CN104084178A - Stationary phase of POSS hybrid capillary monolithic column, and preparation method thereof - Google Patents
Stationary phase of POSS hybrid capillary monolithic column, and preparation method thereof Download PDFInfo
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Abstract
The invention provides a stationary phase of a POSS hybrid capillary monolithic column, and a preparation method thereof. A porous POSS hybrid capillary monolithic column is prepared based on a thiol-ene click chemistry reaction by using alkenyl-containing POSS as functional monomers and a thiol compound as a cross-linking agent under co-presence of an initiator and a pore-foaming agent. A preparation process of the POSS hybrid capillary monolithic column is simple and mild in reactions, and can select different alkenyl POSS monomers and thiol cross-linking agents according to different applications to prepare a corresponding stationary phase of the porous POSS hybrid capillary monolithic column. The POSS hybrid capillary monolithic column prepared by the method has the advantages of good selectivity, high column efficiency, wide pH adaptive range and wide application range. The stationary phase can be used as the stationary phase of high performance liquid chromatography or capillary electrochromatography, is suitable for rapid separation and analysis of neutral, acid and alkaline organic compounds, and has very good application potentials in the field of separation science.
Description
Technical field
The present invention relates to chromatographic stationary phases, specifically a kind of method that adopts sulfydryl-alkene clicking chemistry technology to prepare the fixing phase of POSS hydridization capillary monolithic column.
Background technology
Polyhedron oligomerization sesquialter silane (polyhedral oligomeric silsequioxane, POSS) is the compound of a cage-like shape, and the core being made up of silicon and oxygen atom is contained in inside; That to meet experience structure formula be R to a class
n(SiO
1.5)
ncompound, wherein R represents a series of organic functional group, n is more than or equal to 4 even number.POSS reagent is considered to minimum hydridization silica particles, and its size, at 1～3nm, can be incorporated in conventional organic polymer by the method for copolymerization, grafting or mixing, can effectively improve mechanical strength and the heat endurance of polymer.In recent years, the report of the existing pertinent literature of the application study of POSS aspect monolithic column stationary phase, as (Minghuo Wu, Ren ' an Wu, Ruibing Li, Hongqiang Qin, Jing Dong, Zhenbin Zhang, Hanfa Zou. such as Wu
anal. Chem.2010,82,5447-5454) taking POSS as crosslinking agent, N-(2-(methacryloxypropyl) ethyl)-dimethyl stearyl bromine (MDOAB) is organic monomer, heat causes radical polymerization and has prepared poly (MDOA-co-POSS) hydridization capillary monolithic column, and is applied to the chromatography of little molecule and large biological molecule; (Hui Lin, Junjie Ou, Zhenbin Zhang, Jing Dong, the Hanfa Zou. such as Lin
chem. Commun. 2013,49
,231-233) taking POSS as monomer, diamine compounds is crosslinking agent, prepares POSS hydridization capillary monolithic column by ring-opening polymerization, is applied to capillary liquid chromatography analysis.At present, the research of POSS aspect chromatographic stationary phases has obtained larger success, has widened its range of application in separation science field.
Click chemistry is described as chemical reaction process simple as clicking the mouse, efficient, general visually, it mainly has following characteristics: reaction raw materials is easy to get, react very reliable, insensitive to oxygen, water, product stereoselectivity is good, productive rate is high, post-reaction treatment and product separation are simple and convenient, and byproduct of reaction is environmentally friendly.In recent years, click chemistry has caused that in preparative chromatography parting material field people study interest greatly.The reaction of sulfydryl-alkene clicking chemistry is a kind of novel click chemistry reaction, does not need to use metallic copper to make catalyst, has a good application prospect.Existing more bibliographical information employing sulfydryl-alkene clicking chemistry, prepare organic-inorganic hybrid monolithic capillary column (Yixuan Liu, Yingzhuang Chen, Huihui Yang by " one kettle way " or " two step method ", Lihua Nie, Shouzhuo Yao.
j. Chromatogr. A, 2011,1218,7982-7988; Ming-Luan Chen, Jun Zhang, Zheng Zhang, Bi-Feng Yuan, Qiong-Wei Yu, Yu-Qi Feng.
j. Chromatogr. A2013,1284,118-125; Yongqin Lv, Zhixing Lin, Frantisek Svec.
analyst2012,137,4114-4118; Inga Tijunelyte, Julien Babinot, Mohamed Guerrouache, Gintaras Valincius, Benjamin Carbonnier.
polymer2012,53,29-36), the organic-inorganic hybrid integral post making has had the advantage of organic whole post and monolithic silica column concurrently, has the advantages such as the wide pH scope of application, good permeability, mechanical stability and solvent resistance.But " one kettle way " the alternative hydrophily alkenyl monomer kind based on sulfydryl-alkene clicking chemistry is less, " two step method " complex operation, the reaction time is long, is seriously restricting the popularization of the method.
