydrous.Functional group is extremely inhomogeneous in the silica gel surface arrangement.Once more, toxicity is stronger mostly for the organic solvent (as toluene, pyridine etc.) that grafting is used, and brings certain influence to environment.
At present, the research of preparation amine propyl group hybridization mesoporous material concentrates on the organic catalysis field basically, its research focus mainly is the control to its mesoporous passage, and concrete pattern is not very paid attention to [Lei Zhang, et al.Direct synthesis of highlyordered amine-functionalized mesoporous ethane-silicas.Micropor MesopMat.2008,109:172-183].
Commercially available amino chromatographic column mainly contains two defectives: in the moving phase water ratio must not be higher than 25% and the pH use range at 2-8.For improving the shortcoming of above-mentioned grafting, the hybridisation silica gel that adopts one step of multiple silicon source copolycondensation to prepare multiple organo-functional group modification has caused analytical chemistry worker's interest.
Summary of the invention
The invention discloses a class hybrid ordered mesoporous silica gel, it has regular slick spherical morphology, fusion has ethylene group in the skeleton of silica gel, has weak hydrophobicity, thereby use in mutually in high water proportional flow, silica gel dissolved phenomenon can not occur, and can tolerate bigger pH scope (1-11).Moreover its mesopore orbit distributes in order, thereby can accelerate mass transfer and lower post to press, and is applicable to the sharp separation analysis under the high water ratio.
Hybrid ordered mesoporous silica gel of the present invention is on the basis of ordered mesoporous silica gel, the hydroxyl that original hybrid ordered mesoporous silica gel molecular surface is linked to each other with Siliciumatom substitutes with the amine propyl group, or take by weighing generation, promptly the Siliciumatom of hybrid ordered mesoporous silica gel molecular surface directly with amine propyl group bonding mutually.
As follows with the hybrid ordered mesoporous silica gel molecular structure behind the amine propyl group bonding:
The skeleton fusion of hybrid ordered mesoporous silica gel of the present invention ethylene group, the charge capacity of ethylene group is preferably 4-10mmol/g, surface bond the amine propyl group, the charge capacity of amine propyl group is preferably 0.1-4 μ mol/m
2
Hybrid ordered mesoporous silica gel of the present invention is a spheric, has high-specific surface area, reaches as high as 1500m
2/ g.And have orderly duct, the duct is between 2-10nm.
Hybrid ordered mesoporous silica gel of the present invention can prepare with following method: by amine propyl-triethoxysilicane and 1,2-two (triethoxy is silica-based) ethane is as the silicon source, with alkali as hydrolyst, with tensio-active agent as template, with alcohol is organic additive, make through hydrothermal synthesis method one step copolycondensation, remove template with hydrochloric ethanolic soln, drying is promptly made.
Amine propyl-triethoxysilicane wherein: 1,2-two (triethoxy is silica-based) ethane: tensio-active agent: alkali: alcohol: the mol ratio of water is preferably 0.1～0.6: 0.4～0.5: 0.6～0.9: 1.0～2.4: 30～150: 300～500.In this scope, by changing different amine propyl-triethoxysilicanes and 1, the ratio of 2-two (triethoxy is silica-based) ethane can obtain the hybrid ordered mesoporous silica gel that different chromatographic stationary requires mutually.
Described tensio-active agent preferred structure is the quaternary ammonium salt shown in following:
R wherein
1, R
2, R
3And R
4Independently be selected from C respectively
1-C
22A kind of in the alkyl, and R
1, R
2, R
3And R
4In have one at least for C
12-C
22Alkyl; X is a halogen, and F, Cl, Br or I all can.
The preferred ammoniacal liquor of alkali, sodium hydroxide or potassium hydroxide.
Alcohol particular methanol or ethanol.
More preferably the preparation method is as follows:
1, under the room temperature, takes by weighing proper amount of surfactant and place round-bottomed flask, add successively in the aqueous solution of deionized water, methyl alcohol and sodium hydroxide, under 20-60 ℃, be stirred to make it to dissolve fully and obtain transparent settled solution, reduce to room temperature;
2, respectively with amine propyl-triethoxysilicane and 1,2-two (triethoxy is silica-based) ethane is added drop-wise in the above-mentioned reaction solution, at room temperature stirs 1-6 hour;
3, above-mentioned reaction solution is transferred in the poly-tetrafluoro reactor, left standstill hydro-thermal reaction 5-30 hour at 50-120 ℃;
4, filter, use the deionized water thorough washing, 90 ℃ of constant pressure and dries;
5, remove template with hydrochloric ethanolic soln, 90 ℃ of constant pressure and dries promptly.
The advantage of hybrid ordered mesoporous silica gel of the present invention is:
1, spheroidal particle smooth surface, and particle diameter is even, sees Fig. 1 and Fig. 2, has high-specific surface area and highly ordered mesosize pores passage, sees Fig. 3 to Fig. 6.
