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WO2000010916A1 - Silicates mesoporeux et procede de fabrication associe - Google Patents

Silicates mesoporeux et procede de fabrication associe Download PDF

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Publication number
WO2000010916A1
WO2000010916A1 PCT/US1999/019256 US9919256W WO0010916A1 WO 2000010916 A1 WO2000010916 A1 WO 2000010916A1 US 9919256 W US9919256 W US 9919256W WO 0010916 A1 WO0010916 A1 WO 0010916A1
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inorganic oxide
reaction mixture
mesoporous
particles
carbon atoms
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Karl W. Gallis
Christopher C. Landry
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University of Vermont
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University of Vermont
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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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—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 form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • 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
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/265—Adsorption chromatography
    • 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
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 and B01D15/30 - B01D15/36, e.g. affinity, ligand exchange or chiral chromatography
    • B01D15/3833—Chiral chromatography
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01J20/283—Porous sorbents based on silica
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates

Definitions

  • the present invention relates to acid prepared mesoporous silica spheres and methods of synthesizing the same.
  • Porous silica is commonly use as a matrix material for chromatographic separations. With surface areas in the neighborhood of 300 m 2 /g, commercially available chromatographic grade silicas possess a relatively high surface area. Mesoporous materials, which typically possess surface areas in excess of 1000 m 2 /g and even as high as 1600 m 2 /g, are commonly used as adsorbents, catalysts, and catalytic supports. With such high surface areas, these materials should provide superior separating ability as a chromatographic matrix in liquid chromatography (LC), flash liquid chromatography (FLC), and high performance liquid chromatography (HPLC).
  • LC liquid chromatography
  • FLC flash liquid chromatography
  • HPLC high performance liquid chromatography
  • the material seems to possess desirable characteristics, a high surface area (1042 m 2 /g) and ⁇ 5 ⁇ m particle size, for use as a chromatographic matrix, but the long synthesis time (16 hours) and the use of a mixture of surfactants rather than one does not seem desirable for use on a commercial scale.
  • SBA-3 is similar to the more widely known MCM-41, which has an identical arrangement of pores but is synthesized in basic solution ("Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-Crystal Templating Mechanism," Kresge et al., Nature, 1992, 359, 710). While mesoporous silica having such ordered pores has use in a variety of contexts, the processes for synthesizing such materials tends to take longer, or be more complex, than is commercially desired.
  • the present invention relates to acid-prepared mesoporous silicates and methods of synthesizing same.
  • One aspect of the present invention is a method of forming mesoporous inorganic oxide particles in which at least 50% of the particles are spherical.
  • the method involves first preparing a reaction mixture capable of forming said mesoporous inorganic oxide particles.
  • the reaction mixture comprises: i. a mineral acid selected from the group consisting of HC1, HBr and HI; ii. an inorganic oxide source consisting of a compound having a formula
  • Rl, R2, R5 and R6 represent alkyl chains consisting of 1 to 6 carbon atoms
  • R3 represents an alkyl chain of 12 to 24 carbon atoms
  • R4 represents an alkyl chain of 3 to 16 carbon atoms
  • R7 represents an alkyl chain of 1 to 24 carbon atoms
  • X- represents a counterion to the surfactant which may be C1-, Br-, I- or OH-
  • EO x PO y EO z where EO is polyethylene oxide, PO is polypropylene oxide and x ranges from 5 to 106, y ranges from 30 to 85 and z ranges from 5 to 106; and iv.
  • the reaction mixture is mixed sufficiently so that mesostructured inorganic oxide particles may be formed in a subsequent heating step.
  • This latter step involves heating the reaction mixture at a temperature and for a time sufficient to form mesostructured inorganic oxide particles, at least 50% of which are spherical.
  • organic material is removed from the mesostructured inorganic oxide particles so as to form mesoporous inorganic oxide particles.
  • Another aspect of the present invention is a method of performing a liquid chromatographic separation of a liquid or dissolved solid compound using the mesoporous inorganic oxide synthesized using the process described above.
  • This method involves packing a chromatography column with a slurry of such mesoporous inorganic oxide.
  • the slurry includes an organic solvent selected as a function of the liquid or dissolved solid compound to be separated.
  • the liquid or dissolved solid compound is added to the slurry of mesoporous inorganic oxide.
  • a mobile phase of the liquid or dissolved compound is retrieved from the chromatography column.
