DE2426306A1 - PROCESS FOR CHEMICAL MODIFICATION OF SOLID SURFACES - Google Patents
PROCESS FOR CHEMICAL MODIFICATION OF SOLID SURFACESInfo
- Publication number
- DE2426306A1 DE2426306A1 DE19742426306 DE2426306A DE2426306A1 DE 2426306 A1 DE2426306 A1 DE 2426306A1 DE 19742426306 DE19742426306 DE 19742426306 DE 2426306 A DE2426306 A DE 2426306A DE 2426306 A1 DE2426306 A1 DE 2426306A1
- Authority
- DE
- Germany
- Prior art keywords
- functional groups
- aryl
- solid
- groups
- reactive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
- B01J31/0238—Amines with a primary amino group
-
- 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
- B01J20/10—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
- B01J20/28002—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 physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
- B01J20/3259—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulfur with at least one silicon atom
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
- B01J20/3261—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
- B01J20/3263—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. an heterocyclic or heteroaromatic structure
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0217—Mercaptans or thiols
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
Dr. Imrich Sebestian
6602 DuduieilerDr. Imrich Sebestian
6602 Duduieiler
Verfahren zur chemischen Modifizierung von FestkörperoberflächenProcess for the chemical modification of solid surfaces
Die Erfindung bezieht sich auf die chemische Modifizierung der reaktionsfähigen Festkörperoberflächen mit siliciumorganischen Reagenzien. Auf diese Weise modifizierte Festkörper werden z.B. als Katalysatoren, Sorptionsmittel, usw. eingesetzt.The invention relates to the chemical modification of the reactive solid body surfaces with organosilicon Reagents. Solids modified in this way are used, for example, as catalysts, sorbents, etc.
Die Katalysatoren beschleunigen chemische Reaktionen; u.a. werden durch ihre Wirkung die Reaktionsbedingungen, wie z.B. Temperatur, Druck, gemildert.The catalysts accelerate chemical reactions; Among other things, the reaction conditions, such as temperature, Pressure, mitigated.
Bei Sorptionsvorgängen treten die Probesubstanzen in Wechselwirkung mit dem Sorptionsmittel. Sie können auch irreversibel sorbiert werden und bleiben somit auf dem Sorptionsmittel (selektive Sorption). Bei reversibler Sorption haben verschiedene Probesubstanzen, je nach deren Affinität, unterschiedliche Verweilzeiten am Sorptionsmittel. Diese Tatsache wird z.B. bei chromatographischen Trennungen ausgenutzt. Die Trennung erfolgt in einer Trennsäule, die mit einem geeigneten Sorptionsmittel (sogenannte stationäre Phase) gefüllt ist und von einem Trägermedium (Gas oder Flüssigkeit, sogenannte mobile Phase) dieses bedingt den Transport der Probekomponenten durch die Säule durchströmt wird.In the case of sorption processes, the sample substances interact with the sorbent. They can also be irreversibly sorbed and thus remain on the sorbent (selective sorption). In the case of reversible sorption, different sample substances, depending on their affinity, have different residence times on the sorbent. This fact is used e.g. in chromatographic separations. The separation takes place in a separation column which is filled with a suitable sorbent (so-called stationary phase) and from a carrier medium (gas or liquid, so-called mobile phase), which causes the transport of the sample components to flow through the column will.
Die Anwendung von chemisch modifizierten Festkörpern bietet für derartige Prozesse die Möglichkeit, die Selektivität des Sorptionsmittels zu variieren. Die Herstellung erfolgt durch die chemische Bindung von funktioneilen Gruppen an die Festkörperoberfläche.The use of chemically modified solids offers the possibility of varying the selectivity of the sorbent for such processes. The manufacture is done by chemical Binding of functional groups to the solid surface.
