WO2015111797A1 - Method for preparing organic monolith powder and organic monolith powder prepared thereby - Google Patents

Abstract

The present invention relates to a method for preparing an organic monolith powder and an organic monolith powder prepared thereby and, more specifically, to a method for preparing an organic monolith powder, the method comprising the steps of: mixing a functional monomer and a cross-linking monomer with a solvent to prepare a mixture solution, and removing oxygen in the mixture solution (step 1); mixing the mixture solution with a pore inducing material having a molecular weight of 20,000 to 1,000,000 and a polymerization initiator, followed by a polymerization reaction (step 2); and separating organic monolith from the mixture solution in which the polymerization reaction has been conducted in step 2 (step 3). The method for preparing an organic monolith powder according to the present invention uses the pore induction material having a molecular weight of 20,000 to 1,000,000, thereby preparing an organic monolith powder which has few meso-sized pores and a large total volume of macro-sized pores. Here, the macropores are stuck into a surface region of the monolith while being absent inside the monolith pores, and thus the material transfer rate is fast, and the flow of the charging solvent is fast and strong due to the monolith form, thereby improving charging efficiency and obtaining a maximally dense charging structure. Therefore, the use of the organic monolith powder as a stationary phase of chromatography can obtain excellent separation efficiency, which is similar to that of a 5 μm-silica powder with C18 attachment.

Description

 [Specification】

 [Name of invention]

 Manufacturing method of organic monolith powder and oil monolith powder manufactured according to this

 The present invention relates to a method for preparing an organic monolith powder and to an organic monolith powder prepared according to the present invention. Specifically, the present invention comprises macroporous pores by using a pore-forming material having a molecular weight of 20,000 to 1 million. The present invention relates to a method for preparing an organic monolith powder having excellent separation efficiency by having a large volume of pores and an organic monolith powder prepared accordingly.

 Background Art

<2> Monolith is a macropore (also known as a through-flow channel) with an organic or inorganic polymer in a 3 ^" dimensional body, having a diameter of 1 卿 or more, and mesopores less than 1 in diameter ( A monolith that is well made in metal or silica capillaries can be used for liquid chromatography, capillary electrochromatography, and solid phase extraction ^. commonly used as stationary phases in extract ions etc. Organic and monolithic studies are very extensive.

 <3>

 <4> Non-patent documents 1 to 7 disclose a bulk organic monolit, and non-patent documents 8 to 11 disclose a bulk inorganic monolit. However, research on powdered monolit is very limited.

 <5>

 On the other hand, Non-Patent Documents 12 to 18 and Patent Document 1 describe a method for producing a chromatographic stationary phase using powdered silica monolite.

In addition, Non-Patent Document 19 reports the world's first basic research using organic monolit powder as a low-cost chromatography stationary phase.

However, in Non-Patent Document 19, a good chromatographic separation efficiency of the monolithic powder was not produced, and the theoretical column number of the chromatography column (30 cm length) filled with the powder was about 4,000 at maximum. The results were well below the theoretical number of 10, 000-20, 000 of the column filled with the most commonly used C18 attached spherical porous silica (5 IM size) powder. <9>

 In addition, the pore size of the organic monolith powder obtained in the above study was suitable as 20-50 nm, but the total pore volume was only 0.02 mL / g, and the number of pores was increased to 0.5 mL / It was difficult to produce more than g.

<ιι> Organic monoliths are found to be very weak compared to silica monoliths, so when the total pore volume of mesopores is increased to some extent, the structure is very fragile and unbearable when powdered.

 <12>

 Therefore, while the present inventors are studying a method for preparing an organic monolith powder having excellent separation efficiency, the present inventors select macroporous materials having a large molecular size, but predominantly induce macropores by optimizing the molecular weight and the amount of use of the covalent materials. It was confirmed that the organic monolith powder having a high total pore volume and high strength can be prepared, thereby completing the present invention.