  • FIG. 1 is a graph showing, in solid line, the absorbance of Ferrocene (Fc) and Acetylferrocene (AcFc) per volume of eluent achieved in liquid chromatography using as the stationary phase commercially available liquid chromatography silica particles, and in dotted line, the absorbance of Fc and AcFc per volume of eluent achieved using a commercially available flash liquid chromatography silica;
  • Fc Ferrocene
  • AcFc Acetylferrocene
  • FIG. 2 is a graph showing, in solid line, the absorbance of the same amount of Fc and AcFc per volume of eluent achieved in liquid chromatography using as the stationary phase mesoporous silica particles made in accordance with the method of the present invention, and in dotted line, the absorbance of Fc and AcFc per volume of eluent achieved using SBA-3 silica;
  • FIG. 3 is a graph showing the absorbance of (a) uracil, (b) benzene, (c) naphthalene and (d) biphenyl using as the stationary phase commercial reverse phase silica by reverse phase high pressure liquid chromatography;
  • FIG. 4 is a graph showing the absorbance of (a) uracil, (b) benzene, (c) naphthalene and (d) biphenyl using as the stationary phase mesoporous silica particles made in accordance with one aspect of the method of the present invention.
  • FIG. 5 is a graph showing the results of powder X-ray diffraction analysis of material produced by the method of the present invention, upper line a, and of SBA-3 silica.
  • the present invention is a method of synthesizing a highly porous, i.e., mesoporous, non- crystalline, inorganic oxide (MIO) using an acidic aqueous reaction procedure in a significantly shorter period of time than is required with known acidic solution syntheses for similar oxides.
  • MIO differs from conventional porous inorganic oxides in that their surface areas are significantly greater than those of conventional porous inorganic oxides, i.e., a surface area in excess of 600 m 2 /g and in some cases as high as 1,600 m 2 /g.
  • a well known inorganic oxide, conventional chromatographic grade silicas generally have a surface area less than 500 ⁇ r/g, and commonly less than 300 m 2 /g.
  • MIO prepared in accordance with the present method has a high percentage of spherical particles as determined by scanning election microscopy (SEM). At least 50% of the MIO particles produced by the present method are spherical, with 80-90% of the particles typically being spherical. In addition, there is a relatively narrow particle size distribution, i.e., virtually all of the MIO prepared with the method of the present invention has a particle size falling in the range 1-15 ⁇ m. The process is typically controlled to yield MIO with particle diameters in the 3-8 ⁇ m range.
  • SEM scanning election microscopy
  • Pore volumes of MIO synthesized using the present method lie in the range 0.35-0.75 cm 3 /g. Also, the relative placement of pores of the MIO is highly disordered. Powder X-ray diffraction reveals a notable absence of discernible peaks in the MIO; occasionally one unusually broad peak of low intensity is produced. The large surface area and particle size in the range of about 5 ⁇ m makes the MIO highly desirable in chromatography, as discussed more below.
  • MIO is synthesized using a three-step process involving an initial mixing of a reaction mixture containing an inorganic oxide source, one or more surfactants, a mineral acid and water.
  • the reaction mixture may also contain a metal salt.
  • the reaction mixture is heated for a selected time and temperature, and then the resulting product is collected, dried and calcined.
  • the inorganic oxide source is a compound of the type Si(ORl)(OR2)(OR3)(OR4), where Si is silicon, O is oxygen, and Rn represents an alkyl chain containing 1 to 4 carbon atoms.
  • the four OR groups may be identical, each may be different from the others, or some may be the same and others different.
  • the inorganic oxide source may consist of a mixture of these compounds.
  • One suitable inorganic oxide source is TEOS (tetraethoxysilane).
  • the surfactant may consist of a molecule with the formula R1R2R3R4N+X-, where Rl, R2 and R3 represent alkyl chains consisting of 1 to 6 carbon atoms, R4 represents an alkyl chain consisting of 12 to 24 carbon atoms, and X- represents a counterion to the surfactant which may be C1-, Br-, I- or OH-.
  • the surfactant may also consist of a molecule with the formula [R1R2R3N+R4N+R5R6R7]X-X-, where Rl, R2, R5 and R6 represent alkyl chains consisting of 1 to 6 carbon atoms, R3 represents an alkyl chain of 12 to 24 carbon atoms, R4 represents an alkyl chain of 3 to 16 carbon atoms, R7 represents an alkyl chain of 1 to 24 carbon atoms, and X- represents a counterion to the surfactant which may be C1-, Br-, I- or OH-.
