CN105536294A - Organic substrate capillary tube monolithic column and preparation method of organic substrate capillary tube monolithic column - Google Patents
Organic substrate capillary tube monolithic column and preparation method of organic substrate capillary tube monolithic column Download PDFInfo
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- CN105536294A CN105536294A CN201610056707.3A CN201610056707A CN105536294A CN 105536294 A CN105536294 A CN 105536294A CN 201610056707 A CN201610056707 A CN 201610056707A CN 105536294 A CN105536294 A CN 105536294A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/84—Capillaries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/86—Sorbents applied to inner surfaces of columns or capillaries
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention discloses an organic substrate capillary tube monolithic column and a preparation method of the organic substrate capillary tube monolithic column. The preparation method sequentially comprises preparation of a polymerization solution, pre-treatment of a capillary tube, and polymerization preparation. The polymerization preparation specifically comprises the following steps: filling the pre-treated capillary tube with a polymerization solution until the polymerization solution in the pre-treated capillary tube is at 10cm, and carrying out microwave polymerization for 15 minutes under the conditions that the temperature is 80 DEG C and the power is 700W. According to the organic substrate capillary tube monolithic column prepared by the method, the porosity is 0.53 to 0.57. A microwave polymerization manner is used for replacing a traditional external heating manner in a monolithic column preparation process, and polymerization reaction time can be shortened for hundreds of times, so that the efficiency of producing the monolithic column is greatly improved, and common chromatography workers can possibly prepare the satisfied monolithic columns within a few minutes.
Description
Technical field
The present invention relates to Micro-Column Separation technology, be specifically related to a kind of organic substrate capillary monolithic column and preparation method thereof.
Background technology
Capillary liquid chromatography is a kind of Micro-Column Separation technology between conventional liquid phase chromatogram and micro-fluidic chip.Due to its institute the sample that consumes and mobile phase few, consumables cost is low, advantages of environment protection, has become a kind of Micro-Column Separation analysis means of fast development in recent years.Preparative separation chromatographic isolation bed of good performance is the core of this technology, research preparation a kind of good solution beyond doubt of integral material.
From the classification of Monolithic Columns, organic polymer integral post, monolithic silica column and organic-inorganic hybrid material integral post can be divided into.The preparation of Organic Polymer Monolithic Columns is injected in capillary void column by monomer mixture and pore-foaming agent, causing through heat, ultraviolet light, microwave or gamma-rays makes monomer mixture be polymerized in capillary, then with the monomer that suitable solvent (methyl alcohol, ethanol or acetone and other organic solvent) removes the pore-foaming agent in cylinder and remains.In polyblend, add specific monomer or carry out chemical modification after polymerisation and can improve the selective of chromatographic column.This kind of integral post because of selection extensively, the advantage such as pH value range of application is wide and preparation is simpler compared with monolithic silica column.(these awards are called " neoteric Oscar " and " Nobel Prize in application " by insider) can have been gone up since priority obtains " PtticonEditors " best product gold medal and " R & DWorldAward " in the international chromatogram that the U.S. holds from the liquid phase chromatography integral post of calendar year 2001 Merck KGaA company development, this new technology to chromatographic theory and application, and even all creates great impact to whole analysis field.A lot of personage thinks that overall liquid-phase chromatographic column and capillary monolithic electric chromatographic column are expected to replace traditional graininess liquid-phase chromatographic column and electric chromatographic column in the following several years comprehensively in the industry, will bring the new revolution of the Theory and applications in chromatographic isolation field.
The research work of current integral post concentrates on the application aspect of Development of Novel Monolithic Columns and expansion integral post mostly, and relatively less to the research of integral post preparation method.Organic polymer integral post preparation method conventional both at home and abroad all adopts the mode of uv photopolymerization and thermal polymerization substantially.In principle, adopt gamma-rays, X-ray, ultraviolet, infrared, microwave even ultrasonic wave carry out radiation or irradiation original position in stainless steel tube or capillary to carry out organic polymer be possible.