Es sind schon mehrere Methoden zur Modifizierung von Festkörpern ausgearbeitet worden. In der DT-PS 1 902 226 ist die Veresterung von Siliciumdioxid mit substituierten Alkoholen beschrieben. Die organischen Molekel sind an der Festkörperoberfläche durch *Si-0-C* -Bindung gebunden, die bekanntlich nicht hinreichend hydrolyse- und temperaturstabil ist·Several methods of modifying solids have been devised. In DT-PS 1 902 226, the esterification is of silicon dioxide with substituted alcohols. The organic molecules are through to the surface of the solid * Si-0-C * bond bound, which is known to be insufficient is hydrolysis and temperature stable
. . : S09849/0843. . : S09849 / 0843
Nach der deutschen Patentanmeldung P-2236862.3-41 werden die Silanolgruppen vom Siliciumdioxid (z.B. Silicagel) durch Chlorierung in die =Si-Cl- Gruppen umgewandelt. Diese reaktiven Gruppen werden in zweiter Stufe mit Aminen unter Ausbildung der ' =Si-N= -Bindung umgesetzt. Solche Produkte sind nur in einem pH-Bereich von 4-8 hydrolysestabil, d.h. in der praktischen Anwendung nur begrenzt verwendbar. Es ist nicht möglich, die für die Katalyse, den Ionenaustausch und die Chromatographie uichtigen-SO„H-Gruppen zu regenerieren (-SO Na + HCl —»-SO H + NaCl), weil für die Regenerierung verdünnte Säuren mit einem pH-liiert <■ 1 verwendet werden. Bei den flüssigkeitschromatographischen Trennungen werden oft Pufferlösungen verwendet, deren pH-Wert außerhalb der Stabilitätsgrenzen solcher stationärer Phasen liegt. Unter diesen Bedingungen wird die 5Si-N= -Bindung rasch gespalten.According to the German patent application P-2236862.3-41, the silanol groups are converted from silicon dioxide (eg silica gel) into the = Si-Cl groups by chlorination. In the second stage, these reactive groups are reacted with amines to form the '= Si-N = bond. Such products are only stable to hydrolysis in a pH range of 4-8, that is to say they can only be used to a limited extent in practical application. It is not possible to regenerate the SO "H groups which are essential for catalysis, ion exchange and chromatography (-SO Na + HCl -» - SO H + NaCl), because dilute acids are pH-linked for regeneration <■ 1 can be used. In liquid chromatographic separations, buffer solutions are often used whose pH is outside the stability limits of such stationary phases. Under these conditions the 5Si-N = bond is quickly cleaved.
Ein anderes Verfahren zur Modifizierung von anorganischen Festkörpern ist in der deutschen Patentanmeldung P 2313073.6 beschrieben. Nach diesem l/erfahren werden Festkörper mit Alkylchlorsilanen umgesetzt, danach werden durch Halogenierung in die an der Oberfläche des Festkörpers gebundenen Alkylketten Halogenatome eingeführt 'A und diese anschließend durch funktionelle Gruppen substituiert. Es ist bekannt, daß die ESi-CS -Bindung besonders hydrolyse— und temperaturstabil ist. Da die organischen Molekel durch diese Bindung an der Oberfläche gebunden sind, zeichnen sich derartige modifizierte Festkörper durch große Stabilität aus. Ein Nachteil dieses Verfahrens ist der große Zeitaufwand bei derartigen Umsetzungen; die Flodifizierungs— reaktionen nehmen mehr als zehn Tage in Anspruch. Ein weiterer Nachteil besteht darin, daQ die Bindung der funktioneilen Gruppen an den Festkörper über Alkylketten durch mehrstufige Umsetzungen an der Fest— körperoberfläche geschieht. Bei mehrstufigen Reaktionen sind die Ausbeuten jedoch niedriger, so daß die gewünschte maximale Oberflächen— konzentration von funktioneilen Gruppen nach diesem Verfahren nicht erreichbar ist.Another method for modifying inorganic solids is described in German patent application P 2313073.6. Solids are reacted with alkylchlorosilanes After this l / out, then be introduced by halogenation in the groups attached to the surface of the solid alkyl chains halogen atoms "A and subsequently substituted by functional groups. It is known that the ESi-CS bond is particularly stable to hydrolysis and temperature. Since the organic molecules are bound to the surface by this bond, such modified solids are characterized by great stability. A disadvantage of this method is the large amount of time required for such conversions; the flodification reactions take more than ten days to complete. Another disadvantage is that the functional groups are bonded to the solid via alkyl chains through multistage reactions on the surface of the solid. In the case of multistage reactions, however, the yields are lower, so that the desired maximum surface concentration of functional groups cannot be achieved by this process.
Ziel dieser Erfindung sind chemisch oberflächenmodifizierte Festkörper, die gefenüber bekannten chemisch modifizierten Festkörpern den Vorteil haben, daß sie hydrolyse- und temperaturstabil sind und sich durch große Oberflächenkonz«nt»«tion von funktionellen Gruppen auszeichnen.The aim of this invention are chemically surface-modified solids, the advantage over known chemically modified solids have that they are hydrolysis and temperature stable and through large surface concentration of functional groups.
509849/0 8 43509849/0 8 43
Derartige chemisch modifizierte Festkörper können z.B. als Katalysatoren, Ionenaustauscher oder Sorptionsmittel verwendet 'werden.Such chemically modified solids can be used, for example, as catalysts, Ion exchangers or sorbents can be used.
Es wurde nun gefunden, daß solche chemische Modifizierung der reaktionsfähigen Festkörperoberflächen erreicht wird, wenn man die an der Oberfläche vorhandenen Hydroxylgruppen mit substituierten Alkyl-, Aryl-, oder Aralkylalkoxysilanen unter Einwirkung won Katalysatoren umsetzt.It has now been found that such chemical modification of the reactive Solid surface is achieved when looking at the surface existing hydroxyl groups with substituted alkyl, aryl, or aralkylalkoxysilanes under the action of which converts catalysts.