 <14>

 <15> 〈Previous Technical Documents〉

<16> <Patent Documents>

 (Patent Document 1) Korean Patent No. 10-1116566;

<18>^'<Non-PatentDocuments>

 (Non-Patent Document l ') Svec et al., J. Chromatogr. A 2000, 887, 3;

 (Non-Patent Document 2) Zou et al., J. Chromatogr. A 2002, 954, 5;

 <2i> (Non-Patent Document 3) Legido-Quigl ey et al., Electrophoresis 2) 3, 24, 917;

 (Non-Patent Document 4) Klodz et al., J. Chromatogr. A 2006, 1109, 51;

 (Non-Patent Document 5) Zhu et al., J. Sep. Sci. 2007, 30, 792;

 (Non-Patent Document 6) Aoki et al., J. Sep. Sci. 2009, 32, 341;

 (Non-Patent Document 7) Ni schang et al., Anal. Bioanal. Chem. 2010, 397, 953;

 (Non-Patent Document 8) Cabrera, J. Sep. Sci. 2004, 27, 843;

 (Non-Patent Document 9) Kato et al., J. Sep. Sci. 2005, 28, 1983;

 (Non-Patent Document 10) E 'Safty, J. Porous Mater. 2008, 15, 369;

 (Non-Patent Document 12) Wi stuba, J. Chromatogr. A 2010, 1217, 941;

 (Non-Patent Document 13) Ko et al., J. Chromatogr. A 2007, 1144, 269;

 <3i> (Non-Patent Document 14) Han et al., Bull. Korean Chem. Soc. 2008, 29, 2281;

(Non-Patent Document 15) Kim et al., Bul l. Korean Chem. Soc. 2009, 30, 722; (Non-Patent Document 16) Hwang et al., Bul l. Korean Chem. Soc. 2009, 30, 722;

 (Non-Patent Document 17) Lee et al., Bull. Korean Chew. Soc. ^, 2943, 2010;

 (Non-Patent Document 18) Al i et al., J. Chromatogr. A, 2013, 1303, 9;

 (Non-Patent Document 19) Chio et al., Bui 1. Korean Chem. Soc. 2013, 34, 291;

 <37>

 [Detailed Description of the Invention]

 [Technical problem]

 <38> The purpose of the present invention is

 It is to provide a method for producing an organic monolit powder.

 <40>

 <41> Another object of the present invention is

 It is to provide an organic monolith powder prepared according to the above production method.

<43>

 Technical Solution

 In order to achieve the above object, the present invention,

 <45> mixing a functional monomer, a crosslinking monomer, and a solvent to prepare a mixed solution, and removing oxygen in the mixture solution (step 1);

(46) mixing the covalent substances having a molecular weight of 20,000 to 1 million with a polymerization initiator and a polymerization initiator in the mixed solution, and then performing a polymerization reaction (step 2); And

 It provides a method for producing an organic monolith powder, comprising the step (step 3) of separating the organic monolith from the mixed solution subjected to the polymerization reaction in step 2.

 <48>

 In addition, the present invention,

 It provides an organic monolit powder prepared according to the above production method.

 <51>

 Advantageous Effects

 In the method for preparing the organic monolith powder according to the present invention, by using a pore-forming material having a molecular weight of 20,000 to 1 million, there are almost no meso-sized pores and a macro-sized organic monolith powder having a large total pore volume. It can be manufactured.

At this time, since the macropores exist in the form of a monolithic surface near the surface of the monolith without being present inside, the mass transfer rate is high, and the monolithic form allows the flow of the layered solvent to be fast and strong, thus providing good filling efficiency. Getting the most compact filling structure Excellent separation similar to that of C18-attached silica powder can be obtained. Efficiency can be obtained.

 <54>

 [Brief Description of Drawings]

 1 is a photograph of an organic monolit powder prepared in step 3 of Example 1 observed with a scanning electron microscope;

 FIG. 2 is a photograph of an organic monolit powder prepared in Step 3 of Example 1 observed with a transmission electron microscope; FIG.

 FIG. 3 is a graph showing a volume-based particle size distribution diagram of the organic monolit powder prepared in Step 3 of Example 1; FIG.

4 is a graph showing a pore size distribution of the organic monolit powder prepared in Step 3 of Example 1;

5 is a graph showing chromatograms obtained with the micro columns prepared in Examples 1, 2 and 3;

 Figure 6 is a graph showing the chromatogram obtained by the micro column prepared in Examples 1, 4, 5.

