WO2005046834A1 - Verfahren zur herstellung von monolithischen formkörpern - Google Patents
Verfahren zur herstellung von monolithischen formkörpern Download PDFInfo
- Publication number
- WO2005046834A1 WO2005046834A1 PCT/EP2004/011627 EP2004011627W WO2005046834A1 WO 2005046834 A1 WO2005046834 A1 WO 2005046834A1 EP 2004011627 W EP2004011627 W EP 2004011627W WO 2005046834 A1 WO2005046834 A1 WO 2005046834A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gelling
- mold
- gelling mold
- particles
- sol
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 238000005530 etching Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 43
- 239000011521 glass Substances 0.000 claims description 25
- 238000000465 moulding Methods 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 10
- 238000003980 solgel method Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 238000007385 chemical modification Methods 0.000 claims description 6
- 238000013375 chromatographic separation Methods 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000005350 fused silica glass Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000002594 sorbent Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- 238000004587 chromatography analysis Methods 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000002202 Polyethylene glycol Substances 0.000 description 13
- 239000000499 gel Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 7
- -1 C1 to C20 alkyl Chemical class 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000003599 detergent Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 229910002020 Aerosil® OX 50 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012636 effector Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000005417 glycidoxyalkyl group Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000002470 solid-phase micro-extraction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- FOQJQXVUMYLJSU-UHFFFAOYSA-N triethoxy(1-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)[Si](OCC)(OCC)OCC FOQJQXVUMYLJSU-UHFFFAOYSA-N 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- NLMKTBGFQGKQEV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO NLMKTBGFQGKQEV-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000006323 alkenyl amino group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000012435 analytical chromatography Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 238000011209 electrochromatography Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004237 preparative chromatography Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- OSAJVUUALHWJEM-UHFFFAOYSA-N triethoxy(8-triethoxysilyloctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCCCC[Si](OCC)(OCC)OCC OSAJVUUALHWJEM-UHFFFAOYSA-N 0.000 description 1
- NIINUVYELHEORX-UHFFFAOYSA-N triethoxy(triethoxysilylmethyl)silane Chemical compound CCO[Si](OCC)(OCC)C[Si](OCC)(OCC)OCC NIINUVYELHEORX-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
Classifications
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
-
- 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
-
- 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
- B01J20/28023—Fibres or filaments
-
- 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
- B01J20/28042—Shaped bodies; Monolithic structures
-
- 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
- B01J20/28047—Gels
-
- 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
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/82—Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/84—Capillaries
Definitions
- the invention relates to a process for the production of monolithic moldings, such as chromatography columns or capillaries with monolithic sorbents, which are produced directly in their
- the invention further relates to moldings, such as chromatography columns or capillaries with monolithic sorbents, which were produced by the process according to the invention.
- Monolithic sorbents are becoming increasingly important in the field of chromatography, in particular HPLC, micro-LC or electrochromatography. They show significantly better mass transport properties than columns or capillaries with particulate sorbents. For this reason, columns with monolithic
- Sorbents can be operated at a higher linear flow rate with constant performance.
- Monolithic sorbents can be formed on the basis of organic or inorganic polymers. Due to the different properties of the polymers, different processes are currently used to manufacture chromatography columns based on monolithic sorbents.
- Polymers with low shrinkage rates can be produced directly in the tubes used for chromatography as a gelling mold.
- Hjerten et al. (Nature, 356, pp. 810-811, 1992) describe, for example, monoliths made of a polyacrylamide material, which are produced within a chromatographic tube.
- Frechet et al. (Anal. Chem., 64, pp. 820-822, 1992) describe the preparation of polyacrylate materials and polystyrene / divinylbenzene copolymers which are described in The presence of porogens become monolithic materials with a macroporous structure and can remain in the form used after production.
- Monolithic porous inorganic moldings or, in some cases, strongly cross-linked, hard organic polymer gels show significantly better separation properties.
- these materials shrink during their manufacture so that they cannot be manufactured directly in the chromatography tubes.
- the resulting dead volume between the molded body and the chromatography tube would reduce the separation performance too much.
- the shrinkage after aging is, for example, up to 20% of the starting diameter. Therefore, the materials must be removed from the gelling molds after they have been manufactured and then covered with tight-fitting tubes.