Erfindungsgemäß werden die getrockneten Festkörper mit einer reaktionsfähigen Oberfläche in einem getrockneten Lösungsmittel (z.B. Toluol, Dimethylformamid, usw.) suspendiert und mit Alkoxysilan und Katalysator (&min oder Sulfonsäure) versetzt. Die Suspension wird einige Stunden lang unter Luftfeuchtigkeitsausschluß bei erhöhter Temperatur (z.B. 110 C) gehalten. Die Festkörper mit modifizierten Oberflächen werden abfiltriert, durch Waschen mit geeigneten Lösungsmitteln vom überschüssigen Alkoxysilan, Katalysator und Lösungsmittel befreit und getrocknet.According to the invention, the dried solids with a reactive Surface suspended in a dried solvent (e.g. toluene, dimethylformamide, etc.) and treated with alkoxysilane and catalyst ('or sulfonic acid) added. The suspension will last for a few hours Maintained at elevated temperature (e.g. 110 C) with exclusion of air moisture. The solids with modified surfaces are filtered off, freed from excess alkoxysilane, catalyst and solvent by washing with suitable solvents and dried.
Es wurde festgestellt, daß die chemische Modifizierung der reaktionsfähigen Festkörperoberflächen mit den reaktionsträgen substituierten Alkoxysilanen mit Hilfe von Katalysatoren beschleunigt und die Reaktionstemperatur gemildert wird. Dadurch ist es möglich, auch solche Silane für die Modifizierungsreaktionen zu verwenden, die funktioneile Gruppen enthalten.It was found that the chemical modification of the reactive Solid surfaces with the inert substituted alkoxysilanes are accelerated with the aid of catalysts and the reaction temperature is reduced. This makes it possible to also use such silanes to use for the modification reactions that contain functional groups.
Als katalytisch wirksame Reagenzien haben sich organische Amine und Sulfonsäuren erwiesen. Aus sterischen Gründen werden primäre Amine bevorzugt (z.B. n-Butylamin, Äthylendiamin usw.). Von Sulfonsäuren werden sowohl aliphatische (z.B. Dodecylsulfonsäure) als auch aromatische (z.B. Benzolsulfonsäure) verwendet.Organic amines and have proven to be catalytically active reagents Sulfonic acids proved. For steric reasons, primary amines are preferred (e.g. n-butylamine, ethylenediamine, etc.). Of sulfonic acids become both aliphatic (e.g. dodecylsulfonic acid) and aromatic (e.g. benzenesulfonic acid) is used.
Erfindungsgemäß werden für die Modifizierungsreaktionen substituierte Alkyl-, Aryl-, oder Aralkylalkoxysilane verwendet. Unter diesen siliciumorganischen Verbindungen versteht man Reagenzien, bei denen die funk— tionellen Gruppen über Alkyl-, Aryl- und Aralkylresten an das Siliciumatom gebunden sind. Außerdem ist an das Siliciumatom mindestens eine Alkoxygruppe (z.B. Methoxy-, Äthoxygruppe) gebunden.According to the invention, substituted for the modification reactions Alkyl, aryl, or aralkylalkoxysilanes are used. Among these organosilicon Compounds are understood as reagents in which the functional groups are attached to the silicon atom via alkyl, aryl and aralkyl radicals are bound. In addition, there is at least one on the silicon atom Alkoxy group (e.g. methoxy, ethoxy group) attached.
509649/0843509649/0843
Aus der großen Zahl der in Frage kommenden siliciumorganischen Reagenzien seien die folgenden genannt:From the large number of possible organosilicon The following reagents are mentioned:
3-Cyanopropyltriäthoxysilan, bis—(N,N,-Dimethyl 3-aminopropyl)-dimethoxysilan, 4-Aminobutylmethyldiäthoxysilan, 3-Wercaptopropylmethyldimethoxyailan, Octadecyldimethylpropoxysilan, (p-Nitrophenyl-N —aminomethyl)dimethyläthoxysilan, Dimethoxymethylsilyl(4-butylsulfonsäure Na-SaIz), (N,N,N, Trimethylemonium-S-propylhydrochloridJ-methyldimethaxysilan, 3—Phenylpropylraethyldiinethoxysilan, £N-2(Aminoäthyl)-3-afflinopropyl]trimethoxysilan, 3-Glycidoxypropylmethyldimethoxysilan usu. Diese Aufstellung ist jedoch keinesfalls limitativ.3-cyanopropyltriethoxysilane, bis- (N, N, -dimethyl 3-aminopropyl) -dimethoxysilane, 4-aminobutylmethyl diethoxysilane, 3-wercaptopropylmethyldimethoxyailane, Octadecyldimethylpropoxysilane, (p-nitrophenyl-N -aminomethyl) dimethylethoxysilane, dimethoxymethylsilyl (4-butylsulfonic acid Na-Salz), (N, N, N, Trimethylemonium-S-propylhydrochlorideJ-methyldimethaxysilane, 3-phenylpropylraethyldiinethoxysilane, £ N-2 (aminoethyl) -3-afflinopropyl] trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane etc. However, this list is by no means limiting.
