EP2164821A1 - Mixture and method for preserving porous materials - Google Patents

Mixture and method for preserving porous materials

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Publication number
EP2164821A1
EP2164821A1 EP08759298A EP08759298A EP2164821A1 EP 2164821 A1 EP2164821 A1 EP 2164821A1 EP 08759298 A EP08759298 A EP 08759298A EP 08759298 A EP08759298 A EP 08759298A EP 2164821 A1 EP2164821 A1 EP 2164821A1
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EP
European Patent Office
Prior art keywords
mixture
ormosil
composition according
substance
added
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.)
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Application number
EP08759298A
Other languages
German (de)
French (fr)
Inventor
Hermann Wolf Ibach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HERMES HOLDING GmbH
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Heimdall Holding GmbH
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Publication date
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Publication of EP2164821A1 publication Critical patent/EP2164821A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents

Definitions

  • the invention relates to a methylmethacrylate-free mixture for preserving porous substances, in particular objects made of stone or wood. Furthermore, the invention relates to a method for preserving porous substances.
  • TEOS tetraethoxysilane
  • KSE silica ester
  • the object of the invention is to produce a resistant protective layer in the pore system against the attack of water and pollutants in porous materials, in particular bodies and at the same time build up missing binder in the pore system.
  • the mixture contains at least two substances from the group of organically modified silicas, in particular organo (alkoxy) silanes (Ormosile).
  • the substance mixtures have a very good penetration behavior due to their molecular size and are able to achieve even very small pores.
  • these mixtures harden by hydrolysis and polycondensation, so that a solids content between 4% up to 69%, in particular between 8% to 30% remains as a film lining the pore walls in the pore space.
  • the curing which takes place by means of hydrolysis and polycondensation is surprisingly easy to control, in particular in the case of large-volume objects, by means of a program-controlled temperature and moisture control.
  • the resulting silica in the pore space verifiably covers the pore walls as a crack-free, transparent, water-insoluble film with good adhesion, so that the hoped-for lining effect of the pore occurs.
  • the required water can be added just before the impregnation, without affecting the penetration in the required penetration more negative.
  • a coupling agent in particular an organosilane. It is also important that a liquid acrylate-free mixture is achieved.
  • the liquid composition according to the invention is used for the preservative impregnation of porous substances, in particular of objects made of wood or stone.
  • the two components of the active ingredient system consisting of glycidyl-propyltrimethoxysilane (GLYMO) and aminopropyltriethoxysilane (APTS) in alcoholic solution are combined in stoichiometric amounts before injection into the pore system of the substance to be preserved and react with elimination of water to form an intermediate with six alkoxigram groups.
  • Partial hydrolysis activates the active substance system and condenses, with elimination of water and alcohol, to form a silica gel, in whose structure the organic component is bound between Si atoms, and acts as a spacer to build up a low-stress gel structure (Figure).
  • the preserving liquid may be composed differently, wherein the mixture contains at least one substance from the group of organo (alkosy) silanes (Ormosile).
  • the following mixtures are particularly advantageous:
  • a substance of the mixture is an Ormosil containing at least one epoxide unit.
  • One substance of the mixture is a 3-glycidyloxypropyltrimethoxysilane (GLYMO).
  • GLYMO 3-glycidyloxypropyltrimethoxysilane
  • a substance of the mixture is an Ormosil containing at least one amine function.
  • One substance of this mixture is a gammaaminopropyltriethoxysilane (APTS).
  • APTS gammaaminopropyltriethoxysilane
  • alcohol having one to six carbon atoms especially ethanol or methanol, is added.
  • the mass ratio of the Ormosil containing at least one epoxide moiety to the Ormosil containing at least one amine function is 1: 0.2 to 1:10, preferably 1: 0.7 to 1: 1, 7, and more preferably a mass ratio of 1 : 1, 07 on.
  • the porous substance in the form of an object eg. As a stone or a piece of wood, is first dried and then immersed in a liquid which consists of at least two Ormosilen plus a solvent liquid preferably ethanol.
  • a liquid which consists of at least two Ormosilen plus a solvent liquid preferably ethanol.