- WO 99/38006 and WO 99/50654 disclose processes for the production of capillaries which are filled with monolithic silica material. This material can remain directly in the capillary after manufacture. However, the methods disclosed there are only suitable for the production of capillary columns with a smaller diameter.
- the object of the present invention was therefore to provide a method for
- the method should be particularly suitable for inorganic materials and allow the filling of column tubes with a diameter between 0.05 mm and 100 mm.
- monolithic shaped articles can be produced in their gelling form without shrinkage resulting in a dead volume between the shaped article and the gelling form if the inner surface of the gelling form is activated before the synthesis.
- Suitable activation methods are e.g. Etching, enlargement or chemical modification of the inner surface of the gelling mold. In this way, the monolith can remain in the original gelling form and be used directly for the chromatographic separation.
- the present invention therefore relates to a process for producing monolithic porous moldings which completely fill their gelling mold, characterized by the following process steps: a) providing a gelling mold; b) activation of the gelling mold by etching, enlarging the surface and / or chemical modification; c) filling the gelling mold with monomer sol; d) polymerizing the monomer sol and aging the resulting gel to form pores.
- a gelling mold made of glass, glass-coated stainless steel or fused silica is provided in step a).
- the activation takes place in step b) by enlarging the inner surface of the gelling mold by treating the inner surface with alkoxysilanes and / or organoalkoxysilanes and / or slurries of particles.
- the activation takes place in step b) by chemical modification of the inner surface of the gelling mold by treating the surface with bifunctional reagents.
- a sol-gel process is used to produce the monolithic porous moldings.
- a monomer sol is used in step c), the particles and / or fibers and / or
- the present invention also relates to monolithic porous moldings which are polymerized into their gelling mold and can be produced by the process according to the invention.
- the present invention relates to the use of the moldings according to the invention in the gelling mold for the chromatographic separation of at least two substances.
- the process according to the invention is particularly suitable for the production of inorganic porous monolithic moldings by a sol-gel process.
- WO 95/03256 and particularly WO 98/29350 disclose preferred methods according to the invention for the production of inorganic monolithic moldings by a sol-gel process.
- This Materials contain mesopores with a diameter between 2 and 100 nm and macropores with an average diameter of over 0.1 ⁇ m and are therefore particularly well suited for chromatographic applications.
- the method according to the invention is also suitable for the production of materials with a different pore distribution.
- materials with a monomodal pore distribution can also be produced, e.g. Materials with an average pore diameter between 10 nm and 200 nm.
- the shaped articles can be produced, for example, by using alkoxysilanes in a gelling mold under acidic conditions in the presence of a pore-forming phase, e.g. an aqueous solution of an organic polymer, hydrolysed to a porous gel body and polycondensed.
- a pore-forming phase e.g. an aqueous solution of an organic polymer
- the gel is then aged and the pore-forming substance is finally separated off.
- the polymerization or polycondensation leads to a change in the gel structure and to a shrinking of the gel. This results in a dead volume between the gelling mold and the shaped body in the prior art methods.
- pore formers Depending on the type of monomers used and, if appropriate, pore formers, the specific implementation of the process according to the invention can vary. For example, when organoalkoxysilanes are used, an additional mesopore former (eg urea) can be dispensed with. In such cases, it is often not possible to differentiate between a gelling step and an aging step carried out independently of it, since aging takes place during the gelling step. According to the invention "Polymerizing the monomer sol and aging the resulting gel to form pores" therefore means that gelling and aging can take place in succession, for example under different temperature conditions, or also virtually in parallel, in that no further changes in the gelation conditions
- the gelling mold is the form into which the monolithic moldings are completely, i.e. polymerized with a perfect fit without dead volume. Since the molded bodies copolymerized according to the invention are preferably used as separation columns for chromatography, the gelling mold also represents the sheathing of the chromatography column. According to the invention, it is no longer necessary to remove the shaped bodies from the gelling mold for chromatographic use and to provide them with a new sheathing.
- the gelling form is therefore typically of a size and shape customary for capillaries, analytical or preparative chromatography columns.
- the gelling mold can also be used for other applications
- Shapes e.g. Have a conical or cuboid shape.