Summary of the invention
The object of this invention is to provide a kind of method that adopts sulfydryl-alkene clicking chemistry technology to prepare the fixing phase of high performance POSS hydridization capillary monolithic column, prepare that a kind of separating property is good, post effect is high, the pH scope of application is wide and be widely used and novel chromatographic stationary phases that cost is low.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for the fixing phase of POSS hydridization capillary monolithic column, comprises the steps:
(1) by thiazolinyl POSS monomer, dimercaptan crosslinking agent, initator is dissolved in binary pore-foaming agent solvent, and normal temperature sonic oscillation 10 min make it fully dissolve and mix, and obtain prepolymerization liquid;
(2) step (1) gained prepolymerization liquid is injected in the quartz capillary of vinyl functionalization, sealing is placed on reaction in thermostat water bath, after question response completes, rinse and remove pore-foaming agent and unreacted reactant with methyl alcohol or acetonitrile again, obtain the fixing phase of POSS hydridization capillary monolithic column.
Described thiazolinyl POSS function monomer is the cage type mixture (n=8 that POSS-methacryl replaces, 10,12, POSS-MA), eight vinyl-POSS or POSS-(1-propyl group methacrylate)-seven isobutyl groups replace (Bu-POSS);
Described dimercaptan crosslinking agent be BDO two (mercaptoacetates) (BMAB), 1,6-ethanthiol, 1, pungent two mercaptan of 8-, 1,10-mercaptan in the last of the ten Heavenly stems two, 1,12-, 12 mercaptan or 1,16-, 16 mercaptan;
Described initator is azodiisobutyronitrile (AIBN);
Described binary pore-foaming agent is toluene-lauryl alcohol, cyclohexanol-lauryl alcohol, propyl alcohol-positive ten alcohol, the tert-butyl alcohol-positive ten alcohol and the tert-butyl alcohol-PEG400, and the mass ratio of two kinds of pore-foaming agents is 0.4～0.8:1.
Reactant ratio described in step (1) is: 9 ~ 19% (w/w) thiazolinyl POSS, 1 ~ 7% (w/w) dimercaptan, 77 ~ 87% (w/w) pore-foaming agent, 1 ~ 4% AIBN (w/w accounts for total monomer content).
The described polymeric reaction temperature of step (2) is 50 ~ 60 DEG C of water-baths, and the reaction time is 8 ~ 24h.
The present invention has the following advantages:
The preparation method of the fixing phase of POSS hydridization capillary monolithic column provided by the invention have preparation process simple, fast, favorable reproducibility and the life-span long, reacting a step by sulfydryl-alkene clicking chemistry completes, original position preparation be can realize, capillary liquid chromatography, capillary electric chromatogram and conventional high performance liquid chromatography are applicable to.
2. POSS hydridization capillary monolithic column provided by the invention is fixed and is had mutually good separating property.Can under simple chromatographic condition, meet rapidly and efficiently separating of neutrality, acidity and alkali compounds, and there is the advantages such as post effect is high, the pH scope of application is wide.In addition, this monolithic column stationary phase to the separation of alkali compounds without obvious conditions of streaking.
3. the prepared POSS hydridization capillary monolithic column of the present invention is examined or check through chromatogram, and its feature showing is consistent with the chromatogram retention properties of sulfydryl crosslinking agent organic functional group used.In this experiment, select different sulfydryl crosslinking agents, adopt this preparation method all can obtain the POSS hybrid integral post of porous, and all show with added sulfydryl crosslinking agent and have the consistent chromatographic characterization of functional group.
Brief description of the drawings
Fig. 1 be the monolithic column stationary phase in embodiment 1 scanning electron microscope (SEM) photograph A 3000 × B 20000 ×;
Fig. 2 is the chromatographic fractionation figure to 5 kinds of benzene compounds in embodiment 3;
Fig. 3 is the chromatographic fractionation figure to 5 kinds of aromatic amine compounds in embodiment 4.