  • the mass ratio of the Ormosil, which contains at least one epoxide unit to the Ormosil, which contains at least one amine function 1: 1, 07th
  • An advantageous mixture consists of 2.4 g Ormosil 1, 2.3 g Ormosil 2 and 28 g ethanol. In the case of 28 g of ethanol, a solids separation of approx. 9.5 - approx. 10% is achieved in the object.
  • the proportion of ethanol can be chosen here between 0 - 5O g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Forests & Forestry (AREA)
  • Wood Science & Technology (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Paints Or Removers (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Silicon Polymers (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to a liquid mixture for preserving porous materials, in particular objects made of stone or wood, wherein the mixture contains at least two materials from the group consisting of organically modified silicon dioxides, in particular organo(alkoxy)silanes (ormosil). The invention further relates to a method of preserving porous materials.

Description

20.06.2008 CO/cu 670153WO B 20.06.2008 CO / cu 670153WO B
IBACH Steinkonservierung GmbH & Co. KGIBACH Steinkonservierung GmbH & Co. KG
Alte ZiegeleiOld brickyard
D 96110 ScheßlitzD 96110 Scheßlitz
Stoffmischung und Verfahren zum Konservieren poröser StoffeSubstance mixture and process for preserving porous substances
Die Erfindung betrifft eine methylmethacrylatfreie Stoffmischung zum Konservieren poröser Stoffe, insbesondere von Objekten aus Stein oder Holz. Ferner betrifft die Erfindung ein Verfahren zum Konservieren poröser Stoffe.The invention relates to a methylmethacrylate-free mixture for preserving porous substances, in particular objects made of stone or wood. Furthermore, the invention relates to a method for preserving porous substances.
Der Schutz vor Verwitterung und die Konservierung von bereits verwittertem Naturstein geht immer wieder von der Vorstellung aus, die Oberfläche des Gesteins - d. h. die sichtbaren Flächen - durch Zufuhr von Schutzstoffen zu schützen und zu festigen. Jede Zufuhr von Schutzstoffen führt jedoch in den erreichten Zonen zu einer Änderung der physikalischen Eigenschaften des Gesteins. Mit dieser Änderung der physikalischen Eigenschaften sind häufig Folgeschäden verbunden. Ziel jeder Konservierungsmaßnahme sollte es deshalb sein, diese Änderung möglichst gering zu halten und eine Konservierung über den gesamten Querschnitt des Gesteins - d. h. bis in den Kern - herzustellen, um Zonen mit unterschiedlichen physikalischen Eigenschaften zu vermeiden.The protection against weathering and the preservation of already weathered natural stone is always based on the idea that the surface of the rock - d. H. the visible surfaces - to protect and consolidate by supply of protective materials. However, any supply of protective substances will change the physical properties of the rock in the zones it reaches. This change in physical properties often involves consequential damage. The aim of every conservation measure should therefore be to minimize this change and to preserve it over the entire cross-section of the rock - d. H. to the core - to produce zones with different physical properties.