Als besonders geeignete Materialien mit reaktionsfähiger Oberfläche haben sich die folgenden erwiesen:As particularly suitable materials with a reactive surface have proven the following:
Silicagel, Metalloxide (Al2O3, TiO«, ZrO-), poröses Glas, Trägermaterialien (Glaskugeln, Glasplatten, gemahlene Ziegelsteine usu.), die an der Oberfläche eine poröse Siliciumdioxid- oder Ftetalloxidschicht haben, usw.Silica gel, metal oxides (Al 2 O 3 , TiO «, ZrO-), porous glass, carrier materials (glass spheres, glass plates, ground bricks, etc.) that have a porous silicon dioxide or PTFE layer on the surface, etc.
Die nach dieser Erfindung modifizierten Festkörper enthalten an der Oberfläche über die hydrolyse- und temperaturstabile S-Si-CS —Bindung gebundene organische Molekeln» Durch Einführung von verschiedenen funktioneilen Gruppen wird die chemische Beschaffenheit der Oberfläche und dadurch die Selektivität der modifizierten Festkörper variiert. Dies ist besonders vorteilhaft bei Verwendung solcher Produkte als , Sorptionsmittel, z.B. in der Chromatographie, Umweltschutz, lonenaus- ; tausch oder als Katalysatoren. Da die funktionellen Gruppen erfindungsgemäß in einer Einechrittreaktion und bei milden Reaktionsbedingungen an die Festkörperoberflache gebunden werden, ist ihre Oberflächenkonzentration sehr groß. The solids modified according to this invention contain at the Surface via the hydrolysis and temperature stable S-Si-CS bond bound organic molecules »By introducing different functional groups, the chemical composition of the surface and thereby the selectivity of the modified solids varies. This is particularly advantageous when using such products as sorbents, e.g. in chromatography, environmental protection, ion removal ; exchange or as catalysts. Since the functional groups according to the invention in a one-step reaction and under mild reaction conditions are bound to the solid surface, their surface concentration is very high.
Es .ist weiterhin in vielen Fällen möglich die funktionellen Gruppen, j die an der Oberfläche des Festkörpers gebunden sind, in einer nachfolgenden Reaktion weiter umzusetzen und dadurch neue funktioneile Gruppen einzuführen. Die Selektivität und die Sorptionseigenschaften des modifizierten Festkörpers können somit zusätzlich in gewünschter ■ Weise verändert werden.In many cases it is still possible to use the functional groups j which are bound to the surface of the solid, in a subsequent To implement the reaction further and thereby introduce new functional groups. The selectivity and the sorption properties of the modified solid can thus additionally be changed in the desired manner.
Die chemische Modifizierung von Festkörperoberflachen nach der Erfindung wird durch nachfolgende Beispiele erläutert.The chemical modification of solid surfaces according to the invention is explained by the following examples.
509849/0843509849/0843
20 g Silicagel mit einer spezifischen Oberfläche von 310 m /g werden20 g of silica gel with a specific surface area of 310 m / g 12 Stunden lang bei 150 C getrocknet, mit 100 ml getrocknetem Xylol,Dried for 12 hours at 150 C, with 100 ml of dried xylene, 5 ml 3-Cyanopropylmethyldiäthoxysilan und 1 ml Ä'thylendiamin (Katalysator)5 ml 3-cyanopropylmethyl diethoxysilane and 1 ml ethylenediamine (catalyst) versetzt und 5 Stunden lang unter Luftfeuchtigkeitsausschluß beiadded and for 5 hours with exclusion of humidity 115 C gehalten.115 C held.
gewaschen und im Vakuum bei 140 C getrocknet.washed and dried in vacuo at 140.degree.
und enthält chemisch gebundene -CN-Gruppan.and contains chemically bound -CN groups.
20 g getrocknetes Silicagel werden mit 100 ml Toluol, 5 ml bis-(N,N-Dimethyl-3-aminopropyl)dimethoxysilan und 2 ml Butylamin (Katalysator) versetzt und unter Luftfeuchtigkeitsausschluß 3 Stunden lang bei 110 C gehalten. Das Produkt uiird analog Beispiel 1 gewaschen und getrocknet.20 g of dried silica gel are mixed with 100 ml of toluene, 5 ml of bis- (N, N-dimethyl-3-aminopropyl) dimethoxysilane and 2 ml of butylamine (catalyst) added and with exclusion of humidity for 3 hours at 110 ° C held. The product is washed and dried analogously to Example 1.