2, good stability: have the performance of very high acid-fast alkali-proof, not only can be directly as liquid chromatography stuffing, its pendant amine propyl group is an active function groups, can modify for next step derivatize to facilitate.The hybrid ordered mesoporous silica gel of the present invention's preparation dashed 240 hours at the flow velocity of 50mM triethylamine solution (pH=10) with 1ml/min, it still is original more than 95% that post is imitated, and common amine propyl group mesoporous silica gel dashes after 10 hours under these conditions, and post is imitated and dropped to original 50%.
3, water-tolerant:, be that certain positive effect is all being arranged aspect economy or the environmental protection in the medium-term and long-term use of the flow phase system of high water ratio.The hybrid ordered mesoporous silica gel of the present invention preparation flow velocity with 1ml/min under the moving phase condition of methanol=10/90 (v/v) dashed 500 hours, and it still is original more than 95% that post is imitated.
4, following table is the comparison of hybrid ordered mesoporous silica gel of the present invention and common silica gel
5, post forces down: have the mesoporous passage of high-sequential, can accelerate mass transfer, press thereby reduce post.The results are shown in Figure 7,, when flow velocity is 5ml/min, adopt the hybrid mesoporous silica gel self-control of amine propyl group of the present invention post post pressure that 18MPa is only arranged, and commercially available nh 2 column has reached this pressure at flow velocity 1.5ml/min when moving phase is methanol=50/50 (v/v).This shows, as the chromatographic stationary phase, be applicable to the real-time analysis under the high flow rate with hybrid ordered mesoporous silica gel of the present invention.
6, separation efficiency is good: adopt the amine propyl group hybrid ordered mesoporous silica gel and the commercially available nh 2 column of the present invention's preparation to contrast, the mixing solutions of separation of methylbenzene, biphenyl and three kinds of materials of anthracene, method: high performance liquid chromatograph, UV-detector, absorbing wavelength 254nm, moving phase is methanol=50/50 (v/v), flow velocity 1ml/min.The results are shown in Figure 8,1 is toluene among Fig. 8, the 2nd, and biphenyl, the 3rd, anthracene can be realized these 3 kinds of compounds are separated fully as chromatographic column from the visible amine propyl group hybrid ordered mesoporous silica gel of the present invention of Fig. 8, and separation performance is better than commercially available nh 2 column.
Description of drawings
Fig. 1 and Fig. 2 are the scanning electron microscope pictures of amine propyl group hybrid ordered mesoporous silica gel of the present invention
Fig. 3 is the transmission electron microscope photo of amine propyl group hybrid ordered mesoporous silica gel of the present invention
Fig. 4 is the powder x-ray diffraction collection of illustrative plates of amine propyl group hybrid ordered mesoporous silica gel of the present invention
Fig. 5 is the nitrogen adsorption-desorption collection of illustrative plates of amine propyl group hybrid ordered mesoporous silica gel of the present invention
Fig. 6 is the pore size distribution curve of amine propyl group hybrid ordered mesoporous silica gel of the present invention
Fig. 7 is the flow velocity of amine propyl group hybrid ordered mesoporous silica gel chromatograph post of the present invention and the relation that post is pressed
Fig. 8 is the chromatographic fractionation figure of amine propyl group hybrid ordered mesoporous silica gel of the present invention to toluene, biphenyl and anthracene
Embodiment
Synthesizing of amine propyl group hybrid ordered mesoporous silica gel
Under the room temperature, take by weighing 1.23gN-trimethylammonium octadecyl ammonium chloride and place the 100ml round-bottomed flask, add successively deionized water 24.0ml, methyl alcohol 19.1ml and sodium hydroxide solution (0.66M, 14.0ml), constantly vigorous stirring makes it to mix, and obtains clear solution.Under vigorous stirring, add 1 rapidly, 2-two (triethoxy is silica-based) ethane 1.50ml and amine propyl-triethoxysilicane 0.35ml, at room temperature continue to stir 5 hours, then reaction solution is transferred in the poly-tetrafluoro reactor in 90 ℃ and left standstill 21 hours, filter, use the deionized water thorough washing, 90 ℃ of constant pressure and dries 10 hours, obtain amine propyl group hybridisation silica gel, this material has the spherical morphology of homogeneous grain diameter, sees Fig. 1 and Fig. 2.Its transmission electron microscope picture is seen Fig. 3, and visible duct distributes in order.Its powder x-ray diffraction collection of illustrative plates is seen Fig. 4.Its nitrogen adsorption-desorption collection of illustrative plates is seen Fig. 5, has typical IV curve, and it is mesoporous to prove that it has.Its pore size distribution curve is seen Fig. 6, and Fig. 6 proves that its aperture is concentrated and is distributed in 2.9nm, between the 1.7-3.0nm.