Realisiert wird diese Anforderung in wesentlichen Punkten mit dem seit 1972 entwickelten Acrylharzvolltränkungs-Verfahren, bei dem in einem Vollbad das vorher vollkommen getrocknete Gestein unter Zuhilfenahme von Vakuum und Druck bis in den Kern mit Methylmethacrylat (MMA) getränkt und anschließend das MMA zu Acrylglas polymerisiert wird. Da bei diesem Verfahren die gesamte Tränklösung zur Aushärtung gebracht wird, werden die Poren vollkommen mit PMMA ausgefüllt, so dass die Wasseraufnahme und Luftdurchlässigkeit vollkommen unterbunden werden. Die Denkmalpflege wünscht seit vielen Jahren ein offenporiges Konservierungsverfahren, bei dem die Schutzwirkung und die festigende Wirkung durch einen Schutzfilm im Inneren des Porensystems - durch eine Auskleidung der Porenwandung - erreicht wird. Mit dem von der Denkmalpflege tolerierten Einsatz von Tetraethoxysilan (TEOS) - besser bekannt unter dem Begriff Kieselsäureester (KSE) - dessen „Endprodukt" nach Ablauf der Reaktion ein aus reinem SiO2 bestehendes Kieselgel ist, wird dieses Ziel der Auskleidung der Porenwandung nicht erreicht. Mit vollständiger Reaktion der Hydrolyse und Polykondensation wird dieses Gel brüchig und rissig, und das entstehende SiO2 liegt bruchschollenartig im Porenraum. Die Schutzwirkung und die festigende Wirkung ist deshalb vielfach gering, es wird darüber hinaus ein zusätzliches Mikro-Porensystem erzeugt, so dass das Wasseraufnahme- und Wasserabgabe- Verhalten unkontrollierbar beeinflusst wird. Versuche, diese Kieselgelbildung so zu modifizieren, dass ein ausreichend elastisches, filmbildendes Gel entsteht, konnte nicht realisiert werden. Zur Beschichtung von inneren Oberflächen sind nur solche Systeme geeignet, die aus Monomeren bestehen und somit in der Lage sind, auch sehr kleine Poren zu erreichen. Lacksysteme in Form von Monomer-Polymersysteme, in der äußeren Anwendung bewährte Nanosysteme, scheiden aufgrund der mangelnden Eindringfähigkeit für viele Porensysteme insbesondere für Gesteine aus.This requirement is realized in essentials with the acrylic resin full impregnation process developed since 1972, in which the previously completely dried rock is impregnated with methylmethacrylate (MMA) into the core with the aid of vacuum and pressure and then the MMA is polymerized to acrylic glass , Since this process causes the entire impregnation solution to cure, the pores are completely filled with PMMA, so that water absorption and air permeability are completely prevented. For many years, the preservation of historic monuments requires an open-pored preservation process in which the protective effect and the firming effect are achieved by a protective film inside the pore system - through a lining of the pore wall. With the use of tetraethoxysilane (TEOS) - better known under the term silica ester (KSE) - whose "end product" is a pure silica consisting of pure SiO 2 after expiration of the reaction, this goal of lining the pore wall is not achieved. With complete reaction of the hydrolysis and polycondensation, this gel becomes brittle and cracked, and the resulting SiO 2 is pebble-like in the pore space.The protective effect and the strengthening effect is therefore often low, it is also an additional micro pore system generated, so that the water absorption Attempts to modify this silica gel formation to produce a sufficiently elastic, film-forming gel could not be realized, but only systems consisting of monomers are suitable for the coating of internal surfaces Are able, even very small pores to reach. Paint systems in the form of monomer polymer systems, proven nanosystems for outdoor application, are not used for many pore systems, especially for rocks, due to their lack of penetration.
Aufgabe der Erfindung ist es, bei porösen Stoffen insbesondere Körpern eine beständige Schutzschicht im Porensystem gegen den Angriff von Wasser und Schadstoffen zu erzeugen und zugleich fehlendes Bindemittel in dem Porensystem aufzubauen.The object of the invention is to produce a resistant protective layer in the pore system against the attack of water and pollutants in porous materials, in particular bodies and at the same time build up missing binder in the pore system.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, dass die Mischung wenigstens zwei Stoffe aus der Gruppe der organisch modifizierten Siliziumdioxide insbesondere Organo(alkoxy)silane (Ormosile) enthält.This object is achieved in that the mixture contains at least two substances from the group of organically modified silicas, in particular organo (alkoxy) silanes (Ormosile).
Überraschend hat sich herausgestellt, dass sich unterschiedliche Kombinationen von Organo(alkoxy)silanen (auch „Ormosile" genannt, d. h. organic modified silica = organisch modifiziertes SiO2) für eine derartige Beschichtung von inneren Oberflächen eignen. Die Stoffmischungen haben im Gegensatz zu den Nanosystemen und den aus Lösemittel und Feststoffen bestehenden „Lack"- Systemen aufgrund der Molekülgröße ein sehr gutes Eindringverhalten und sind in der Lage, auch sehr kleine Poren zu erreichen.Surprisingly, it has been found that different combinations of organo (alkoxy) silanes (also called "ormosils", ie organic modified silica = organically modified SiO 2 ) for such a coating of internal Surfaces are suitable. In contrast to the nanosystems and the "paint" systems consisting of solvents and solids, the substance mixtures have a very good penetration behavior due to their molecular size and are able to achieve even very small pores.