Die Oberfläche des Festkörpers ist durch die gebundenen -N(CH„)2-Gruppen basisch und das Produkt ist ein Anionenaustauscher. '■The surface of the solid is basic due to the bound -N (CH “) 2 groups and the product is an anion exchanger. '■
20 g getrocknetes Silicagel werden mit 5 ml 3-Mercaptopropylmethyldimethoxysilan nach Beispiel 1 umgesetzt, gewaschen und getrocknet. Durch Oxidation (z.B. mit HNO-) werden die oberflächenständigen -SH-Gruppen in -S0_H-Gruppen umgewandelt. Das Produkt ist ein stark saurer Kationenaustauscher.20 g of dried silica gel are reacted with 5 ml of 3-mercaptopropylmethyldimethoxysilane according to Example 1, washed and dried. By oxidation (e.g. with HNO-) the surface-related -SH groups converted into -S0_H groups. The product is a strong one acidic cation exchanger.
20 g getrocknetes Aluminiumhydroxid werden mit 100 ml getrocknetem Dimethylformamid, 4 g (N,N,N Trimethyl-3-ammoniumpropyl)-methyldimethoxy- ;silanchlorid und 3 ml Dipropylamin (Katalysator) versetzt und 5 Stunden lang unter Luftfeuchtigkeitsausschluß bei 110 C gehalten, dann analog20 g of dried aluminum hydroxide are dried with 100 ml Dimethylformamide, 4 g (N, N, N trimethyl-3-ammoniumpropyl) -methyldimethoxy- ; silane chloride and 3 ml dipropylamine (catalyst) added and 5 hours Maintained at 110 ° C. for a long time with exclusion of air humidity, then analogously
{Beispiel 1 gewaschen und getrocknet.{Example 1 washed and dried.
Das Produkt enthält oberflächenständige -R(CfO-Cl -Gruppen und ist ein stark basischer Anionenaustauscher·The product contains surface-R (CfO-Cl groups and is a strongly basic anion exchanger
509849/0843509849/0843
20 g mit porösem SiO- überzogene Glaskügelchen mit-einer spezifischen Oberfläche won 15 m /g werden mit 100 ml getrocknetem Dimethylsulfoxid, 3 g Dimethoxymethylsilyl 4-fautylsulfonsäure Natriumsalz und 0,5 g Benzolsulfansäure (Katalysator) versetzt, dann umgesetzt, gewaschen und getrocknet nach Beispiel 1.20 g of porous SiO-coated glass beads with a specific surface area of 15 m / g are mixed with 100 ml of dried dimethyl sulfoxide, 3 g of dimethoxymethylsilyl 4-fautylsulfonic acid, sodium salt and 0.5 g of benzenesulfanic acid (catalyst), then reacted, washed and dried Example 1.
Das Produkt wird mit 1 N Salzsäure und Wasser gewaschen und ist ein stark saurer Kationenaustauscher.The product is washed with 1 N hydrochloric acid and water and is a strongly acidic cation exchanger.
20 g getrocknetes poröses Glas mit einer spezifischen Oberfläche von 60 m /g werden mit 100 ml Dimethylformamid, 4 g Dimethoxymethylsilyl-3 propylisothiouroniumchlorid und 1 ml Äthylendiamin (Katalysator) versetzt und nach Beispiel 1 umgesetzt, gewaschen und getrocknet. Durch Oxidation (z.B. mit HNO , H Q) werden die an der Oberfläche gebundenen Propylisothiouroniumchlorid-Gruppen zu Propylsulfonsäure-Gruppen umgesetzt. Das Produkt ist ein stark saurer Kationenaustauscher. 20 g of dried porous glass with a specific surface area of 60 m / g are mixed with 100 ml of dimethylformamide, 4 g of dimethoxymethylsilyl-3 propylisothiouronium chloride and 1 ml of ethylenediamine (catalyst) and reacted according to Example 1, washed and dried. The propylisothiouronium chloride groups bound to the surface are converted into propylsulfonic acid groups by oxidation (eg with HNO, H Q). The product is a strongly acidic cation exchanger.
Eine mit Titanhydroxid belegte Glasplatte (7x5 cm) wird bei 150 C 12 Stunden lang getrocknet, mit 50 ml Xylol, 3 g (p-Nitrophenyl N-aminomethyl)-dimethyläthoxysilan und 2 ml Benzylamin (Katalysator) versetzt und unter Luftfeuchtigkeitsausschluß bei 120 C 8 Stunden lang gehalten.A glass plate (7x5 cm) covered with titanium hydroxide is heated to 150.degree Dried for 12 hours, with 50 ml of xylene, 3 g of (p-nitrophenyl N-aminomethyl) -dimethylethoxysilane and 2 ml of benzylamine (catalyst) are added and the mixture is kept at 120 ° C. for 8 hours with exclusion of atmospheric moisture.