 <61>

 [Best form for implementation of the invention]

 <62> The present invention

 Mixing a functional monomer, a crosslinking monomer, and a solvent to prepare a mixed solution, and removing oxygen in the mixed solution (step 1);

Mixing the gas-covalent material having a molecular weight of 20,000 to 1 million and a polymerization initiator with the mixed solution, and then performing a polymerization reaction (step 2); And

 It provides a method for producing an organic monolith powder, comprising the step (step 3) of separating the organic monolith from the mixed solution subjected to the polymerization reaction in step 2.

 Hereinafter, a method for preparing an organic monolith powder according to the present invention will be described in detail for each step.

 <68>

In the method for preparing an organic monolith powder according to the present invention, step 1 is a step of preparing a mixed solution by mixing a functional monomer, a crosslinking monomer, and a solvent, and removing oxygen from the mixed solution. Specifically, the functional monomer and the crosslinking monomer are placed in a reaction vessel, and stirred with a solvent and heated to prepare a complete solution.

 <71>

 The mixed solution of Step 1 is based on 100 parts by weight of the solvent, the functional monomer 3 to

20 parts by weight and 5 to 20 parts by weight of crosslinking monomer may be included.

 If the mixed solution contains less than 3 parts by weight of the functional monomer with respect to 100 parts by weight of the solvent, there is a problem in that the monolit is not well formed in the subsequent step, and if it contains more than 20 parts by weight. There is a problem that too hard monolit is formed.

 In addition, when the mixed solution contains less than 5 parts by weight of the crosslinking monomer with respect to 100 parts by weight of the solvent, there is a problem in that the monolit is not well formed in a subsequent step, and when it contains more than 20 parts by weight. There is a problem that too hard monolit is formed.

 <75> '

Mixing of Step 1 may be performed for 10 minutes to 1 hour at a temperature of 50 to 80 ^° C.

 If the mixing of the step 1 is carried out at a temperature of less than 50 V, there is a problem that the subsequent polymerization reaction is not performed properly, if the mixing of the step 1 is carried out at a temperature of more than 80 seconds There is a problem of overheating due to the rapid progress of the polymerization reaction in the process.

 In addition, when the mixing of the step 1 is performed for less than 10 minutes, there is a problem that does not become a complete solution, and if it is performed for more than 60 minutes, there is a problem that energy is wasted.

 <79>

 After the preparation of the mixed solution of Step 1, oxygen in the mixed solution is removed.

 If the oxygen in the mixed solution is not removed, subsequent polymerization reactions cannot be performed smoothly.

 Removal of oxygen in the mixed solution may be carried out by purging with nitrogen, but the method of removing oxygen is not limited thereto.

 <83>

 At this time, nitrogen purging may be performed for 10 to 120 minutes.

If the nitrogen purging is performed for less than 10 minutes, oxygen There is a problem that can not be properly removed, there is a problem that energy is wasted when the nitrogen purging is performed for more than 60 minutes.

 <86>

 On the other hand, the solvent is selected from the group consisting of isooctane, toluene, xylene, methyl isobutyl ketone, methyl isopropyl ketone, cyclopentanone and propyl acetate

One or more solvents may be used, but the solvent is not limited thereto, and a material having a boiling point of 60 V or more in the known solvents may be appropriately selected and used. In particular, nonpolar or weakly polar solvents are preferred, and more preferably a boiling point of at least so.

 <88>

 The functional monomer may be acrylic acid, methacrylic acid, methyl methacrylate, methyl methacrylate, vinyl alcohol, vinyl acetate, vinyl acetone, styrene, 4-ethyl styrene, 4-hydroxy styrene, 4-amino styrene, One or more selected from the group consisting of 4-vinylpyridine, 2-vinylpyridine, 1-vinylimidazole, acrylamide, and methacrylamide may be used, but the functional monomers are not limited thereto. Compounds having a double bond can be appropriately selected and used. In particular, it is preferable that molecular weight is 500 or less.

 <90>

 The crosslinking monomer may be ethylene glycol dimethacrylate, ethylene dimethacrylate, divinylbenzene, Ν, Ν'-methylenediacrylamide, Ν, Ν'-1,4-phenylenediacrylamide, 1 ， 3-Diisopropenylbenzene, 3, 5-bis (acrylamido) benzoic acid, tetramethylenedimethacrylate, 2, 6-bisacryloylamidopyridine, Ν, Ο-bisacryloyl-phenyl Alanine, 1, 4- diacryloylpiperazine, trimethyl propane trimethacrylate and pentaerythritol may be used at least one selected from the group consisting of tetraacrylate, but the crosslinking monomer is It is not restrict | limited, The compound which has a 2 or more double bond can be selected suitably, and can be used. In particular, it is preferable that molecular weight is 500 or less.