Nach Erreichen der inneren Hohlräume härten diese Stoffmischungen durch Hydrolyse und Polykondensation aus, so dass ein Feststoffgehalt zwischen 4 % bis zu 69 %, insbesondere zwischen 8 % bis 30 % als ein die Porenwandungen auskleidender Film im Porenraum verbleibt.After reaching the internal cavities, these mixtures harden by hydrolysis and polycondensation, so that a solids content between 4% up to 69%, in particular between 8% to 30% remains as a film lining the pore walls in the pore space.
Die durch Hydrolyse und Polykondensation ablaufende Aushärtung ist insbesondere bei großvolumigen Objekten durch eine programmgesteuerte Temperatur und Feuchteführung überraschend gut zu steuern.The curing which takes place by means of hydrolysis and polycondensation is surprisingly easy to control, in particular in the case of large-volume objects, by means of a program-controlled temperature and moisture control.
Versuche haben gezeigt, dass unter - zeitlich ausreichender -Aufrechterhaltung des guten Eindringverhaltens bei gut saugenden porösen Stoffen überraschenderweise zur Initialisierung der Hydrolyse ein entsprechender Wasseranteil zugegeben werden kann.Experiments have shown that while sufficient retention of the good penetration behavior with well-absorbent porous materials surprisingly, a corresponding amount of water can be added to the initialization of the hydrolysis.
Das im Porenraum entstehende Kieselgel überzieht die Porenwandungen nachweislich als rissfreien, transparenten, wasserunlöslichen Film mit guter Verhaftung, so dass der erhoffte Auskleidungseffekt der Pore eintritt.The resulting silica in the pore space verifiably covers the pore walls as a crack-free, transparent, water-insoluble film with good adhesion, so that the hoped-for lining effect of the pore occurs.
Überraschenderweise kann das benötigte Wasser kurz vor der Tränkung zugegeben werden, ohne das Eindringverhalten in der benötigten Eindringzeit stärker negativ zu beeinflussen.Surprisingly, the required water can be added just before the impregnation, without affecting the penetration in the required penetration more negative.
Besonders vorteilhaft ist die Zugabe von 1 bis 10 % eines Haftvermittlers, insbesondere eines Organosilans. Auch ist von Bedeutung, dass eine flüssige acrylatfreie Stoffmischung erreicht wird.Particularly advantageous is the addition of 1 to 10% of a coupling agent, in particular an organosilane. It is also important that a liquid acrylate-free mixture is achieved.
Vorteilhafte Ausgestaltungen der Erfindung sind in den Unteransprüchen aufgeführt. Ausführungsbeispiele der Erfindung werden im Folgenden näher beschrieben.Advantageous embodiments of the invention are listed in the subclaims. Embodiments of the invention will be described in more detail below.
Die erfindungsgemäße flüssige Stoffmischung wird zum konservierenden Tränken poröser Stoffe insbesondere von Objekten aus Holz oder Stein verwendet.The liquid composition according to the invention is used for the preservative impregnation of porous substances, in particular of objects made of wood or stone.
Die beiden Komponenten des aus Glycidylofypropyltrimethoxisilan (GLYMO) und Aminopropyltriethoxisilan (APTS) in alkoholischer Lösung bestehenden Wirkstoffsystems werden vor der Injektion in das Porensystem des zu konservierenden Stoffes in stöchiometrischen Mengen zusammengeführt und reagieren unter Wasserabspaltung zu einem Zwischenprodukt mit sechs randständigen Alkoxigruppen. Durch partielle Hydrolyse wird das Wirkstoffsystem aktiviert und kondensiert unter Wasser- und Alkoholabspaltung zu einem Kieselgel, in dessen Struktur die organische Komponente zwischen Si-Atomen eingebunden ist, und quasi als Abstandshalter zum Aufbau einer spannungsarmen Gelstruktur beträgt (Abbildung).The two components of the active ingredient system consisting of glycidyl-propyltrimethoxysilane (GLYMO) and aminopropyltriethoxysilane (APTS) in alcoholic solution are combined in stoichiometric amounts before injection into the pore system of the substance to be preserved and react with elimination of water to form an intermediate with six alkoxigram groups. Partial hydrolysis activates the active substance system and condenses, with elimination of water and alcohol, to form a silica gel, in whose structure the organic component is bound between Si atoms, and acts as a spacer to build up a low-stress gel structure (Figure).