Microwave be a kind of in heating, have that firing rate is fast, homogeneous heating be without thermograde, without features such as hysteresis effects.The acceleration key factor of microwave to chemical reaction is heat the selection of polar organic matter, i.e. the thermal effect of microwave.Other viewpoint thinks that microwave is very complicated to chemical reaction effect, is that reactant molecule absorbs microwave energy on the one hand, improves molecular motion velocities, cause molecular motion disorderly and unsystematic, cause the increase of entropy; Microwave is to the effect of polar molecule in addition, forces it to move according to electromagnetic field effect mode, result in the increase of entropy, and therefore microwave can not only describe with microwave thermal effect the mechanism of action of chemical reaction.
General microwave causes employing common microwave stove, although preparation is efficient, reappearance is poor, even if the integral post post effect that identical experiment condition prepares also exists larger difference.
Summary of the invention
In order to solve the deficiencies in the prior art, the invention provides a kind of organic substrate capillary monolithic column and preparation method thereof.
Technical scheme of the present invention is: a kind of preparation method of organic substrate capillary monolithic column, comprise the preparation of polymer fluid successively, pretreatment and polymerization preparation, described polymerization preparation is specially: 10cm in the capillary after polymer fluid is filled with pretreatment, temperature be 80 DEG C, power be 700W condition under Microwave Emulsifier-Free Polymerization 15min.
Further improvement of the present invention comprises:
The preparation of described polymer fluid specifically comprises: be dissolved in by MAA and the 1mL of 4mL olivetol in 8mL toluene and 2mL lauryl alcohol, first ultrasonic process 30min, after be cooled to room temperature, add ethylene glycol dimethacrylate and the 0.04g azodiisobutyronitrile of 20mmol again, after mixing, logical nitrogen gets rid of the oxygen dissolved in solution.
Described pretreatment specifically comprises: the NaOH using 1M successively, H
2the HCL solution of O, 0.1M rinses 0.5h; After recycling methanol solution rinses 0.5h, nitrogen dries up; By γ-methacryloxypropyl trimethoxy silane and methyl alcohol according to the mixed mixed solution of volume ratio 1:1, inject in capillary with syringe, and the two ends rubber stopper of capillary is sealed, be placed in 60 DEG C of water-baths and react 12h; Capillary nitrogen after alkenyl dries up stand-by.
Another object of the present invention is to provide a kind of organic substrate capillary monolithic column, obtain according to above-mentioned method.
Described a kind of organic substrate capillary monolithic column, its porosity is 0.53-0.57.
The present invention adopts Microwave Emulsifier-Free Polymerization mode to substitute traditional external heating mode in integral post manufacturing process, can the shortening polymerization reaction time of hundreds of times, thus greatly improve the efficiency manufacturing integral post, making common chromatogram worker all can prepare the integral post wanted within a few minutes becomes possibility.
The capillary monolithic column that so suitable controlled microwave reaction condition prepares stability and high efficiency is exactly main innovate point of the present invention.The present invention has prepared methacrylic acid-ethylene glycol dimethacrylate integral post by temperature control microwave, and adopts the capillary miniflow liquid chromatographic system of self assembly to carry out chromatographic evaluation to it, adopts ESEM to carry out Morphological Characterization to integral material.Experimental result shows, the integral post prepared by this method can baseline separation thiocarbamide, phenanthrene, naphthalene, anthracene four kinds of materials, and the minimum theoretical plate height of anthracene reaches 4.8 μm; The RSD repeating 7 times under identical chromatographic conditions is 3.27%.Compared with the method for reacting with conventional microwave, the reaction condition of this method is controlled, and the capillary monolithic column favorable reproducibility of preparation, greatly improves reaction efficiency.