<92>

 In the method for preparing an organic monolith powder according to the present invention, step 2 is a step of advancing a polymerization reaction after mixing a covalent material having a molecular weight of 20,000 to 1 million and a polymerization initiator in the mixture solution. .

 <94>

In the present invention, by using a group covalent material having a molecular weight of 20,000 to 1 million In addition, it is possible to produce organic monolithic powder having almost no meso-sized pores and having a large macro-sized total pore volume. At this time, since the macropores do not exist inside but are embedded in the monolit surface, the mass transfer speed is high, and the monolat form allows the flow of the layered solvent to be fast and strong, resulting in a high layer density and maximum density. Since one-layer structure can be obtained, excellent separation efficiency similar to that of C18 attached 5 silica powder can be obtained. In the present invention, the covalent material having a molecular weight of 20,000 to 1 million in the mixed solution of step 1 is mixed.

 If, when mixing the covalent material having a molecular weight of less than 20,000 in the mixed solution of step 1 may cause a problem that the average pore size and total volume is too small, more than 1 million in the mixed solution of step 1 In the case where all the covalent substances having a molecular weight of M are mixed, there may be a problem that the covalent substances do not dissolve in the reaction solvent.

 The molecular weight of the pore-conducting material included in the mixed solution of step 1 may vary depending on the type of pore inducing material used. At this time, the pore-forming material of step 2 is 0.5 to 5 parts by weight based on 100 parts by weight of the solvent of step 1, the polymerization initiator of step 2 is 0.1 to 2 parts by weight based on 100 parts by weight of the solvent of step 1 It may be included in the amount of parts.

 If the pore-conducting material is contained in an amount of less than 0.5 parts by weight with respect to 100 parts by weight of the solvent, there is a problem in that the pore generation of monolit is insufficient, and when it contains more than 5 parts by weight, macropore of too large size is generated. This may cause a problem that the monolith function is impaired.

In addition, when the polymerization initiator is contained in less than 0.01 parts by weight with respect to 100 parts by weight of the solvent, the polymerization does not proceed well, and when included in excess of 2 parts by weight of the polymer is too low molecular weight The problem may arise that the structure of the monolith is inadequate. Mixing of step 2 may be performed for 10 to 30 minutes at a temperature of 50 to 80 ^° C. Step 2 may be performed in a nitrogen stream, but is not limited thereto. If the mixing of the step 1 is carried out at a temperature of less than 50 ^° C there is a problem that the subsequent polymerization is not performed properly, the mixing of the step 1 is carried out at a temperature of more than 80 ^° C In this case, there is a problem of overheating due to the rapid progress of the polymerization reaction in the subsequent process.

 In addition, when the mixing of the step 1 is carried out for less than 10 minutes, there is a problem that the dissolution is incomplete, if it is performed for more than 30 minutes to disturb the structure of the initial monolit formation There is a problem.

 <108>

The polymerization reaction of step 2 may be performed for 6 to ₄₈ hours at a temperature of 50 to 80 ^° C after stopping the mixing.

<ιιο> If the mixing of the step 1 is carried out at a temperature of less than 50 ^° C, there is a problem that the polymerization reaction is not performed properly, if the mixing of the step 1 is carried out in the silver of more than 80 ^° C There is a problem of overheating due to the rapid progress of the polymerization reaction.

< ^η ι> In addition, when the mixing of the step 1 is performed for less than 6 hours, there is a problem that the formation of the monolit is incomplete, and if it exceeds 48 hours, time and energy are wasted.

 <1 12>

 On the other hand, the polymerization initiator is an azo initiator such as azobisisobutyronitrile or azobisdimethyl-valeronit¾, an organic peroxide-based initiator such as benzoyl peroxide or lauroyl peroxide, potassium persulfate And one or more selected from the group consisting of water-soluble initiators such as ammonium persulfate, but the polymerization initiator is not limited thereto, and may be appropriately selected from known materials. In particular, azobisisobutyronitrile is accessible. In general, the most preferable.