- the method according to the invention is also suitable for providing monolithic moldings for use in SPE (Solid Phase Extraction) or SPME (Solid Phase Microextraction) or generally for sample preparation.
- the gelling form is, for example, a cartridge or pipette tip.
- the gelling mold can consist of metal (eg stainless steel) or plastic or preferably of materials that are coated on the inside with glass (eg stainless steel with glass inliner), ceramic, glass or other silica materials, such as fused silica. Those skilled in the art will be able to choose from these materials based on the intended application To meet conditions for the activation of the surface of the gelling mold, the reaction conditions and the reactants used.
- completely means i.e. polymerized in a precisely fitting manner without dead volume, so that the gelling mold is filled by the molded body in such a way that the chromatographic separation performance is no longer impaired by cavities which occur in the edge regions between the monolithic molded body and the gelling mold due to shrinkage processes.
- the method according to the invention can be used for the production of chromatography columns with internal diameters of 50 ⁇ m to 100 mm, preferably between 0.5 mm and 50 mm.
- the inventive activation of the inner surface of the gelling mold intensifies the contact between the monomer sol or the resulting monolithic shaped body and the surface of the gelling mold. This is preferably done by increasing the formation of chemical bonds between the molded body and the gelling mold. It has been found that various types of activation of the surface of the gelling mold are suitable. Which type of activation is suitable for the particular synthesis depends on the material of the gelling mold and the composition of the monomer sol.
- This method is particularly suitable for gelling molds made of ceramic, glass or other silica-based materials or for molds coated with such materials. At least the inner surface of the gelling molds is etched with strong acids or strong bases. In this way, e.g. increasingly activated
- Silanol groups on the inner surface of the mold, which are associated with the monomer sol can react. Furthermore, strong bases partially dissolve the silicate structure of the glass, which results in an increase in surface area. Examples of suitable strong acids or bases are HF, HCl, HN0 3 or H 2 S0 4) NaOH, KOH, NH 4 OH, preferably HF and HCl or NaOH. The duration of the
- Treatment depends on the material of the gelling mold. As a rule, the molds are treated at temperatures between 25 ° C and 80 ° C between 5 minutes and 24 hours. The treatment can be carried out by immersing the entire mold or rinsing or filling the inside of the gelling mold. Finally, when using a base with dilute acid (for neutralization), with water and finally with an organic solvent, e.g. Rinsed ethanol or, in the case of acid, rinsed with water and an organic solvent and the mold filled with monomer sol.
- a base with dilute acid for neutralization
- an organic solvent e.g. Rinsed ethanol or, in the case of acid, rinsed with water and an organic solvent and the mold filled with monomer sol.
- Another very effective method for the production of monolithic chromatography columns according to the invention is the enlargement of the inside surface of the mold.
- the gelling mold is pretreated with a solution or slurry.
- the solution consists of a monomer sol similar to that which will later be used to form the monolithic shaped body, ie, like the monomer sol, it contains alkoxysilanes. These alkoxysilanes can react with the inner surface of the gelling mold and be polymerized and / or sintered there. In this way, a coating of the inner surface of the gelling mold is formed, which increases the inner surface due to its structure and structure.
- Suitable alkoxysilanes are tetraalkoxysilanes (RO) 4 Si, where R is typically an alkyl, alkenyl or aryl radical, such as C1 to C20 alkyl, C2 to C20 alkenyl or C5 to C20 aryl, preferably a C1 to C8 alkyl radical. Tetraethoxy and in particular tetramethoxysilane are particularly preferred.
- the tetraalkoxysilane can also contain various alkyl radicals.
- organoalkoxysilanes or mixtures of organoalkoxysilanes with tetraalkoxysilanes can be used.
- Suitable organoalkoxysilanes are those in which one to three, preferably one, alkoxy groups of a tetraalkoxysilane are replaced by organic radicals, such as preferably C1 to C20 alkyl, C2 to C20 alkenyl or C5 to C20 aryl.
- Further organoalkoxysilanes are disclosed, for example, in WO 03/014450 or US 4,017,528.
- the alkoxysilanes or organoalkoxysilanes can also be used in prepolymerized form, for example as oligomers.
- the tetraalkoxysilanes or organoalkoxysilanes are typically used as a 2 to 25%, preferably 5 to 10% (wt.%) Solution in an organic solvent such as e.g. Toluene used.