Auswaschen und Trocknen erfolgt nach Beispiel 1.Washing out and drying is carried out according to Example 1.
Derartige oberflächenporöse Platten mit chemisch gebundenen Nitrogruppen finden Verwendung in der Dünnschichtchromatographie.Such surface-porous plates with chemically bound nitro groups are used in thin layer chromatography.
20 g getrocknetes poröses Glas mit einer spezifischen Oberfläche von 150 m /g werden mit 5 g N-2(Aminoäthyl)-3-aminopropyl trimethoxysilan analog Beispiel 1 umgesetzt, gewaschen und getrocknet. Das Produkt wird mit 100 ml Äthanol, 5 g Chloressigsäure und 5 ml Tripropylamin (HCl-Binder) versetzt und 10 Stunden lang unter Rückfluß gekocht, dann mit Methanol, blasser, Methanol mehrmals gewaschen und im Vakuum bei 600C getrocknet.20 g of dried porous glass with a specific surface area of 150 m / g are reacted with 5 g of N-2 (aminoethyl) -3-aminopropyl trimethoxysilane analogously to Example 1, washed and dried. The product is treated with 100 ml of ethanol, 5 g of chloroacetic acid and 5 ml of tripropylamine (HCl-binder) and 10 hours boiled under reflux, then with methanol, pale, methanol several times and dried in vacuo at 60 0 C dried.
Dar modifizierte Festkörper.enthält an der Oberfläche chemisch gebundene 7- Gruppen, die die Schwermetallionen binden.The modified solid body contains 7 chemically bound groups on the surface, which bind the heavy metal ions.
509849/0843509849/0843
20 g getrocknetes Zirkoniumhydroxid warden mit 100 ml Cumol,
5 ml 3—Phenylpropyldimethylpropaxysilan und 1 ml Hexamethylendiamin
(Katalysator) versetzt und 10 Stunden lang unter Luftfeuchtigkeitsausschluß bei 130 C gehalten. Auswaschen und Trocknen erfolgt nach
Beispiel 1. Die modifizierte Festkörperoberflache ist hydrophob und
enthält chemisch gebundene Phenylpropylgruppen,20 g of dried zirconium hydroxide are mixed with 100 ml of cumene,
5 ml of 3-phenylpropyldimethylpropaxysilane and 1 ml of hexamethylenediamine (catalyst) were added and the mixture was kept at 130 ° C. for 10 hours with exclusion of atmospheric moisture. Wash out and dry afterwards
Example 1. The modified solid surface is hydrophobic and contains chemically bound phenylpropyl groups,
509849/0843509849/0843
Claims (12)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19742426306 DE2426306B2 (en) | 1974-05-29 | 1974-05-29 | METHOD FOR CHEMICAL MODIFICATION OF SOLID SURFACES USING SILANES |
CH664375A CH614136A5 (en) | 1974-05-29 | 1975-05-23 | Process for the chemical modification of surfaces of solids |
FR7516702A FR2275252A1 (en) | 1974-05-29 | 1975-05-28 | METHOD FOR CHEMICAL MODIFICATION OF THE SURFACE OF SOLID BODIES |
GB2347775A GB1506226A (en) | 1974-05-29 | 1975-05-29 | Method of chemically modifying the surface of solids |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19742426306 DE2426306B2 (en) | 1974-05-29 | 1974-05-29 | METHOD FOR CHEMICAL MODIFICATION OF SOLID SURFACES USING SILANES |
Publications (2)
Publication Number | Publication Date |
---|---|
DE2426306A1 true DE2426306A1 (en) | 1975-12-04 |
DE2426306B2 DE2426306B2 (en) | 1977-06-23 |
Family
ID=5916934
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19742426306 Ceased DE2426306B2 (en) | 1974-05-29 | 1974-05-29 | METHOD FOR CHEMICAL MODIFICATION OF SOLID SURFACES USING SILANES |
Country Status (4)
Country | Link |
---|---|
CH (1) | CH614136A5 (en) |
DE (1) | DE2426306B2 (en) |
FR (1) | FR2275252A1 (en) |
GB (1) | GB1506226A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0062527A2 (en) * | 1981-04-07 | 1982-10-13 | Exxon Research And Engineering Company | Granular filter medium for removing oil from oily water |
EP0180563A2 (en) * | 1984-10-30 | 1986-05-07 | Exploaterings AB T.B.F. | An amphiphathic gel-product for chromatographic and batchwise adsorption |
EP0245222A2 (en) * | 1986-02-13 | 1987-11-11 | Gelinnovation H.B. | Nitrilophoric Electron-Donor-Acceptor-adsorbents |
US4741830A (en) * | 1984-07-28 | 1988-05-03 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Separation materials for thin layer chromatography |