 <1 14>

 When the organic monolith is formed, it is not contained in the organic monolith, but has affinity with the organic monolith, so that it is embedded in the form of a large lump of molecular groups near the outer wall of the organic monolith. It can be made to form pores on the surface.

At this time, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate, polyvinyl acetone, polyvinylpyridine, polyacrylamide, polyacrylonitrile, polyethylenediamine, polyvinyl chloride, polycaprolactam And made of polyester One or more selected from the group consisting of one or more may be used. However, the group-covalent material is not limited thereto, and in consideration of the components of the organic monolith and the physical properties of the solvent, generally known materials may be appropriately selected and used. In particular, it is preferable to use a polymer material having a molecular weight of 10, 000 to 1,000, 000, of which polyethylene glycol is generally the most preferable in terms of accessibility.

 <1 17>

 In the method for preparing an organic monolith powder according to the present invention, step 3 is a step of separating the organic monolith from the mixed solution in which the polymerization reaction was performed in step 2.

<1 19>

 In this case, the separation of step 3 may be performed by stirring the mixed solution in which the polymerization reaction of step 2 is performed, and removing the supernatant after the precipitate is precipitated. This is not limited to this.

 By performing the agitation, the soft monolith produced in step 2 may be pulverized, and the organic monolith, the pore inducing substance, and the mixed solution may be separated through a multi-step precipitation and supernatant removal process.

 <122>

 The stirring may be performed for 1 to 60 minutes, preferably 25 minutes to

It can be done for 35 minutes.

 The organic monolit powder production method of the present invention provides a reactor having a structure in which an exchangeable filter is attached to the bottom and connected to a valve and a vacuum device thereunder, wherein the steps can be continuously performed in the reactor. have.

 As such, most of the processes can be carried out continuously in simple steps in one reaction vessel, thereby reducing the manufacturing cost.

 In this case, the agitation may also be performed by the reactor of the present invention. The bottom valve under the reactor may be opened and a vacuum may be applied to remove the reaction solvent through the bottom filter, and the bottom valve may be closed, and subsequent processes may be continuously performed. You can proceed.

 <127>

 After removing the supernatant, the method may further include introducing at least one washing solution selected from the group consisting of acetone, acetonitrile and methanol before performing stirring again.

Specifically, the washing solution is poured to the extent that the precipitate is immersed and stirred for 25 to 35 minutes, it can be carried out by filtration, it is preferable to repeat about two times All.

 In this case, the washing solution is not limited thereto, and a low boiling point solvent may be appropriately selected. The method may further include introducing a polar mixed solvent after removing the supernatant and before performing stirring again. Through this step, it is possible to completely remove the group covalent material contained in the organic monolit.

 Specifically, the polar mixed solvent may be poured into the precipitate sufficiently so that the precipitate is submerged, heated, and stirred at reflux conditions for 2 (Γ to 30 hours, then filtered in a hot state and then cooled.

 In this case, a mixed solvent in which 2-propanol / acetic acid is mixed at a ratio of 9/1 may be used as the polar mixed solution, for example, but the polar mixed solvent is not limited thereto. On the other hand, after the separation of the step 3, may further comprise the step of drying the separated organic monolith.

 Specifically, it can be carried out by spreading the purified organic monolith powder obtained in the step 3 to room temperature drying under a dust protective film. Preferably, it is preferable to dry at room temperature for 24 hours or more, and to store the prepared powder in a shielded and dry container. The present invention,

 It is manufactured according to the manufacturing method,

An organic monolit powder having a pore size of 0.3 to 10 mm 3 and a total pore volume of 1 to 4 ml / g is provided. ^The present invention provides an organic monolith powder having a particle size (size of agglomerated spherical particles) of 0.5 to 100, a pore size of 0.2 to 10 1, and a total pupil volume of 1 to 4 mL / g. It can be used as a stationary phase in chromatography or solid phase extraction.

For high performance liquid chromatography columns, organic monolith powders with particle sizes of 1 to 40 and pore sizes of 0.5 to 3 mm 3 are preferred for stationary phase performance. All.