O O O O I IO O O O I I
■ O - Si - H - Si - O - Si - - Si - O I I I I ■ O - Si - H - Si - O - Si - - Si - OIIII
0 O O O I I I I0 O O O I I I I
O - Si - SJ - Si - O - Si - - Si - O -O - Si - Si - Si - O - Si - - Si - O -
1 I I I O O O O1 I I O O O O
= organischer Anteil= organic share
Die konservierende Flüssigkeit kann unterschiedlich zusammengesetzt sein, wobei die Mischung wenigstens einen Stoff aus der Gruppe der Organo(alkosy)silane (Ormosile) enthält. Hierbei sind die folgenden Mischungen besonders vorteilhaft:The preserving liquid may be composed differently, wherein the mixture contains at least one substance from the group of organo (alkosy) silanes (Ormosile). Here, the following mixtures are particularly advantageous:
a) Ein Stoff der Mischung ist ein Ormosil, das wenigstens eine Epoxideinheit enthält. b) Ein Stoff der Mischung ist ein 3-Glycidyloxypropyltrimethoxysilan (GLYMO). c) Ein Stoff der Mischung ist ein Ormosil, das mindestens eine Aminfunktion enthält. d) Ein Stoff dieser Mischung ist ein Gammaaminopropyltrieethoxysilan (APTS). e) Zwei Stoffe dieser Mischung bestehen aus den zuvor unter a) und c) gekennzeichneten Ormosilen. f) Zwei Stoffe dieser Mischung bestehen aus den zuvor unter b) und d) gekennzeichneten Ormosilen.a) A substance of the mixture is an Ormosil containing at least one epoxide unit. b) One substance of the mixture is a 3-glycidyloxypropyltrimethoxysilane (GLYMO). c) A substance of the mixture is an Ormosil containing at least one amine function. d) One substance of this mixture is a gammaaminopropyltriethoxysilane (APTS). e) Two substances of this mixture consist of the ormosils identified above under a) and c). f) Two substances of this mixture consist of the ormosils identified above under b) and d).
Vorzugsweise wird als hydrophiles Lösungsmittel Alkohol mit ein bis sechs Kohlenstoffatomen insbesondere Ethanol oder Methanol zugegeben.Preferably, as the hydrophilic solvent, alcohol having one to six carbon atoms, especially ethanol or methanol, is added.
Das Masseverhältnis von dem Ormosil, das wenigstens eine Epoxideinheit enthält, zu dem Ormosil, das wenigstens eine Aminfunktion enthält, weist 1 : 0,2 bis 1 : 10 vorzugsweise 1 : 0,7 bis 1 : 1 ,7 und insbesondere ein Masseverhältnis von 1 : 1 ,07 auf.The mass ratio of the Ormosil containing at least one epoxide moiety to the Ormosil containing at least one amine function is 1: 0.2 to 1:10, preferably 1: 0.7 to 1: 1, 7, and more preferably a mass ratio of 1 : 1, 07 on.
Eine weitere Alternative besteht darin, dass neben dem Ormosil, das wenigstens eine Epoxideinheit aufweist, und neben dem Ormosil, das mindestens eine Aminfunktion enthält, noch wenigstens ein weiteres Ormosil enthalten ist. Hierbei ist das weitere OrmosilAnother alternative is that in addition to the Ormosil having at least one epoxy unit, and in addition to the Ormosil, which contains at least one amine function, at least one other Ormosil is included. Here is the other Ormosil
- ein gamma-Methacryloxypropyltrimethoxysilan,a gamma-methacryloxypropyltrimethoxysilane,
- ein Vinyltriethoxysilan,a vinyltriethoxysilane,
- ein Dimethyldiethoxi-Silan und/odera dimethyldiethoxysilane and / or
- ein Dimethyldimethoxi-Silan.a dimethyldimethoxysilane.