- the treatment of the gelling mold is preferably carried out at an elevated temperature between 50 and 150 ° C, e.g. is refluxed in toluene.
- the duration of the treatment is usually between 1 to 40 hours, typically 10 to 25 hours.
- the solution additionally contains particles and is therefore a particle suspension or slurry.
- the particles typically have a diameter between 25 nm and 10 ⁇ m, preferably between 50 nm and 1 ⁇ m and typically consist of plastic, ceramic, glass or inorganic oxides, such as Ti, Al, Zr or Si oxides. They preferably have a hydrophilic surface.
- hydrophobically derivatized particles for example with C1-C20 alkyl residues, are also particularly suitable if the monomer sol consists of organoalkoxysilanes and or mixtures of organoalkoxysilanes with alkoxysilanes. Due to hydrophobic interactions, the polymerization takes place at the beginning, preferably on the inner surface.
- the particles can be non-porous or porous. Spherical or irregularly shaped particles are suitable. Are particularly preferred
- the gels are treated with the solution or slurry at temperatures between 25 ° C and 100 ° C for 1 to 24 hours.
- the treatment can be carried out by immersing the entire mold or rinsing or filling the inside of the gelling mold. Then the gelling molds from the
- the gelling molds can still be heated.
- Tetraalkoxysilanes or purely inorganic particles can be calcined up to 600 ° C. If organoalkoxysilanes or particles with organic components were used, the temperatures should be between 100 and 300 ° C, unless the organic residues are to be burned out.
- the inner surface of the gelling mold is treated with reagents that have at least two, preferably three or four, functionalities.
- suitable reagents with at least two functionalities are referred to as bifunctional reagents.
- the reduction in shrinkage after treatment of the surface with these reagents is believed to result from the fact that at least one functionality reacts with the surface of the gelling mold and at least one functionality is available for reaction with the monomer sol.
- Alkoxysilanes or organoalkoxysilanes are suitable. Are particularly preferred
- R is typically an alkyl, alkenyl or aryl radical, such as C1 to C20 alkyl, C2 to C20 alkenyl or C5 to C20 aryl, preferably a C1 to C8 alkyl radical and n is preferably 1 to 8.
- bis (triethoxysilyl) ethane bis (triethoxysilyl) methane and bis (triethoxysilyl) octane.
- R and R ' are typically independently of one another an alkyl, alkenyl or aryl radical, preferably a C1 to C8 alkyl radical, and R * has a Si-OH-reactive group, such as an amino or an epoxy group. That is, R * is, for example, alkylamino, alkenylamino or arylamino, preferably a C1 to C8 alkylamino or glycidoxyalkyl, glycidoxyalkenyl or glycidoxyaryl, preferably C1 to C8 glycidoxyalkyl.
- m is 0, 1 or 2
- n + m gives 3.
- Examples of suitable compounds of the formula II are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane or 3-glycidoxypropylmethyldiethoxysilane as well as 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane-3-aminopropyl-aminopropyl-3-aminoxysiloxysilane-3-aminopropyl-3-aminoxysiloxysilane ,
- the bifunctional reagents are typically used as a 2 to 25%, preferably 5 to 10% (% by weight) solution in an organic solvent such as toluene.
- the gelling mold is preferably treated at an elevated temperature between 50 and 150 ° C .; For example, the mixture is boiled under reflux in toluene.
- the duration of the treatment is usually between 1 to 40 hours, typically 10 to 25 hours.
- the treatment can be carried out by immersing the entire mold or rinsing or filling the inside of the gelling mold. Finally, it is rinsed with an organic solvent and the mold is filled with monomer sol.
- the process according to the invention for the production of monolithic moldings in the gelling mold is further supported by the choice of the monomer sol.
- Another possibility of reducing or suppressing the shrinkage of the shaped bodies during their production is the choice of a particular composition of the monomer sol. For example, it has been found that adding particles to the monomer sol greatly reduces the rate of shrinkage.
- Japanese published patent application JP (A) 2002-293657 discloses the addition of particles in sol-gel processes for the production of porous moldings. Here, however, the goal of adding particles is to reduce them the energy expenditure in the production. There is no indication that a similar principle can also be used, under certain conditions, to reduce the shrinkage rate of the shaped bodies during aging.