 <145>

 The organic monolith powder according to the present invention has almost no meso-sized pores, and is composed of macro-sized pores having a large amount of blood, and the macro pores are not present in the monolith. Twisted and twisted monolith particles are produced, which are naturally embedded in the vicinity of the surface, thereby increasing the mass transfer rate and increasing chromatographic separation efficiency. In addition, due to the monolithic form, the flow of the layered solvent is fast and strong, resulting in a better layered efficiency and a more compact layered structure. Thus, an excellent separation efficiency similar to that of C18 attached 5 m silica powder can be obtained. .

 <147>

 In addition, the present invention,

 A microcolumn comprising the organic monolith powder is provided.

 <150>

 A column for liquid chromatography can be prepared by layering the organic monolith powder on a stainless steel tube coated with glass on an inner wall thereof.

 In this case, the layer charge may be a slurry filling method of applying a vibration for 5 minutes at 15, 000 ps i, 10 minutes at 10, 000 ps i, 30 minutes at 8, 000 ps i, but the filling method is It is not limited to this.

 <153>

 [Form for implementation of invention]

 Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for the purpose of setting up the present invention, and the contents of the present invention are not limited to the following examples.

 <155>

 <156> <Example 1>

 Step 1: 1.35 mL of methacrylic acid, 1.14 mL of ethylene glycol dimethacrylate, 2.00 mL of isooctane, and 10.0 mL of toluene were placed in a vessel equipped with a reflux apparatus, followed by 20 minutes of nitrogen purging. Oxygen was removed and heated to 70.

 <158>

Step 2: 100 mg of polyethylene glycol and 50 mg of azobisisobutyronitrile were rapidly added to the heated mixed solution under nitrogen stream and stirred, After dissolving, the stirring was stopped, followed by reaction at 70 for 24 hours to produce a soft organic monolith.

 <160>

 <i6i> Step 3: The mixed solution in which the organic monolith was produced was pulverized by stirring for 30 minutes, and allowed to stand for 10 minutes to settle the precipitate, and then the supernatant was removed with a dropper.

 30 mL of acetone was added to the precipitate, stirred for 30 minutes, allowed to stand for 10 minutes, and then the supernatant was removed twice with a dropper after the precipitate had settled.

 50 mL of a 2—propanol / acetic acid mixed solvent having a volume ratio of 9/1 was added to the precipitate again and stirred for 24 hours at 80 ° C. reflux to completely remove the contained air-covalent substances.

 Finally, 30 mL of acetone was added to the precipitate at room temperature, stirred for 30 minutes, and allowed to stand for 10 minutes, after which the precipitate was settled and removed with a supernatant-ol dropper three times.

 <165>

 Step 4: The precipitate was filtered and dried at room temperature for one night under a protective film to prevent dust from falling and stored in a desiccator to prepare an organic monolit powder.

 <167>

 Step 5: Dispersing the organic monolithic powder in a methanol solution, and dispersing the dispersion in a glass coated stainless steel tube at an inner wall of 5 minutes at 15, 000 psi, 10 minutes at 10, 000 psi and 8, 000. A microcolumn (inner diameter of lmm, length of 30 cm) was prepared by the slurry layer method of applying a vibration for 30 minutes at a pressure of ps i.

 <169>

 <170> <Example 2>

 Except for mixing 50 mg polyethylene glycol in Step 2 of Example 1 was carried out in the same manner as in Example 1 to prepare a micro-column.

 <172>

 <173> <: Example 3>

 A microcolumn was prepared in the same manner as in Example 1, except that 200 mg of polyethylene glycol was mixed in Step 2 of Example 1.

 <1 75>

<176><Example4> A microcolumn was prepared in the same manner as in Example 1 except for mixing polyethylene glycol having a molecular weight of 20,000 in Step 2 of Example 1.

<178>

 <179> <Example 5>

 A microcolumn was prepared in the same manner as in Example 1 except that polyethylene glycol in molecular weight of 400,000 was mixed in Step 2 of Example 1.

<181>

 <182> <Comparative Example 1>

 <183>. Step 1: 270 μί methacrylic acid, 228 μί ethylene glycol dimethacrylate, 400 fxt isooctane, toluene 1.5 ml and 10 mg azobisisobutyronitrile and 24 mg polyethylene glycol 2400 molecular weight were prepared in a vessel, It was performed for 10 minutes.

<184>

Step 2: The mixed solution was reacted at 70 ° C for 24 hours to produce a soft organic monolith.