Von Bedeutung ist, dass der Mischung zur Initialisierung der Hydrolyse ein entsprechender Wasseranteil zugegeben ist. Weiteres Beispiel:It is important that an appropriate amount of water is added to the mixture to initiate the hydrolysis. Another example:
Der poröse Stoff in Form eines Objektes, z. B. ein Stein oder ein Stück Holz, wird zuerst getrocknet und dann in eine Flüssigkeit getaucht, die aus mindestens zwei Ormosilen plus einer Lösungsflüssigkeit vorzugsweise Ethanol besteht. Hierbei ist das Masseverhältnis von dem Ormosil, das wenigstens eine Epoxideinheit enthält, zu dem Ormosil, das wenigstens eine Aminfunktion enthält, 1 : 1 ,07. Eine vorteilhafte Mischung besteht aus 2,4g Ormosil 1 , 2,3g Ormosil 2 und 28g Ethanol. Bei 28 g Ethanol wird im Objekt eine Feststoffabscheidung von ca. 9,5 - ca. 10% erreicht. Der Anteil an Ethanol kann hierbei zwischen 0 - 5O g gewählt werden.The porous substance in the form of an object, eg. As a stone or a piece of wood, is first dried and then immersed in a liquid which consists of at least two Ormosilen plus a solvent liquid preferably ethanol. Here, the mass ratio of the Ormosil, which contains at least one epoxide unit to the Ormosil, which contains at least one amine function, 1: 1, 07th An advantageous mixture consists of 2.4 g Ormosil 1, 2.3 g Ormosil 2 and 28 g ethanol. In the case of 28 g of ethanol, a solids separation of approx. 9.5 - approx. 10% is achieved in the object. The proportion of ethanol can be chosen here between 0 - 5O g.
Durch dieses Verfahren wird neben der höheren Witterungsbeständigkeit auch eine höhere Festigkeit des Objekts erreicht. Dies zeigt sich an einer erheblichen Erhöhung des E-Moduls. By this method, in addition to the higher weather resistance, a higher strength of the object is achieved. This is evidenced by a significant increase in the modulus of elasticity.

Claims

20.06.2008 CO/cu670153WOC20.06.2008 CO / cu670153WOC
Ansprücheclaims
1. Methylmethacrylatfreie flüssige Stoffmischung zum Konservieren poröser Stoffe, insbesondere von Objekten aus Stein oder Holz, dadurch gekennzeich net, dass die Mischung wenigstens zwei Stoffe aus der Gruppe der organisch modifizierten Siliziumdioxide(Ormosile) insbesondere Organo(alkoxy)silane enthält.1. Methylmethacrylate-free liquid composition for preserving porous substances, in particular objects made of stone or wood, characterized in that the mixture contains at least two substances from the group of organically modified silicas (ormosils) in particular organo (alkoxy) silanes.
2. Stoffmischung nach Anspruch 1, dadurch gekennzeichnet, dass ein Stoff der Mischung ein Ormosil ist, das wenigstens eine Epoxideinheit enthält.2. A composition according to claim 1, characterized in that a substance of the mixture is an Ormosil containing at least one epoxide unit.
3. Stoffmischung nach Anspruch 1 oder 2, d a d u r c h gekennzeich net, dass ein Stoff der Mischung ein 3- Glycidyloxypropyltrimethoxysilan (GLYMO) ist.3. A composition according to claim 1 or 2, characterized in that a substance of the mixture is a 3-glycidyloxypropyltrimethoxysilane (GLYMO).
4. Stoffmischung nach einem der vorherigen Ansprüche, dadurch gekennzeich net, dass ein Stoff der Mischung ein Ormosil ist, das mindestens eine Aminfunktion enthält.4. Mixture according to one of the preceding claims, characterized in that a substance of the mixture is an Ormosil containing at least one amine function.
5. Stoffmischung nach einem der vorherigen Ansprüche, dadurch gekennzeich net, dass ein Stoff dieser Mischung ein Gammaaminopropyltrieethoxysilan (APTS) ist.5. A composition according to any one of the preceding claims, characterized in that a substance of this mixture is a Gammaaminopropyltrieethoxysilane (APTS).