- silica particles are preferably used in the present invention, which due to their chemical structure can also form a chemical bond with the monomer sol.
- JP (A) 2002-293657 e.g. Polymerized aluminum oxide particles using a sol-gel process with alkoxysilanes, i.e. here there is only an inclusion of particles but no chemical bond with the silicate network.
- the particles are preferably added at a later point in time, namely when the hydrolysis and polycondensation of the monomer sol has already taken place for about 5 to 120 minutes, preferably 15 to 45 minutes. At this point in time there are already oligomers or a loose network consisting of Si0 2 , into which the particles are then incorporated and mechanically stabilize the network due to their rigid properties. It has been found that with an addition preferred according to the invention in the prepolymerized state of the monomer sol, the particles then added are better distributed and suspended. In addition, this process control has the effect that the macropore size remains largely unaffected by the addition of particles.
- the method according to JP (A) 2002-293657 shows a dependence of the macro pore size on the amount of particles added, for example a macro pore size of 1 ⁇ m for 0.25 g aluminum oxide particles or a size of 0.7 ⁇ m for 0.5 g of the same particles.
- the macroporous size remains largely unaffected by the synthesis guide according to the invention.
- the macro-pore size is not changed for particle quantities of up to 1 g (on 50 ml of tetramethoxysilane).
- fibers are elongated structures whose length is at least 5 times greater than their average diameter.
- the fibers can be round, oval, irregularly shaped or even flat in diameter.
- Suitable fibers are mineral fibers or chemical fibers, such as in particular glass ceramic or particularly preferably glass fibers. It has been found that when fibers are added, the gel or the monolithic shaped body is effectively stabilized and the shrinkage is greatly reduced. This process is also particularly well suited for the production of shaped articles with larger diameters (> 3 mm).
- the fibers are added to the monomer sol in amounts between 1 and 50% by weight, preferably 2-30%.
- the stabilizing effect can be adjusted by choosing the fibers (for example glass fibers with a length of 0.1-5 mm (preferably 0.3-3 mm) and a diameter of 1-25 ⁇ m (preferably 5-10 ⁇ m)).
- the fibers for example glass fibers with a length of 0.1-5 mm (preferably 0.3-3 mm) and a diameter of 1-25 ⁇ m (preferably 5-10 ⁇ m)
- long fibers length> 3 mm
- long fibers for molded articles with larger diameters or a combination of long and shorter fibers.
- the shrinkage rate in the production of monolithic moldings can be reduced if the monomer sol contains not only alkoxysilanes but also at least 10%, preferably 20 to 100%, organoalkoxysilanes.
- Organoalkoxysilanes are silanes in which one to three alkoxy groups, preferably one alkoxy group, of a tetraalkoxysilane by organic
- Residues such as C1 to C20 alkyl, C2 to C20 alkenyl or C5 to C20 aryl, particularly preferably C1 to C8 alkyl, are replaced.
- Further organoalkoxysilanes are disclosed, for example, in WO 03/014450 or US 4,017,528. These documents also disclose the production of particles or monolithic moldings from organoalkoxysilanes. However, there is no indication that the use of Organoalkoxysilanes brings a reduction in shrinkage with aging.
- the concentration of certain substances must be varied slightly, since organoalkoxysilanes show a different polarity, reactivity or solubility than alkoxysilanes and thus influence, for example, the phase separation or the formation of the gel body.
- a water-miscible organic solvent e.g. Ethanol or preferably methanol, the molar ratio of water to solvent typically being between 10: 1 and 1: 5, preferably between 3: 1 and 1: 2.
- the formation of the pores can be influenced in different ways.
- a porogen such as polyethylene glycol
- a detergent can be added (eg cationic detergents such as CTAB (CH 3 (CH 2 ) ⁇ 5 N + (CH 3 ) 3 Br " ), non-ionic detergents such as PEG
- a calcination step is often carried out after the gelation and aging of the gel. This removes all organic compounds or residues remaining in the molded body. Also when using organoalkoxysilanes in the monomer sol
- ' ⁇ can be calcined in the last synthesis step, so that the organic residues are removed from the shaped body and a completely inorganic shaped body is obtained.