  • CTAB cetyltrimethylammonium bromide
  • the surfactant may consist of a triblock co-polymer represented by the formula EO x PO y EO z , where EO represents polyethylene oxide, PO represents polypropylene oxide, and x ranges from 5 to 106, y ranges from 30 to 85 and z ranges from 5 to 106.
  • a suitable composition is EO 2 oPO 70 EO 2 o.
  • the mineral acid may be HC1, HBr or HI.
  • the optional metal salt has the formula MnXy, where M is a metal cation, X is an anion such as chloride, bromide, iodide, acetate, sulfate, nitrate or acetylacetonate, n is 1 or 2, and y is 1 , 2, 3 or 4.
  • M may be any transition metal, including without limitation, cobalt, copper, iron, molybdenum, nickel, palladium, platinum, ruthenium, titanium, zirconium.
  • M may be a rare earth or Group 13 metal cation.
  • the metal cation may also have the formula Al(ORl)(OR2)(OR3), where Al is aluminum, O is oxygen and Rl, R2 and R3 are alkyl chains having 1 to 4 carbon atoms.
  • the constituents of the reaction mixture are combined and then mixed until chemically homogeneous.
  • This mixing may be accomplished by stirring, by sonication involving use of a sonication horn of the type sold by Heat Systems-Ultrasonics Inc., 1938 New Highway, Farmingdale, New York 11735, operating at a frequency and maximum power, respectively, of 20,000 kHz and 475 watts, or by other techniques yielding a chemically homogeneous mixture.
  • the mixing is performed at room temperature for preparations excluding the triblock copolymer, although any temperature in the range 15-30°C for preparations excluding the triblock copolymer is satisfactory.
  • mixing temperatures in the range 25-45 °C, preferably about 30-40°C are used for the mixing step.
  • a chemically homogeneous mixture is achieved with about 3 to 70 minutes of mixing when the triblock copolymer is not used, with mixing time varying with the composition of the RXN mixture.
  • mixing times in the range of 50 to 120 minutes are used, again with the time varying with the chemical composition of the reaction mixture. While it is typically advantageous to achieve chemical homogeneity as quickly as possible, in some cases it may be desirable to extend the mixing period. This can be achieved by reducing the acid concentration.
  • Suitable reduction of acid concentration can increase the period of mixing required to achieve chemical homogeneity such that 12 hours or more is needed.
  • the reaction mixture becomes opaque when the required amount of polymerization of the reaction mixture has been achieved to permit synthesis of the MIO in following steps.
  • an "opaque" mixture means a mixture having a transparent to white color and containing a suspension of very small particles that cannot be captured by Buchner filtration on VWR qualitative filter paper grade 413.
  • the reaction mixture is transferred to a high pressure reaction vessel such as a Teflon®-lined stainless steel autoclave of the type sold by Parr Instruments Co, 211 Fifty-Third Street, Moline, Illinois and identified as model number 4748 or 4749.
  • a high pressure reaction vessel such as a Teflon®-lined stainless steel autoclave of the type sold by Parr Instruments Co, 211 Fifty-Third Street, Moline, Illinois and identified as model number 4748 or 4749.
  • the reaction mixture is heated to a temperature in the range 60-230 °C, preferably 130-190°C, and maintained there for a period of 15 to 80 minutes. Lower temperatures require longer heating times.
  • the reaction mixture is not stirred during this heating step.
  • the product resulting from this step is mesostructured MIO. This material has the desired mesostructure, although the pores are filled with organic material (surfactant) that is removed in the final step.
  • the mesostructured MIO is removed from the reaction vessel and dried by conventional techniques such as vacuum filtration. Then, organic material in the mesostructured MIO is burned away. This is accomplished by heating the material to a temperature in the range 400-600°C with a temperature ramp of 0.2 to 5°C/minute, preferably no more than about 2°C/minute, and then maintaining it at such temperature for at least 6 hours, with longer periods of time generally being required.
  • such removal of organic material is accomplished in a two-step process where the mesostructured MIO is heated at a temperature ramp of about 2°C/minute to a temperature of about 450 °C where it is maintained for about 4 hours. Then, the temperature is elevated at a temperature ramp of about 10°C/minute to 550° C where it is maintained for about 8 hours.