 <186>

 Step 3: The organic monolith-produced mixed solution was pulverized with a spatula, transferred to a back-bottomed flask with reflux, and 30 mL of a 2-propanol / acetic acid mixed solution was added and rippled. Stir for 24 hours under lux. The reflux wash step was performed twice.

 <188>

 Step 4: The washed organic monolit powder was filtered, marched with acetone, and dried at room temperature to prepare an organic monolit powder.

 <190>

 Step 5: Dispersing the organic monolithic powder in a methanol solution, dispersing the dispersion in a glass coated stainless steel tube on the inner wall for 5 minutes at 14,000 psi, 10 minutes at 10,000 psi and 40 minutes at a pressure of 8,000 psi. Then, layered by slurry filling method to give a vibration for 5 minutes at 14,000 psi to prepare a microcolumn (inner diameter 0.5mm, length 30cm).

<192>

 <193> <Comparative Example 2>

 A microcolumn was prepared in the same manner as in Comparative Example 1 except that 36 mg of polyethylene glycol was prepared in Step 1 of Comparative Example 1.

<195> <196><Comparative Example 3>

A microcolumn was prepared in the same manner as in Comparative Example 1 except that 48 mg of polyethylene glycol was prepared in Step 1 of Comparative Example 1.

 <198>

<1 9> <Experimental Example 1> Measurement of the properties of the organic monolit powder

In order to observe the properties of the organic monolith powder prepared in step 3 of Example 1, a scanning electron microscope (Hi tachi (Japan) S-4200 FE-SEM instrument), transmission electron microscope (JE0L (USA) JEM 2100F instrument) to observe the shape of the particles and the results are shown in Figures 1 and 2, the particle size distribution measurement method (Malvern (UK) Masters i zer 2000 instrument) to observe the distribution of the particle size No. 3, pore by BET / BJH nitrate adsorption / desorption method (BEL-Japan (Japan) BELSORP-Max device), mercury infiltration pore measurement method (mercyry intrus ion poros imetry, Mi crometr i cs (USA) Autopore IV device) The distribution of the pores was observed and the results are shown in FIG. 4 and Table 1. FIG.

 <20I>

As shown in FIGS. 1 and 2, spherical elementary particles having a diameter of less than 1 1 combine to form a monolithic structure, and monolithic particles having various shapes having a size of 5 to 30 are generated. It can be seen that pores of 0.2 to 5 kPa are formed in the vicinity of the surface of the lit particles.

 <203>

As shown in FIG. 3, the volume-based particle size distribution shows that the average particle size is 15 and most of the distribution is very wide in the range of 5 to 30.

 <205>

<206> [Table 1]

 <207>

As shown in Table 1, the BET / BJH water adsorption / desorption method showed that the BET specific surface area was 4.2 mVg, and the total volume of meso-sized pores was only 0.007 mL / g.

 <209>

As shown in FIG. 4, the pores having a pore size of less than 0.5 μη \ are the total pore volume ( Contributions to meso and macro-sized pores) are negligible, thus the total pore volume is found to be 3.0 to 3.4 mL / g. Of these, the pore size is approximately 10

The pores above IM are not due to the pores inherent in the particles, but due to the volume of oil present between them, and the actual total pore volume of the particles themselves is somewhat smaller than the above measurement.

About 3.0 mL / g. ,

 <21 1>

 Experimental Example 2 Measurement of Characteristics of Column Made of Organic Monolit Powder

 In order to investigate the chromatographic performance of the microcolumns prepared in Examples 1 to 5 and Comparative Examples 1 to 3, N-methylaniline, phenol, acetophenone, benzene and Using a mixed solution of toluene as a sample, a solution containing 0. trifluoroacetic acid and a mixture of acetonitrile and water at 40/60 volume ¾ in this phase, separated at a flow rate of 15 / min The elution order was N-methylaniline, phenol, acetophenone, benzene and toluene. The results are shown in Tables 2, 5, 3, 6, and 4, respectively.

5 and 6, the theoretical number (N) measured for each solute was calculated by 5.54 (t _R / W _1/2 ) ² , where t _R is the retention time of the material and W _{1 / 2} is the peak width at the point of peak height 1/2 in the chromatogram.

 <215>

 <216> [Table 2]

 <217>

 As shown in Table 2 and FIG. 5, the theoretical singular value was the highest in Example 1, followed by Examples 2 and 200 mg having a polyethylene glycol content of 50 mg. appear.