- this can be used to create pores.
- Calcination is usually carried out at temperatures between 300 and 600 ° C. However, it is also possible to dispense with the calcination step or to choose the temperature so that the organic residues are not attacked. In this way, there is the possibility of the material properties of the shaped bodies 5 e.g. with regard to their chromatographic separation properties.
- the temperatures in this case are typically between 100 and 300 ° C.
- organoalkoxysilanes influences the stability and porosity of the shaped bodies, it can be used for certain applications e.g. be advantageous not only to use organoalkoxysilanes but also mixtures of alkoxysilanes and organoalkoxysilanes. Then a treatment of the gelling mold according to the invention can optionally additionally reduce the shrinkage.
- Particles or fibers are particularly preferably added to a monomer sol containing organoalkoxysilanes.
- a gelling mold is first activated by etching and then filled with a mixture of an organoalkoxysilane (e.g. MTMS), a detergent, an acid (e.g. dilute nitric acid) and methanol. After gelation and parallel aging at elevated temperature, a sorbent which is well suited for chromatography is obtained.
- an organoalkoxysilane e.g. MTMS
- a detergent e.g. dilute nitric acid
- acid e.g. dilute nitric acid
- the shaped articles are also used after aging or calcination for use in chromatography Separation effectors provided.
- the various separation effectors and methods for their introduction are known to the person skilled in the art. Examples can be found, for example, in WO 98/29350.
- the method according to the invention can be used to produce monolithic, homogeneous, porous molded articles which completely fill their gelling mold.
- the shaped bodies can remain in the gelling mold for chromatographic purposes and show an equally homogeneous pore structure and equally good separation performance as subsequently coated shaped bodies.
- the method according to the invention therefore greatly simplifies the production of the monolithic moldings.
- Capillaries which are produced by the method according to the invention show significantly better separation performances than capillaries from the prior art. The reason for this is that through
- the present invention accordingly also relates to monolithic porous moldings which are polymerized into their gelling mold, can be produced by the process according to the invention by activating the surface of the gelling mold and / or adding particles, fibers or organoalkoxysilanes to the monomer sol.
- the moldings according to the invention are distinguished by a structure which is homogeneous over the entire cross section. Furthermore, the activation of the inner surface of the gelling mold forms chemical bonds between the molded body and the gelling mold, which bring about particularly effective stabilization.
- the cartridge was connected to an HPLC system and first washed in overnight with about 200 ml of ethanol (flow rate: 0.2 ml / min). The remaining pore former (polyethylene glycol) was rinsed out. Two substances could be separated. The cartridge was subsequently added to
- the glass cartridge was pretreated with the reaction mixture before filling. Glass cartridges were placed in 1 M HCl solution and treated at 40 ° C. for at least 24 hours. The tubes were then rinsed with water and ethanol and dried in a drying cabinet for 24 hours.
- the mixture thus obtained is then filled into pretreated glass cartridges (3 mm generally, 12.5 cm in length) and kept at 30 ° C. overnight in a water bath. During this time, the monolithic molded body is completely polymerized. It is then dried in a drying cabinet for 2 days and then used directly for chromatography. The monolith sits firmly in the glass cartridge and cannot be removed.
- the glass cartridges were pretreated with the reaction mixture before filling. Three variants were chosen: a) 5% TMOS (tetramethoxysilane) b) 5% BTME (bis (trimethoxysiiyl) ethane) c) 5% glymo (3-glycidoxypropyltrimethoxysilane) 5% solutions of a) -c) in toluene were each prepared. The glass cartridges were dipped into these and boiled under reflux overnight. The tubes were then rinsed with ethanol and dried in a drying cabinet for 24 hours.
- Aerosil Aerosil OX50, Degussa
- 3g particles Monospher ® 500 (monodisperse, non-porous particles, 500 nm, Fa. Merck KGaA) are stirred into the mixture.
- the mixture is then treated with a disperser (Diax 900) for better distribution of the particles.
- the resulting mixtures are filled into the pretreated glass cartridges (3 mm id, 12.5 cm long) and kept at 30 ° C. overnight in a water bath.
- the monolithic molded body is completely polymerized. It is then dried in a drying cabinet for 2 days. The monolith sits firmly in the glass cartridge and cannot be removed.