  • the surfactant may also be removed by ion exchange using dilute HCl dissolved in ethanol.
  • Examples la-lj Water (1 1.1 g, distilled and deionized) was placed in a 150 ml beaker along with CTAB
  • mesoporous silica was produced having a high percentage of spherical particles. Indeed all samples yielded at least 50% spherical particles, with most samples having more than 90% spherical particles.
  • the mesoporous nature of the silica is confirmed by the surface area data; all samples are in excess of 900 m 2 /g surface area as determined using the BET technique. Pore diameter and pore volume data (determined using the BJH technique) are also consistent with mesoporo sity .
  • Example 4 Water (11.1 g, distilled and deionized) was placed in a 150 ml beaker along with CTAB (cetyltrimethylammonium bromide, 0.24 g, Aldrich), HCl (4.0 g, 37%, JT Baker) and TEOS (tetraethoxysilane, 1.13 g, 98%, Aldrich). The mixture was polymerized by stirring at room temperature for 3 minutes (until opaque), and then was transferred to and heated in an autoclave (Parr bomb model 4749) for 40 minutes at 150°C. After heating, the reaction mixture was allowed to cool to room temperature, was filtered, dried and then calcined in air at 550°C.
  • CTAB cetyltrimethylammonium bromide, 0.24 g, Aldrich
  • HCl 4.0 g, 37%, JT Baker
  • TEOS tetraethoxysilane, 1.13 g, 98%, Aldrich
  • Example 5 Water (11.1 g, distilled and deionized) was placed in a 150 ml beaker along with CTAB (cetyltrimethylammonium bromide, 0.16 g, Aldrich), HCl (0.95 g, 37%, JT Baker) and TEOS (tetraethoxysilane, 1.13 g, 98%, Aldrich). The mixture was polymerized by stirring at room temperature until opaque (about 1 hour), and then was transferred to and heated in an autoclave (Parr bomb model 4749) for 40 minutes at 150°C. After heating, the reaction mixture was allowed to cool to room temperature, was filtered, dried and then calcined in air at 550°C.
  • CTAB cetyltrimethylammonium bromide, 0.16 g, Aldrich
  • HCl HCl
  • TEOS tetraethoxysilane, 1.13 g, 98%, Aldrich
  • Example 8a Water (40.0 g, distilled and deionized) was placed in a 150 ml beaker along with a surfactant mixture comprising 75 wt% CTAB/25 wt% triblock copolymer, i.e., CTAB (cetyltrimethylammonium bromide, 0.66 g, Aldrich) and EO 20 PO 70 EO 20 (0.33 g, 5,700g/mol Aldrich), HCl (3.50 g, 37%, JT Baker) and TEOS (tetraethoxysilane, 2.85 g, 98%, Aldrich).
  • CTAB cetyltrimethylammonium bromide, 0.66 g, Aldrich
  • EO 20 PO 70 (0.33 g, 5,700g/mol Aldrich
  • HCl 3.50 g, 37%, JT Baker
  • TEOS tetraethoxysilane
  • the mixture was polymerized by stirring at 35 °C for 110 minutes (until opaque), and then the mixture was transferred to and heated in an autoclave (Parr bomb model 4748) for 40 minutes at 150°C. After heating, the reaction mixture was allowed to cool to room temperature, was filtered, dried and then calcined in air at 550°C.
  • Example 8b This example was performed under conditions identical to those of Example 8a, except that the ratio of CTAB to triblock copolymer was changed to 25 wt% CTAB/ 75 wt% triblock copolymer, (cetyltrimethylammonium bromide, 0.22 g, Aldrich) and EO 20 PO 70 EO 20 (1.00 g, 5,800g/mol Aldrich), with all other conditions being the same.
  • the mixture was polymerized by stirring at room temperature until opaque (about 1 hour), and then the mixture was transferred to and heated in an autoclave (Parr bomb model 4748) for 40 minutes at 150°C. After heating, the reaction mixture was allowed to cool to room temperature, was filtered, dried and then calcined in air at 550°C.
  • Example 9 Variations of this Example 9 were also performed with 50 wt% CTAB/ 50 wt% triblock copolymer and 25 wt% CTAB/ 75 wt% triblock copolymer, with all other conditions being the same. Porosity data similar to that reported below for Example 9 was achieved. Furthermore, the present invention encompasses a broad range of molar ratios for CTAB and triblock copolymer.