EP0404134A1 (en) * | 1989-06-21 | 1990-12-27 | Dow Corning Toray Silicone Company, Limited | Organosilicon compounds and method for their preparation |
WO2005003455A1 (en) * | 2003-07-04 | 2005-01-13 | H.C. Starck Gmbh | Paper production with modified silica gels as microparticles |
EP1961862A1 (en) | 2003-07-04 | 2008-08-27 | Kemira Agro Oy | Paper production with modified solids as microparticles |
DE102007046904A1 (en) | 2007-09-28 | 2009-04-09 | H.C. Starck Gmbh | Particles with core-shell structure for conductive layers |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1531804A (en) * | 1976-03-09 | 1978-11-08 | British Petroleum Co | Oil separation method |
AU532164B2 (en) * | 1978-11-15 | 1983-09-22 | British Petroleum Company Plc, The | Removing metals from solution |
ZA801718B (en) * | 1979-03-27 | 1981-10-28 | British Petroleum Co | Functionalised inorganic oxide products and their use in the removal of heavy metals,transistion metals and actinidemetals from solution |
NZ195265A (en) * | 1979-10-27 | 1983-05-10 | British Petroleum Co | Catalytic esterification of carboxylic acids or anhydrides thereof |
DE3120214C2 (en) * | 1981-05-21 | 1984-09-27 | Degussa Ag, 6000 Frankfurt | Polymeric tertiary or secondary organosiloxane amines, process for their preparation and use |
CA1245208A (en) * | 1984-04-09 | 1988-11-22 | Thomas J. Tangney | Dual surface materials |
EP0161659B1 (en) * | 1984-05-12 | 1990-03-07 | Fuji Photo Film Co., Ltd. | Use of porous glass separation medium for high performance liquid chromatography |
DE3565850D1 (en) * | 1984-06-27 | 1988-12-01 | Nitto Electric Ind Co | Powdered coating composition of epoxy resin and filler |
DE3518881A1 (en) * | 1985-05-25 | 1986-11-27 | Degussa Ag, 6000 Frankfurt | ORGANOPOLYSILOXANES CONTAINING PHENYLENE SULPHONATE GROUPS, METHOD FOR THE PRODUCTION AND USE THEREOF |
DE3800564C1 (en) * | 1988-01-12 | 1989-03-16 | Degussa Ag, 6000 Frankfurt, De | |
DE3800563C1 (en) * | 1988-01-12 | 1989-03-16 | Degussa Ag, 6000 Frankfurt, De | |
US5185006A (en) * | 1990-12-17 | 1993-02-09 | Becton, Dickinson And Company | Lubricated metal articles and assembly containing same |
DE4223539C1 (en) * | 1992-07-17 | 1993-11-25 | Degussa | Shaped organopolysiloxanes containing sulfonate groups, process for their preparation and use |
DE19540497A1 (en) * | 1995-10-31 | 1997-05-07 | Degussa | Inorganic support materials containing sulfonate and mercapto groups, process for their preparation and use as catalysts |
FR2830188B1 (en) | 2001-09-28 | 2005-01-28 | Oreal | TINCTORIAL COMPOSITION CONTAINING A PARA-AMINOPHENOL OR PARA-PHENYLENE DIAMINE COMPOUND SUBSTITUTED WITH A SILANIC RADICAL |
JP5900399B2 (en) * | 2013-03-27 | 2016-04-06 | 信越化学工業株式会社 | Bis (aminoalkyl) silane compound and method for producing the same |
-
1974
- 1974-05-29 DE DE19742426306 patent/DE2426306B2/en not_active Ceased
-
1975
- 1975-05-23 CH CH664375A patent/CH614136A5/en not_active IP Right Cessation
- 1975-05-28 FR FR7516702A patent/FR2275252A1/en active Granted
- 1975-05-29 GB GB2347775A patent/GB1506226A/en not_active Expired
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0062527A3 (en) * | 1981-04-07 | 1982-12-29 | Exxon Research And Engineering Company | Granular filter medium for removing oil from oily water |
EP0062527A2 (en) * | 1981-04-07 | 1982-10-13 | Exxon Research And Engineering Company | Granular filter medium for removing oil from oily water |
US4741830A (en) * | 1984-07-28 | 1988-05-03 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Separation materials for thin layer chromatography |
US4793921A (en) * | 1984-07-28 | 1988-12-27 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Separation materials for thin layer chromatography |
EP0180563A3 (en) * | 1984-10-30 | 1987-02-04 | Exploaterings AB T.B.F. | An amphiphathic gel-product for chromatographic and batchwise adsorption |
