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WO2015111797A1 - Procédé de préparation de poudre de monolithe organique et poudre de monolithe organique préparée par celui-ci - Google Patents

Procédé de préparation de poudre de monolithe organique et poudre de monolithe organique préparée par celui-ci Download PDF

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WO2015111797A1
WO2015111797A1 PCT/KR2014/003185 KR2014003185W WO2015111797A1 WO 2015111797 A1 WO2015111797 A1 WO 2015111797A1 KR 2014003185 W KR2014003185 W KR 2014003185W WO 2015111797 A1 WO2015111797 A1 WO 2015111797A1
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powder
organic monolith
organic
monolith
monolith powder
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Korean (ko)
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정원조
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Inha Industry Partnership Institute
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Inha Industry Partnership Institute
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
    • 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
    • B01J20/282—Porous sorbents
    • B01J20/285—Porous sorbents based on polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • 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.
  • 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.
  • 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 ⁇ 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.
  • Non-patent documents 1 to 7 disclose a bulk organic monolit
  • non-patent documents 8 to 11 disclose a bulk inorganic monolit.
  • research on powdered monolit is very limited.
  • Non-Patent Documents 12 to 18 and Patent Document 1 describe a method for producing a chromatographic stationary phase using powdered silica monolite.
  • Non-Patent Document 19 reports the world's first basic research using organic monolit powder as a low-cost chromatography stationary phase.
  • 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>
  • 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.
  • 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.
  • 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.
  • Patent Document 1 Korean Patent No. 10-1116566
  • 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;
  • 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;
  • 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;
  • step 1 mixing a functional monomer, a crosslinking monomer, and a solvent to prepare a mixed solution, and removing oxygen in the mixture solution (step 1);
  • step 3 of separating the organic monolith from the mixed solution subjected to the polymerization reaction in step 2.
  • 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.
  • 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.
  • Example 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. 3 is a graph showing a volume-based particle size distribution diagram of the organic monolit powder prepared in Step 3 of Example 1;
  • Example 4 is a graph showing a pore size distribution of the organic monolit powder prepared in Step 3 of Example 1;
  • Figure 6 is a graph showing the chromatogram obtained by the micro column prepared in Examples 1, 4, 5.
  • step 1 Mixing a functional monomer, a crosslinking monomer, and a solvent to prepare a mixed solution, and removing oxygen in the mixed solution (step 1);
  • step 2 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
  • step 3 of separating the organic monolith from the mixed solution subjected to the polymerization reaction in step 2.
  • 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.
  • 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.
  • the mixed solution of Step 1 is based on 100 parts by weight of the solvent, the functional monomer 3 to
  • 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.
  • 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.
  • Step 1 Mixing of Step 1 may be performed for 10 minutes to 1 hour at a temperature of 50 to 80 ° C.
  • 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.
  • step 1 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.
  • 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.
  • nitrogen purging may be performed for 10 to 120 minutes.
  • 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.
  • nonpolar or weakly polar solvents are preferred, and more preferably a boiling point of at least so.
  • 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.
  • the crosslinking monomer may be ethylene glycol dimethacrylate, ethylene dimethacrylate, divinylbenzene, ⁇ , ⁇ '-methylenediacrylamide, ⁇ , ⁇ '-1,4-phenylenediacrylamide, 1 , 3-Diisopropenylbenzene, 3, 5-bis (acrylamido) benzoic acid, tetramethylenedimethacrylate, 2, 6-bisacryloylamidopyridine, ⁇ , ⁇ -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
  • 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. .
  • the present invention by using a group covalent material having a molecular weight of 20,000 to 1 million
  • a group covalent material having a molecular weight of 20,000 to 1 million it is possible to produce organic monolithic powder having almost no meso-sized pores and having a large macro-sized total pore volume.
  • 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.
  • the covalent material having a molecular weight of 20,000 to 1 million in the mixed solution of step 1 is mixed.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the polymerization initiator is an azo initiator such as azobisisobutyronitrile or azobisdimethyl-valeronit3 ⁇ 4, 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.
  • azobisisobutyronitrile is accessible. In general, the most preferable.
  • the organic monolith 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.
  • 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.
  • 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.
  • step 3 is a step of separating the organic monolith from the mixed solution in which the polymerization reaction was performed in step 2.
  • 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.
  • 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.
  • the stirring may be performed for 1 to 60 minutes, preferably 25 minutes to
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ( ⁇ to 30 hours, then filtered in a hot state and then cooled.
  • 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.
  • the separation of the step 3 may further comprise the step of drying the separated organic monolith.
  • the purified organic monolith powder obtained in the step 3 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.
  • 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.
  • 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.
  • 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. .
  • a microcolumn comprising the organic monolith powder is provided.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Step 2 of Example 1 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.
  • 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.
  • 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.
  • 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.
  • Step 1 270 ⁇ methacrylic acid, 228 ⁇ 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.
  • Step 2 The mixed solution was reacted at 70 ° C for 24 hours to produce a soft organic monolith.
  • 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.
  • Step 4 The washed organic monolit powder was filtered, marched with acetone, and dried at room temperature to prepare an organic monolit powder.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the pores having a pore size of less than 0.5 ⁇ ⁇ 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.
  • N 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.
  • Example 1 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.
  • 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
  • Example 5 It was shown in the order of Example 5 with 40,000 and Example 4 with 20,000.

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Abstract

La présente invention se rapporte à un procédé de préparation d'une poudre de monolithe organique et à une poudre de monolithe organique préparée par celui-ci et, plus précisément, à un procédé de préparation d'une poudre de monolithe organique, le procédé comprenant les étapes suivantes : le mélange d'un monomère fonctionnel et d'un monomère de réticulation avec un solvant pour préparer une solution de mélange, et l'élimination de l'oxygène dans la solution de mélange (étape 1) ; le mélange de la solution de mélange avec une substance porogène ayant une masse moléculaire de 20 000 à 1 000 000 et un initiateur de polymérisation, suivi d'une réaction de polymérisation (étape 2) ; la séparation de monolithe organique de la solution de mélange dans laquelle la réaction de polymérisation a été effectuée dans l'étape 2 (étape 3). Le procédé de préparation d'une poudre de monolithe organique selon la présente invention utilise la substance porogène ayant une masse moléculaire de 20 000 à 1 000 000, ce qui permet de préparer ainsi une poudre de monolithe organique qui a peu de mésopores et un grand volume total de macro-pores. Selon l'invention, les macropores sont bloqués dans une région de surface du monolithe alors qu'ils sont absents à l'intérieur des pores du monolithe, ainsi la vitesse de transfert de matière est élevée et l'écoulement du solvant de charge est rapide et fort en raison de la forme du monolithe, ce qui améliore l'efficacité de la charge et permet d'obtenir une structure de charge de densité maximale. Par conséquent, l'utilisation de la poudre de monolithe organique en tant que phase stationnaire en chromatographie permet d'obtenir une excellente efficacité de séparation, qui est similaire à celle de poudre de silice de 5 μm pourvue d'un greffage en C18.
PCT/KR2014/003185 2014-01-21 2014-04-14 Procédé de préparation de poudre de monolithe organique et poudre de monolithe organique préparée par celui-ci Ceased WO2015111797A1 (fr)

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KR1020140007238A KR101583358B1 (ko) 2014-01-21 2014-01-21 유기 모노리트 분말의 제조방법 및 이에 따라 제조되는 유기 모노리트 분말
KR10-2014-0007238 2014-01-21

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