  • Example 10 Water (11.1 g, distilled and deionized) was placed in a 150 ml beaker along with CTAB (cetyltrimethylammonium bromide, 0.24 g, Aldrich), HCl (0.95 g, 37%, JT Baker), Al(OPr) 3 (aluminum isopropoxide, 0.02g, Aldrich) and TEOS (tetraethoxysilane, 1.13 g, 98%, Aldrich).
  • This Si:Al mixture 50:1 was polymerized by stirring at room temperature until opaque (about 1 hour), and then was transferred to and heated in an autoclave (Parr bomb model 4749) for about 40 minutes at 150°C. After heating, the reaction mixture was allowed to cool to room temperature, was filtered, dried and then calcined in air at 550°C.
  • CTAB cetyltrimethylammonium bromide, 0.24 g, Aldrich
  • HCl HCl (0.95 g, 37%, JT
  • Example 10 Variations of this Example 10 were also performed with A1C1 3 (aluminum chloride, 0.0 lg, Aldrich) in place of the Al(O'Pr) 3 . Similar porosity data to that reported below in Table 2 was achieved for this variation of Example 10.
  • A1C1 3 aluminum chloride, 0.0 lg, Aldrich
  • Example 12 Water (11.1 g, distilled and deionized) was placed in a 150 ml beaker along with CTAB (cetyltrimethylammonium bromide, 0.24 g, Aldrich), HCl (0.95 g, 37%, JT Baker), NiCl 2 «6H 2 O (nickel(II) chloride hexahydrate, 0.03 g, Aldrich) and TEOS (tetraethoxysilane, 1.13 g, 98%, Aldrich).
  • This Si:Ni mixture 50:1 was polymerized by stirring at room temperature until opaque (about 1 hour), and then was transferred to and heated in an autoclave (Parr bomb model 4749) for about 40 minutes at 150°C. After heating, the reaction mixture was allowed to cool to room temperature, was filtered, dried and then calcined in air at 550°C.
  • CTAB cetyltrimethylammonium bromide, 0.24 g, Aldrich
  • HCl 0.95 g, 3
  • MIO small silica particles, i.e., about 5 ⁇ m, are often used in liquid chromatography when high resolution separations are required, due to the direct relationship between plate height and particle size.
  • MIO made in accordance with the process described above has been determined to function highly effectively as the stationary phase in liquid chromatography ("LC").
  • LC liquid chromatography
  • Such MIO has application in various forms of liquid chromatography including conventional LC, and under the pressurized regimes of normal phase flash liquid chromatography (FLC), and high pressure liquid chromatography (“HPLC”), including reverse phases of both.
  • FLC normal phase flash liquid chromatography
  • HPLC high pressure liquid chromatography
  • a problem with the use of small particles is backpressure; this problem may be alleviated by applying pressure to the column as in FLC and HPLC.
  • a normal phase separation was performed using a sample of 3.5 g of MIO obtained by the method described above in Example 2.
  • the sample was placed in a 50 ml solvent mixture of ethylacetate and hexane (hexane EtOAc, 83/17 v/v%) and mixed to form a slurry.
  • the slurry was added to a fritted glass column having a 10 mm inside diameter and length of 11 cm.
  • a 100 mg sample of ferrocene and acetylferrocene, 50 mg of each, dissolved in the same solvent mixture was separated by flash liquid chromatography. Fractions were taken every 2.0 ml, allowed to dry, resuspended in acetone, and absorbances were read in a Spec 21.
  • FIG. 1 depicts the separation of Fc and AcFc using commercially available liquid chromatography silica, in solid line, and commercially available flash liquid chromatography silica in dotted line.
  • FIG. 2 represents separation data using the MIO of Example 2, in solid line, and SBA-3 (i.e., the type of mesoporous silicate prepared by Stucky et al. , referenced above, and used for comparison here), in dotted line.
  • SBA-3 i.e., the type of mesoporous silicate prepared by Stucky et al. , referenced above, and used for comparison here
  • Example 15 A reverse phase separation of common environmental contaminants was performed using a sample of 3.5 g of MIO obtained using the method described above in Example 2. The sample was suspended in dry toluene containing 1 equivalent of a tertiary amine. Octyldimethylchlorosilane (excess based on SiOH) was then added via syringe and the mixture was heated at reflux overnight. Then, the mixture was cooled, filtered, dried and washed with toluene and methanol. The alkyl chain (C 8 in this case) was covalentiy attached to the pore surfaces of the MIO by reaction with the Octyldimethylchlorosilane.