EP0180563A2 (en) * | 1984-10-30 | 1986-05-07 | Exploaterings AB T.B.F. | An amphiphathic gel-product for chromatographic and batchwise adsorption |
EP0245222A3 (en) * | 1986-02-13 | 1988-02-24 | Gelinnovation H.B. | Nitrilophoric electron-donor-acceptor-adsorbents |
EP0245222A2 (en) * | 1986-02-13 | 1987-11-11 | Gelinnovation H.B. | Nitrilophoric Electron-Donor-Acceptor-adsorbents |
EP0404134A1 (en) * | 1989-06-21 | 1990-12-27 | Dow Corning Toray Silicone Company, Limited | Organosilicon compounds and method for their preparation |
WO2005003455A1 (en) * | 2003-07-04 | 2005-01-13 | H.C. Starck Gmbh | Paper production with modified silica gels as microparticles |
EP1961862A1 (en) | 2003-07-04 | 2008-08-27 | Kemira Agro Oy | Paper production with modified solids as microparticles |
US7708862B2 (en) | 2003-07-04 | 2010-05-04 | Kemira Oyj | Paper production with modified silica gels as microparticles |
US8088830B2 (en) | 2003-07-04 | 2012-01-03 | Kemira Oyj | Paper production with modified silica gels as microparticles |
DE102007046904A1 (en) | 2007-09-28 | 2009-04-09 | H.C. Starck Gmbh | Particles with core-shell structure for conductive layers |
Also Published As
Publication number | Publication date |
---|---|
GB1506226A (en) | 1978-04-05 |
CH614136A5 (en) | 1979-11-15 |
DE2426306B2 (en) | 1977-06-23 |
FR2275252B1 (en) | 1979-03-23 |
FR2275252A1 (en) | 1976-01-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2426306A1 (en) | PROCESS FOR CHEMICAL MODIFICATION OF SOLID SURFACES | |
DE2313073C2 (en) | Process for the chemical modification of surfaces of inorganic solids and their use | |
DE69006464T2 (en) | Pyridine-containing alkoxysilanes bound to inorganic carriers and processes for their use for the removal and concentration of desired ions in liquids. | |
DE2125428C2 (en) | Chromatographic packing and process for its manufacture | |
EP0098947B1 (en) | Polymeric mono-, di-, tri- and tetrasulfide compounds, process for preparing them and their use | |
DE19781813B4 (en) | Mesoporous molecular sieve and process for its preparation | |
DE3120195A1 (en) | POLYMERIC AMMONIUM COMPOUNDS WITH BASIC BASE BASED ON SILICON, METHOD FOR THEIR PRODUCTION AND USE | |
DE2236862B1 (en) | SORPTION AGENTS FOR CHROMATOGRAPHY | |
EP0098946B1 (en) | Organopolysiloxanes which contain sulfonate groups, process for preparing them and their use | |
EP0445604B1 (en) | Separation materials for chromatography | |
EP0327796B1 (en) | Shaped polymeric organosiloxane-ammonium compounds, process for their preparation and their use | |
EP0367105B1 (en) | Organosiloxane amine copolycondensates, process for preparing these and their use | |
DE3706523C2 (en) | ||
EP0367106A2 (en) | Organosiloxane amine copolycondensates, process for preparing these and their use | |
DE2834691C2 (en) | MONOMERS, POLYMERS AND CARRIER-FIXED RHODIUM COMPLEX COMPOUNDS, METHOD FOR THEIR PRODUCTION AND USE AS CATALYSTS | |
EP2210662A2 (en) | Method for producing adsorbent materials for liquid chromatography using zwitterionic silanes | |
DE3606262A1 (en) | SILYLCARBAMATE AND METHOD FOR THE PRODUCTION THEREOF | |
DE2828604A1 (en) | METHOD FOR REDUCING PHOSPHINOXIDES | |
EP0771589A1 (en) | Sulfonate and mercaptan groups containing inorganic support material, process for their preparation and for their use as catalysts | |
DE60303199T2 (en) | UREIDO OR CARBAMATE DERIVATIVES OF CROONETHANE AND SILICON, USEFUL FOR THE MANUFACTURE OF SUPPLEMENTAL MATERIALS FOR THE CHROMATOGRAPHIC SEPARATION OF METALLIC CATION AND AMINE-CONTAINING ORGANIC COMPOUNDS | |
DE2545065C3 (en) | Process for the preparation of monomethyltin trihalides | |
DE3042410C2 (en) | Process for the preparation of supports having ligands and complex catalysts corresponding thereto | |
DE2225904A1 (en) | PROCESS FOR THE PRODUCTION OF ION EXCHANGERS BASED ON SILICON DIOXIDE | |
EP0775670B1 (en) | Crystalline silicate powder | |
DD301777A9 (en) | METHOD FOR PRODUCING ION EXCHANGE |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
8235 | Patent refused |