 From this, the optimum amount of polyethylene glycol was used for the semi-aqueous solution of Example 1

It was found to be 100 mg.

 <220>

분자량 아녘린 페논 <221> [Table 3] PEG N-methyl phenol acetobenzene benzene

Molecular Weight Azarine Phenon

 Example 1 100.000 10.400 16.100 15.300 14.700 13.900 Example 4 20.000 5.300 10.600 10.000 10.200 9.900 Example 5 400.000 9.200 11.100 97,00 10.900 10.800

<222>

 As shown in Table 3 and FIG. 6, the theoretical singular value was the highest in Example 1, and next, except for acetofetone, the polyethylene glycol molecular weight was

It was shown in the order of Example 5 with 40,000 and Example 4 with 20,000.

 From this, it was found that the optimal molecular weight of polycetylene glycol was 100,000.

<225>

 <226> [S-4]

 <227>

 As shown in Table 4, the theoretical singular values of Comparative Examples 1 to 3 were 2500 to 4400, which were considerably lower than those of Examples 1 to 5.

 <229>

 Through this, the results obtained from the column packed with the optimal organic monolith powder of Example 1, the theoretical number of 10,000 to 16,000 can be compared with the commercially available 5 ΛΠ C18 column can obtain a good result I can see that.

Claims

[Scope of Claim] 【Claim 1】 Preparing a mixed solution by mixing a functional monomer, a crosslinking monomer, and a solvent, and removing oxygen in the common solution (step 1); After mixing a pore-inducing material and a polymerization initiator with a molecular weight of 20,000 to 1 million in the mixed solution, proceeding with a polymerization reaction (step 2); and A method for producing organic monolith powder comprising a step (step 3) of separating the organic monolith from the mixed solution in which the polymerization reaction was performed in step 2. [Claim 2] In paragraph 1' The mixed solution of step 1 is a method for producing organic monolith powder, characterized in that it contains 3 to 20 parts by weight of functional monomer and 5 to 20 parts by weight of crosslinking monomer, based on 100 parts by weight of solvent. 【Claim 3】 According to clause 1, A method for producing organic monolith powder, characterized in that the mixing in step 1 is performed at a temperature of 50 to 80 ^° C for 10 minutes to 1 hour. 【Claim 4】 In clause 1, A method for producing organic monolith powder, characterized in that oxygen removal in the mixed solution in step 1 is performed by nitrogen purging. 【Claim 5】 In clause 1, The pore-inducing material of step 2 is 0.5 to 5 parts by weight based on 100 parts by weight of the solvent of step 1, and the polymerization initiator of step 2 is 0.1 to 2 parts by weight based on 100 parts by weight of the solvent of step 1. A method for producing an organic monolith powder comprising: _, 【Claim 6】 In clause 1, A method for producing organic monolith powder, characterized in that the mixing in step 2 is performed for 10 to 30 minutes at a temperature of 50 to 80 ^° C. 【Claim 7】 In clause 1, A method for producing organic monolith powder, characterized in that the polymerization reaction in step 2 is performed for 6 to 48 hours at a temperature of 50 to 80 ^° C after stopping mixing. 【Claim 8】 According to clause 1, The separation in step 3 is performed by repeating the process of stirring the mixed solution in which the polymerization reaction of step 2 was performed and removing the supernatant after the precipitate has settled. 【Claim 9】 In clause 8, A method for producing organic monolith powder, characterized in that the stirring is performed for 1 to 60 minutes. . [Claim 10] In clause 8, A method for producing organic monolith powder, characterized in that it further comprises the step of introducing at least one washing solution selected from the group consisting of acetone, acetonitrile, and methanol after removing the supernatant and before stirring again. [Claim 11] In clause 8, A method for producing an organic monolith powder, characterized in that it further comprises the step of introducing a polar mixed solvent after removing the supernatant and before performing stirring again. 【Claim 12】 In clause U, After the separation in step 3, the method for producing organic monolith powder further comprises the step of drying the separated organic monolith. 【Claim 13】 It is manufactured according to the manufacturing method of paragraph 1, Organic monolith powder with a pore size of 0.3 to 10 and a total pore volume of 1 to 4 ml/g.