  • the mixture was slurry-packed into a conventional 150 x 4.6 mm stainless steel high performance liquid chromatography (HPLC) column with methanol, and a mixture of 5 ⁇ L each of uracil, benezene, biphenyl and naphthalene was injected into the column. Separation was performed by HPLC.
  • the mobile phase was H 2 O/MeOH (35/65 v/v%) at a flow rate of 1 mL/min and a 30°C column temperature. Detection was performed using a UV detector at 254 nm.
  • a separation using a commercially available reverse phase silica (Hypersil MOS-2, 5 ⁇ m particles, 120 A pore diameter, C g bonded organic phase) was performed for comparison.
  • a water/methanol mixture (35/65 v/v%) was then used as the mobile phase.
  • the Hypersil-C 8 used under HPLC conditions shows a relatively short retention time due to its low surface area.
  • the C 8 -MIO provides long retention times and baseline separation of all peaks.
  • Another disadvantage to the use of the Hypersil-C 8 is its expense, which makes it undesirable as a routine "one-time-use" flash HPLC silica.
  • C 8 -MIO has a comparatively low cost, and its peaks may be directly collected (employing UV visualization), eliminating the necessity of using a TLC plate to spot fractions collected from the column.
  • a chiral separation was performed using a sample of 3.5 g of MIO obtained using the method described above in Example 2.
  • the sample was suspended in a CH 2 Cl 2 /toluene (50/50 v/v%) mixture containing triethoxysilyl propylisocyanate (1:3 molar ratio based on SiO 2 ) and refluxed overnight.
  • the resulting product was cooled and allowed to settle, the solvent removed with a double-tipped needle, and dried in vacuo. It was then resuspended in a
  • a chiral separation was performed using a sample of 3.5 g of MIO obtained using the method described above in Example 2.
  • the sample was suspended in a CH 2 Cl 2 /toluene (50/50 v/v%) mixture containing triethoxysilyl propylamine (1:12 molar ratio based on SiO 2 ) and refluxed overnight.
  • the resulting product was cooled and allowed to settle, the solvent removed with a double-tipped needle, and dried in vacuo. It was then resuspended in toluene and R-(-)-N- 3,5-dinitrobenzoyl- ⁇ -phenylglycine (1:1 molar ratio based on propylamine) was added.
  • Detection was performed using a UV detector at 254 nm and partial separation of S-(-)- ⁇ -methyl(3,5- dinitrobenzyl) amine and R-(+)- ⁇ -methyl(3,5-dinitrobenzyl) amine was observed.
  • Example 18 Another chiral separation was performed using the MIO of Example 2.
  • the MIO was slurry- packed into a conventional 100 x 3.2 mm stainless steel high performance liquid chromatography column using MeOH and a mixture of 6 mg S-(+)-N-(3,5-dinitrobenzoyl)- ⁇ - methylbenzylamine (98%, Aldrich) and 3 mg R-(-)-N-(3,5-dinitrobenzoyl)- ⁇ - methylbenzylamine (98%>, Aldrich) and was then separated.
  • the mobile phase was H 2 O/MeOH (50/50 v/v%) containing 20 mM ⁇ -cyclodextrin.
  • XRD powder X-ray diffraction
  • MIO produced in accordance with the present invention has a high concentration of spherical particles and a remarkably narrow particle size distribution.
  • Test data for the various examples provided above indicates at least 50% of the MIO is spherical, with most preparations yielding more than 80%) spheres, and some yielding more than 90% spheres.
  • test data for most preparations indicates MIO particle diameter distribution in the 3-8 ⁇ m range, with all preparations yielding MIO particle diameter distribution in the 1- 15 ⁇ m range.
  • the MIO of the present invention is formed by an emulsion templating method in which the heating step plays an important role. Since the reaction mixture of the present invention uses a relatively low concentration of acid (higher concentrations caused a precipitate to form much more quickly), the polymerization process happens slowly enough that significant amounts of TEOS remain unpolymerized even after 1 hour of stirring at room temperature.