Temperature control microwave is adopted to substitute common microwave reaction synthesizer to prepare capillary monolithic column, effectively can control the reaction condition preparing integral post, thus greatly improve the efficiency of preparation integral post, make common chromatogram worker can prepare the integral post needed fast when condition is controlled.
Accompanying drawing explanation
Fig. 1 is temperature control and the contrastive colours spectrogram of not temperature control.
Fig. 2 a is capillary monolithic column prepared by the present invention.
Fig. 2 b is the partial enlarged drawing of Fig. 2 a.
Fig. 2 c is the partial enlarged drawing of Fig. 2 b.
Fig. 3 a is capillary monolithic column prepared by conventional microwave method.
Fig. 3 b is the partial enlarged drawing of Fig. 3 a.
Fig. 3 c is the partial enlarged drawing of Fig. 3 b.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is elaborated.
Experimental procedure
1. reagent: olivetol (Olivetol, 86.5%), toluene, lauryl alcohol, MAA (methacrylic acid), ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), azodiisobutyronitrile (azo-bis-isobutyl cyanide); Thiocarbamide (500ppm), naphthalene (500ppm), luxuriant and rich with fragrance (500ppm), anthracene (500ppm)
2. preparation process:
The preparation of 2.1 polymer fluids: 4mlMAA and 1ml olivetol is dissolved in 8ml toluene and 2ml lauryl alcohol, first ultrasonic 30min, after be cooled to room temperature, then add 20mmol ethylene glycol dimethacrylate and 0.04g azodiisobutyronitrile, after mixing, logical nitrogen is to get rid of the oxygen in solution.
2.2 pretreatments: (1) use 0.1MNaOH successively, H
2o, 0.1MHCL solution rinses 0.5h; (2) methanol solution rinses 0.5h, and nitrogen dries up; (3) by γ-methacryloxypropyl trimethoxy silane (γ-MAPS) and methyl alcohol mixed solution (γ-MAPS:CH3OH=1:1, v/v) inject in capillary with syringe, and the two ends rubber stopper of capillary is sealed, be placed in 60 DEG C of water-baths react 12h (4) alkenyl after capillary nitrogen dry up stand-by, (5) at room temperature dry up with nitrogen.
2.3 preparation process polymer fluid is filled with pretreatment after capillary 10cm, in microwave catalysis synthesizer, (parameters: temperature: 80 degree, power: 700W, polymerization time: 15min) is polymerized.
. experimental result
As shown in Figure 1, a: temperature control microwave (polymerization length: 7cm, polymerization temperature: 80 DEG C, polymerization time: 15.5min); B: conventional microwave (not temperature control) (polymerization length: 7cm, polymerization temperature: not temperature control, polymerization time: 15min)
Chromatographic condition: capillary: overall length=35cm; Overall column length=7.5cm; Effective length (from capillary inlet to detection window)=26.5cm; 100 μm of I.D.; 375 μm of O.D.
Experiment condition: flow velocity: 1mL/min; ACN:H
2o=50:50 (v/v), determined wavelength: 210nm, room temperature 25 DEG C.1: thiocarbamide, 2: phenanthrene, 3: naphthalene, 4: anthracene
Table 1 conventional microwave and temperature control microwave post are imitated and are contrasted
Imitate in correction data as can be seen from Fig. 1 temperature control and the contrastive colours spectrogram of not temperature control with table 1 conventional microwave and temperature control microwave post, capillary monolithic column post prepared by temperature control microwave method is imitated apparently higher than conventional microwave method, and it is narrower that chromatogram goes out peak-to-peak shape, and separating degree is also higher.
Table 2 conventional microwave and temperature control microwave porosity contrast
As can be seen from Table 2, integral post porosity prepared by temperature control microwave method is 0.5397, less than 0.7434 of conventional microwave.It is better than conventional microwave method that this also just explains the capillary monolithic column post effect why prepared by temperature control microwave method.Porosity is little, and the reserve capability of compound in integral post is just large.