Detailed description of the invention
The present invention prepares a kind of fixing phase of POSS hydridization capillary monolithic column that selectively good, post effect is high, the pH scope of application is wide and have wide range of applications that has in conjunction with the good characteristic of POSS and sulfydryl-alkene clicking chemistry.Can be used as capillary liquid chromatography or capillary electric chromatogram fixing for neutrality, the quick compartment analysis of acidity and alkali compounds, has good application potential in separation science field.
Below by specific embodiment, technical scheme of the present invention is described further, but the present invention is not limited only to this.The raw material that the present invention adopts can be buied in market, or available methods known in the art are synthetic.
Embodiment 1
A preparation method for the fixing phase of POSS hydridization capillary monolithic column, comprises the steps:
(1) vinyl functionalization
Quartz capillary is passed into 0.1mol/L HCl (30min) successively, deionized water (30min), 1 mol/L NaOH (3h), deionized water (30min), methyl alcohol (30min), logical N at 180 DEG C
2dry 1h.Then will
γthe methanol solution (v/v volume ratio is 1:1) of-methacrylic acid oxygen propyl trimethoxy silicane (γ-MAPS) is injected in the capillary of handling well, in 60 DEG C of water-baths, reacts 24h.Reacted rear with washed with methanol capillary column 30min to go out unreacted material, be then placed in 70 DEG C of gas chromatograph column oven nitrogen blowing 3h, obtain the capillary of vinyl functionalization, two sections of sealings are for subsequent use.
(2) preparation of POSS hybrid integral post
By 50mg POSS-MA, 12.6mg 1,4-butanediol two (mercaptoacetates) (BMAB), 1mg AIBN is dissolved in the mixed solution of 110mg toluene and 200mg lauryl alcohol, normal temperature sonic oscillation 10 min make it fully dissolve and mix, and obtain prepolymerization liquid.Then this pre-gathering solutions is injected to above-mentioned vinylated capillary, two ends are tamping with silica gel rubber stopper, be placed in 55 DEG C of constant temperature water baths and react 12h.After having reacted, use washed with methanol capillary column, to remove residual reaction reagent, make POSS-MA-BMAB hydridization capillary monolithic column, its environmental scanning electronic microscope is shown in Fig. 1
Embodiment 2
With 13.0 mg 1, pungent two mercaptan of 8-replace BMAB, are undertaken by the step of embodiment 1, make octyl group POSS hybrid integral post.
Application example:
The POSS-MA-BMAB capillary monolithic column of preparing by EXAMPLE l, intercepting total length is 53cm, effective length is 30cm, under capillary liquid chromatography pattern, with acetonitrile: water (75/15, v/v), for mobile phase, detects under wavelength 214nm condition, 5 kinds of alkylbenzenes are separated, and corresponding peak is t respectively
0thiocarbamide 1. benzene, 2. toluene, 3. ethylbenzene, 4. propyl benzene, 5. butylbenzene.Its spectrogram as shown in Figure 2.
The POSS-MA-BMAB capillary monolithic column of preparing by EXAMPLE l, under capillary liquid chromatography pattern, with acetonitrile: water (55/45, v/v), for mobile phase, detects under wavelength 214nm condition, and 5 kinds of alkaline amino benzenes compounds are separated.Corresponding peak is 1. o-phenylenediamines respectively, 2. aniline, 3. para-totuidine, 4. benzidine, 5. 2,4-dinitroaniline, 6. alpha naphthylamine.Its spectrogram as shown in Figure 3.
Claims (9)
1. a preparation method for the fixing phase of POSS hydridization capillary monolithic column, is characterized in that: described method comprises the steps:
(1) by thiazolinyl POSS function monomer, dimercaptan crosslinking agent, initator is dissolved in binary pore-foaming agent mixed solution, and normal temperature sonic oscillation 10 min make it fully dissolve and mix, and obtain prepolymerization liquid;
(2) step (1) gained prepolymerization liquid is injected in the quartz capillary of vinyl functionalization, sealing is placed on isothermal reaction in thermostat water bath, after question response completes, rinses and removes pore-foaming agent and unreacted reactant again with methyl alcohol or acetonitrile.
2. preparation method as claimed in claim 1, it is characterized in that: described in step (1), reactant ratio is: 9 ~ 19% (w/w) thiazolinyl POSS, 1 ~ 7% (w/w) dimercaptan, 77 ~ 87% (w/w) pore-foaming agent, 1 ~ 4% AIBN (w/w accounts for total monomer content).