  • the heating step then serves to help emulsify the mixture of oil (TEOS) in water, with some surfactant present in both the TEOS and water as well as at the interface. Heating is thought to accelerate the polymerization process, rapidly forming a highly porous silicate bead.
  • Another advantage of the present invention is that highly homogeneous MIO particle size and shape is achievable with the present method. This avoids the need, and added expense, of post-synthesis processing to achieve the desired MIO particle size and shape.
  • MIO having a very high surface area.
  • the MIO has particular application as the stationary phase in liquid chromatography.

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Abstract

L'invention concerne un procédé de préparation de silice mésoporeuse à partir d'un mélange réactionnel comprenant un acide minéral, une source d'oxyde inorganique, un surfactant et de l'eau. Ce mélange réactionnel est mélangé, à température ambiante pendant 30 à 70 minutes environ, jusqu'à ce qu'il soit suffisamment polymérisé, de façon que de la silice mésostructurée puisse se former lors d'une étape de chauffage ultérieure, ce qu'indique le virage à l'opaque du mélange réactionnel. Ce mélange réactionnel est ensuite chauffé dans une enceinte pressurisée pendant une durée et à une pression suffisantes pour former de la silice mésostructurée. La silice mésoporeuse est récupérée par filtrage, séchage et calcination à 400-600 °C à l'air ambiant pendant au moins six heures. Cette silice mésoporeuse présente une distribution poreuse étroite (23-24 Å), mais fortement désordonnée. En outre, cette silice mésoporeuse est sphérique et caractérisée par un diagramme de diffraction des rayons X sur poudre ne présentant pas de crête apparente ou une crête anormalement large à très faible intensité.
PCT/US1999/019256 1998-08-21 1999-08-21 Silicates mesoporeux et procede de fabrication associe Ceased WO2000010916A1 (fr)

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US6607705B2 (en) * 2000-04-13 2003-08-19 Board Of Trustees Of Michigan State University Process for the preparation of molecular sieve silicas
WO2004043861A3 (fr) * 2002-11-08 2004-07-08 Varian Inc Emballage de silice a haute porosite et a zone de grande surface avec une distribution du diametre des pores et des particules etroite et procedes de fabrication de ces emballages
WO2006135339A1 (fr) * 2005-06-16 2006-12-21 Agency For Science, Technology And Research Particules de mousse mesocellulaires
EP2256088A1 (fr) * 2009-05-27 2010-12-01 Korea Institute Of Ceramic Engineering & Technology Procédé de préparation de nanoparticules de silice mésoporeuse utilisant un sel de métal de transition
CN112320809A (zh) * 2020-11-06 2021-02-05 中广核研究院有限公司 一种稀土基气凝胶材料及其制备方法
CN114832800A (zh) * 2022-06-06 2022-08-02 宁波大学 一种固相微萃取探针、制备方法及其在生物胺检测中的应用

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6607705B2 (en) * 2000-04-13 2003-08-19 Board Of Trustees Of Michigan State University Process for the preparation of molecular sieve silicas
WO2004043861A3 (fr) * 2002-11-08 2004-07-08 Varian Inc Emballage de silice a haute porosite et a zone de grande surface avec une distribution du diametre des pores et des particules etroite et procedes de fabrication de ces emballages
WO2006135339A1 (fr) * 2005-06-16 2006-12-21 Agency For Science, Technology And Research Particules de mousse mesocellulaires
US8642006B2 (en) 2005-06-16 2014-02-04 Agency For Science, Technology And Research Mesocellular foam particles
EP2256088A1 (fr) * 2009-05-27 2010-12-01 Korea Institute Of Ceramic Engineering & Technology Procédé de préparation de nanoparticules de silice mésoporeuse utilisant un sel de métal de transition
CN112320809A (zh) * 2020-11-06 2021-02-05 中广核研究院有限公司 一种稀土基气凝胶材料及其制备方法
CN112320809B (zh) * 2020-11-06 2022-03-29 中广核研究院有限公司 一种稀土基气凝胶材料及其制备方法
CN114832800A (zh) * 2022-06-06 2022-08-02 宁波大学 一种固相微萃取探针、制备方法及其在生物胺检测中的应用
CN114832800B (zh) * 2022-06-06 2023-08-01 宁波大学 一种固相微萃取探针、制备方法及其在生物胺检测中的应用

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