Applicant has prepared methacrylic acid-ethylene glycol dimethacrylate integral post by temperature control microwave, and adopts the capillary miniflow liquid chromatographic system of self assembly to carry out chromatographic evaluation to it, adopts ESEM to carry out Morphological Characterization to integral material.Experimental result shows, the integral post prepared by this method can baseline separation thiocarbamide, phenanthrene, naphthalene, anthracene four kinds of materials, and the minimum theoretical plate height of anthracene reaches 4.8 μm; The RSD repeating 7 times under identical chromatographic conditions is 3.27%.Compared with the method for reacting with conventional microwave, the reaction condition of this method is controlled, and the capillary monolithic column favorable reproducibility of preparation, greatly improves reaction efficiency.
As can be seen from Electronic Speculum figure, the bulk polymerization of temperature control microwave is good, and be combined comparatively tight with capillary wall, do not have space, the electromicroscopic photograph that partial enlargement is 6000 times can be found out, integral material polymerization is more closely knit, and there are micropore and mesopore in centre by mobile phase.And on conventional microwave electromicroscopic photograph, between integral material and capillary, have larger space, be combined with capillary wall so not tight, partial enlarged drawing seen hole is larger.
More than show and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (5)
1. the preparation method of an organic substrate capillary monolithic column, it is characterized in that, comprise the preparation of polymer fluid successively, pretreatment and polymerization preparation, described polymerization preparation is specially: 10cm in the capillary after polymer fluid is filled with pretreatment, temperature be 80 DEG C, power be 700W condition under Microwave Emulsifier-Free Polymerization 15min.
2. the preparation method of a kind of organic substrate capillary monolithic column according to claim 1, it is characterized in that, the preparation of described polymer fluid specifically comprises: be dissolved in by MAA and the 1mL of 4mL olivetol in 8mL toluene and 2mL lauryl alcohol, first ultrasonic process 30min, after be cooled to room temperature, add ethylene glycol dimethacrylate and the 0.04g azodiisobutyronitrile of 20mmol again, after mixing, logical nitrogen gets rid of the oxygen dissolved in solution.
3. the preparation method of a kind of organic substrate capillary monolithic column according to claim 1, it is characterized in that, described pretreatment specifically comprises: the NaOH using 1M successively, H
2the HCL solution of O, 0.1M rinses 0.5h; After recycling methanol solution rinses 0.5h, nitrogen dries up; By γ-methacryloxypropyl trimethoxy silane and methyl alcohol according to the mixed mixed solution of volume ratio 1:1, inject in capillary with syringe, and the two ends rubber stopper of capillary is sealed, be placed in 60 DEG C of water-baths and react 12h; Capillary nitrogen after alkenyl dries up stand-by.
4. an organic substrate capillary monolithic column, is characterized in that, obtains according to the method described in any one of claim 1-3.
5. a kind of organic substrate capillary monolithic column according to claim 4, is characterized in that, its porosity is 0.53-0.57.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108479729A (en) * | 2018-03-22 | 2018-09-04 | 河南科技学院 | Application of the low temperature liquid metallic microspheres in preparing adsorbing separation and analyzing high-molecular porous material |
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| JP4266711B2 (en) * | 2003-05-30 | 2009-05-20 | 株式会社カナック | Method and apparatus for producing activated carbon by microwave heating |
| CN103071314A (en) * | 2011-10-25 | 2013-05-01 | 天津科技大学 | Preparation method for novel ionic liquid capillary monolithic column |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479729A (en) * | 2018-03-22 | 2018-09-04 | 河南科技学院 | Application of the low temperature liquid metallic microspheres in preparing adsorbing separation and analyzing high-molecular porous material |
| CN108479729B (en) * | 2018-03-22 | 2020-08-28 | 河南科技学院 | Application of low-temperature liquid metal microspheres in preparation of adsorption separation analysis high-molecular porous material |
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