3. preparation method according to claim 1, it is characterized in that: described thiazolinyl POSS function monomer is the cage type mixture (n=8 that POSS-methacryl replaces, 10,12, POSS-MA), eight vinyl-POSS or POSS-(1-propyl group methacrylate)-seven isobutyl groups replace (Bu-POSS).
4. preparation method according to claim 1, it is characterized in that: described dimercaptan crosslinking agent is 1,4-butanediol two (mercaptoacetates) (BMAB), 1,6-ethanthiol, 1, pungent two mercaptan of 8-, 1,10-mercaptan in the last of the ten Heavenly stems two, 1,12-12 mercaptan or 1,16-, 16 mercaptan.
5. preparation method according to claim 1, is characterized in that: described initator is azodiisobutyronitrile (AIBN).
6. preparation method according to claim 1, is characterized in that: described binary pore-foaming agent is toluene-lauryl alcohol, cyclohexanol-lauryl alcohol, propyl alcohol-positive ten alcohol, the tert-butyl alcohol-positive ten alcohol and the tert-butyl alcohol-PEG400.
7. preparation method according to claim 6, is characterized in that: the mass ratio of described two kinds of pore-foaming agents is 0.4～0.8:1.
8. preparation method according to claim 1, is characterized in that: isothermal reaction described in step (2) is 50 ~ 60 DEG C of water-baths, and the reaction time is 8 ~ 24h.
9. the fixing phase of POSS hydridization capillary monolithic column of preparing by the preparation method one of claim 1-8 Suo Shu.
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| CN106693931A (en) * | 2017-02-27 | 2017-05-24 | 福州大学 | Glucosamine oligosaccharide-functionalized hybrid silica monolithic column and preparation method |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306263A (en) * | 2008-01-22 | 2008-11-19 | 广西师范大学 | Alkylamine silica gel capillary monolithic column and preparation method and use thereof |
| EP2368894A1 (en) * | 2010-03-01 | 2011-09-28 | Evonik Degussa GmbH | Polysilsesquioxane (POSS)-linked Imidazole-based Carbene and Phosphine Ligands for Transition Metal Catalysts |
| CN102225249A (en) * | 2011-04-06 | 2011-10-26 | 福州大学 | Preparation method of organic-inorganic hybrid monolithic capillary column |
| CN102500346A (en) * | 2011-11-03 | 2012-06-20 | 广西师范大学 | Preparation method for ionic liquid silica gel capillary monolithic column stationary phase |
| CN102872613A (en) * | 2012-09-21 | 2013-01-16 | 武汉大学 | Preparation method of organic-inorganic hybridization monolithic column |
| US20140128495A1 (en) * | 2012-11-08 | 2014-05-08 | New Sitech Llc | Organic-inorganic hybrid material compositions and polymer composites |
-
2014
- 2014-06-23 CN CN201410282354.XA patent/CN104084178B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306263A (en) * | 2008-01-22 | 2008-11-19 | 广西师范大学 | Alkylamine silica gel capillary monolithic column and preparation method and use thereof |
| EP2368894A1 (en) * | 2010-03-01 | 2011-09-28 | Evonik Degussa GmbH | Polysilsesquioxane (POSS)-linked Imidazole-based Carbene and Phosphine Ligands for Transition Metal Catalysts |
| CN102225249A (en) * | 2011-04-06 | 2011-10-26 | 福州大学 | Preparation method of organic-inorganic hybrid monolithic capillary column |
| CN102500346A (en) * | 2011-11-03 | 2012-06-20 | 广西师范大学 | Preparation method for ionic liquid silica gel capillary monolithic column stationary phase |
| CN102872613A (en) * | 2012-09-21 | 2013-01-16 | 武汉大学 | Preparation method of organic-inorganic hybridization monolithic column |
| US20140128495A1 (en) * | 2012-11-08 | 2014-05-08 | New Sitech Llc | Organic-inorganic hybrid material compositions and polymer composites |
Non-Patent Citations (1)
| Title |
|---|
| 欧俊杰 等: "含多面体低聚倍半硅氧烷杂化毛细管整体柱的制备及修饰", 《色谱》 * |
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Inventor after: Ye Fanggui Inventor after: Shen Shufen Inventor after: Zhang Cong Inventor after: Zhao Shulin Inventor before: Ye Fanggui Inventor before: Shen Shufen Inventor before: Zhang Cong Inventor before: Zhao Shulin |
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