Synthesizing of amine propyl group hybrid ordered mesoporous silica gel
Under the room temperature about 25 ℃, take by weighing 1.47g N-trimethylammonium octadecyl ammonium chloride and place the 100ml round-bottomed flask, (0.66M, 17.0ml) constantly vigorous stirring makes it to mix, and obtains clear solution to add deionized water 28.8ml, methyl alcohol 22.8ml and sodium hydroxide solution successively.Under vigorous stirring, add 1 rapidly, 2-two (triethoxy is silica-based) ethane (1.44ml) and amine propyl-triethoxysilicane 0.66ml, at room temperature continue to stir 4 hours, then reaction solution is transferred in the poly-tetrafluoro reactor and left standstill 16 hours in 120 ℃, filter, use the deionized water thorough washing, 90 ℃ of constant pressure and dries 10 hours, obtain amine propyl group hybridisation silica gel, this material has the spherical morphology of homogeneous grain diameter.
Template is removed in solvent extraction
Taking by weighing the spherical amine propyl group of 0.5g embodiment 2 synthetic hybrid ordered mesoporous silica gel raw product respectively is suspended in the 150ml acidic ethanol (the 200ml dehydrated alcohol contains 3ml 36% concentrated hydrochloric acid), stirring reaction is 10 hours under the room temperature, filter, use the dehydrated alcohol thorough washing, 90 ℃ of constant pressure and dries; Repeat this operation once, make amine propyl group hybrid ordered mesoporous silica gel.
Get the amine propyl group hybrid ordered mesoporous silica gel of embodiment 3 preparation, adopt the homogenate method to load that (50mm * 4.6mm, I.D.), dress column pressure is 35MPa, and adopts this self-control post to carry out chromatographic property and test, and the results are shown in Figure 7 and Fig. 8 in the stainless steel column jecket.
Claims (7)
1. hybrid mesoporous orderly silica gel, it is characterized in that: the surface of hybrid mesoporous orderly silica gel and the hydroxyl of silicon atom bonding are substituted by the amine propyl group, described hybrid mesoporous orderly silica gel be to use ethylene group hydridization, the ethylene group charge capacity of heterozygosis is 4～10mmol/g in the hybrid mesoporous orderly silica gel skeleton, and described hybrid mesoporous orderly silica gel is spheroidal particle.
2. the hybrid mesoporous orderly silica gel of claim 1 is characterized in that: hybrid mesoporous silica gel bonded in order amine propyl group charge capacity is 0.01～4 μ mol/m
2
3. the hybrid mesoporous orderly silica gel of claim 1, it is characterized in that: described hybrid mesoporous orderly silica gel has orderly duct, and the duct is between 2-10nm.
4. the preparation method of each hybrid mesoporous orderly silica gel in the claim 1 to 3, comprise: by amine propyl-triethoxysilicane and 1,2-two (triethoxy is silica-based) ethane is as the silicon source, with alkali as hydrolyst, as template, is organic additive with alcohol with tensio-active agent, makes crude product through hydrothermal synthesis method one step copolycondensation, remove template with hydrochloric ethanolic soln, drying is promptly made.
5. the preparation method of claim 4, wherein alkali is ammoniacal liquor, sodium hydroxide or potassium hydroxide; Alcohol is methyl alcohol or ethanol; Surfactant structure is the quaternary ammonium salt shown in following:
R wherein
1, R
2, R
3And R
4Independently be selected from C respectively
1-C
22A kind of in the alkyl, and R
1, R
2, R
3And R
4In have one at least for C
12-C
22Alkyl; X is a halogen.
6. the preparation method of claim 4, amine propyl-triethoxysilicane wherein: 1,2-two (triethoxy is silica-based) ethane: tensio-active agent: alkali: alcohol: the mol ratio of water is 0.1～0.6: 0.9～0.4: 0.4～0.9: 1.0～3.0: 30～150: 300～500.
7. each hybrid mesoporous orderly silica gel is used for the purposes of preparative chromatography stationary phase in the claim 1 to 3.
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| CN102247821B (en) * | 2010-05-21 | 2013-06-26 | 月旭材料科技(上海)有限公司 | High pH tolerance chromatographic filler and preparation method thereof |
| CN102241823B (en) * | 2011-04-29 | 2012-10-10 | 中国药科大学 | Binaphthylamine derivative hybrid mesoporous silica gel chiral stationary phase |
| CN102276840B (en) * | 2011-05-06 | 2012-08-01 | 中国药科大学 | Camphor sulfonamide doped ethane bridge bond spherical mesoporous silica gel |
| CN104138751A (en) * | 2013-05-09 | 2014-11-12 | 中国药科大学 | Chiral core-shell chromatography stationary phase and preparation method |
| CN105080517A (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 | Hybrid mesoporous silica gel matrix coated type polysaccharide chiral stationary phase and preparation method therefor |
| CN105233811B (en) * | 2015-10-16 | 2018-03-09 | 苏州大学 | A kind of bonding type chromatographic column fixed phase and preparation method thereof |
| CN113797903A (en) * | 2020-06-12 | 2021-12-17 | 江苏汉邦科技有限公司 | Preparation method of hybrid silica gel chromatographic packing |
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