- the glass cartridges were pretreated as described in Example 2 before filling with the reaction mixture. Three variants were chosen for this:
- the glass cartridges were pretreated as described in Example 2 before filling with the reaction mixture. Three variants were chosen for this:
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/578,193 US7666336B2 (en) | 2003-11-06 | 2004-10-15 | Process for the production of monolithic mouldings |
CA2541284A CA2541284C (en) | 2003-11-06 | 2004-10-15 | Process for the production of monolithic mouldings |
AT04765974T ATE555834T1 (de) | 2003-11-06 | 2004-10-15 | Verfahren zur herstellung von monolithischen formkörpern |
EP04765974A EP1680201B1 (de) | 2003-11-06 | 2004-10-15 | Verfahren zur herstellung von monolithischen formkörpern |
JP2006537115A JP5052894B2 (ja) | 2003-11-06 | 2004-10-15 | モノリシック成形品の製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10351798.7 | 2003-11-06 | ||
DE10351798A DE10351798A1 (de) | 2003-11-06 | 2003-11-06 | Verfahren zur Herstellung von monolithischen Formkörpern |
Publications (1)
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WO2005046834A1 true WO2005046834A1 (de) | 2005-05-26 |
Family
ID=34559383
Family Applications (1)
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PCT/EP2004/011627 WO2005046834A1 (de) | 2003-11-06 | 2004-10-15 | Verfahren zur herstellung von monolithischen formkörpern |
Country Status (7)
Country | Link |
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US (1) | US7666336B2 (de) |
EP (1) | EP1680201B1 (de) |
JP (2) | JP5052894B2 (de) |
AT (1) | ATE555834T1 (de) |
CA (1) | CA2541284C (de) |
DE (1) | DE10351798A1 (de) |
WO (1) | WO2005046834A1 (de) |
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JPWO2005051864A1 (ja) * | 2003-11-28 | 2007-06-21 | 日本碍子株式会社 | 多孔質成形体、多孔質焼結体、その製造方法及びその複合部材 |
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JP4683554B2 (ja) * | 2003-11-28 | 2011-05-18 | 日本碍子株式会社 | 多孔質チタニア成形体の製造方法 |
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JP2007139652A (ja) * | 2005-11-21 | 2007-06-07 | Pentax Corp | カラムの製造方法およびカラム |
ES2302649A1 (es) * | 2007-01-11 | 2008-07-16 | Instituto Nacional De Investigacion Y Tecnologia Agraria Y Alimentacion (Inia) | Procedimiento para la preparacion de fibras polimericas para micro-extraccion en fase solida y producto obtenido. |
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ES2302649B1 (es) * | 2007-01-11 | 2009-06-08 | Instituto Nacional De Investigacion Y Tecnologia Agraria Y Alimentacion (Inia) | Procedimiento para la preparacion de fibras polimericas para micro-extraccion en fase solida y producto obtenido. |
EP2125196A1 (de) * | 2007-03-13 | 2009-12-02 | Varian, Inc. | Verfahren und vorrichtungen mit schrumpfbarem träger für poröse monolithische materialien |
DE102014216500A1 (de) | 2014-08-20 | 2016-02-25 | Hochschule Offenburg | Poröse monolithische oder faserförmige Produkte aus anorganischen Polymeren und deren Herstellung |
WO2016026923A1 (de) | 2014-08-20 | 2016-02-25 | Seal-Tec Gmbh | Poröse monolithische oder faserförmige produkte aus anorganischen polymeren und deren herstellung |
Also Published As
Publication number | Publication date |
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EP1680201A1 (de) | 2006-07-19 |
JP2012153893A (ja) | 2012-08-16 |
CA2541284A1 (en) | 2005-05-26 |
JP2007516821A (ja) | 2007-06-28 |
US20070065356A1 (en) | 2007-03-22 |
DE10351798A1 (de) | 2005-06-09 |
EP1680201B1 (de) | 2012-05-02 |
JP5052894B2 (ja) | 2012-10-17 |
ATE555834T1 (de) | 2012-05-15 |
CA2541284C (en) | 2012-07-24 |
US7666336B2 (en) | 2010-02-23 |
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