6. Stoffmischung nach einem der vorherigen Ansprüche, gekennzeich net durch Zugabe eines hydrophilen Lösungsmittels, vorzugsweise eines Alkohols mit ein bis sechs Kohlenstoffatormen.6. A composition according to any one of the preceding claims, gekennzeich net by adding a hydrophilic solvent, preferably an alcohol having one to six carbon atoms.
7. Stoffmischung nach Anspruch 6, dadurch gekennzeichnet, dass der Alkohol Ethanol oder Methanol ist. gekennzeich net, dass das Masseverhältnis von dem Ormosil, das wenigstens eine Epoxideinheit enthält, zu dem Ormosil, das wenigstens eine Aminfunktion enthält, 1 : 0,2 bis 1 : 10 vorzugsweise 1 : 0,7 bis 1 : 1,7 und insbesondere ein Masseverhältnis von 1 : 1,07 aufweist.7. A composition according to claim 6, characterized in that the alcohol is ethanol or methanol. that the mass ratio of the Ormosil, which contains at least one epoxy unit, to the Ormosil, which contains at least one amine function, 1: 0.2 to 1: 10, preferably 1: 0.7 to 1: 1.7 and in particular a Mass ratio of 1: 1.07.
9. Stoffmischung nach einem der vorherigen Ansprüche, dadurch gekennzeich net, dass neben dem Ormosil, das wenigstens eine Epoxideinheit aufweist, und neben dem Ormosil, das mindestens eine Aminfunktion enthält, noch wenigstens ein weiteres Ormosil enthalten ist.9. A composition according to any one of the preceding claims, characterized in that in addition to the Ormosil having at least one epoxy unit, and in addition to the Ormosil containing at least one amine function, at least one other Ormosil is included.
10. Stoffmischung nach Anspruch 9, dadurch gekennzeichnet, dass das der Mischung beigegebene weitere Ormosil ein gamma- Methacryloxypropyltrimethoxysilan ist.10. A composition according to claim 9, characterized in that the mixture added further Ormosil is a gamma-methacryloxypropyltrimethoxysilane.
11. Stoffmischung nach Anspruch 9, dad urch gekennzeichnet, dass das der Mischung beigegebene weitere Ormosil ein Vinyltriethoxysilan ist.11. A composition according to claim 9, dad urch in that the added Ormosil the mixture is a vinyltriethoxysilane.
12. Stoffmischung nach Anspruch 9, d a d u rc h gekennzeichnet, dass das der Mischung beigegebene weitere Ormosil ein Dimethyldiethoxi-Silan ist.12. A composition according to claim 9, d a d u rc h characterized in that the mixture added further Ormosil is a dimethyldiethoxysilane.
13. Stoffmischung nach Anspruch 9, dad urch gekennzeichnet, dass das der Mischung beigegebene weitere Ormosil ein Dimethyldimethoxi-Silan ist.13. A composition according to claim 9, dad urch in that the added Ormosil the mixture is a dimethyldimethoxysilane.
14. Stoffmischung nach einem der vorherigen Ansprüche, dadurch gekennzeich net, dass der Mischung zur Initialisierung der Hydrolyse ein entsprechender Wasseranteil zugegeben ist.14. A composition according to any one of the preceding claims, characterized in that the mixture for initializing the hydrolysis, a corresponding amount of water is added.
15. Verfahren zum Konservieren poröser Stoffe mit einer Mischung nach einem der vorherigen Ansprüche durch Tränken des porösen Stoffs mit einem Ormosil und anschließendem Trocknen. 15. A method of preserving porous materials with a mixture according to any one of the preceding claims by impregnating the porous material with an Ormosil and subsequent drying.
EP08759298A 2007-07-02 2008-06-20 Mixture and method for preserving porous materials Withdrawn EP2164821A1 (en)

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CN101831076B (en) * 2010-04-23 2012-07-04 华东理工大学 Silica gel particle surface artemisinin molecularly imprinted polymer and preparation and application method thereof
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RU2010103205A (en) 2011-08-10
CA2691909C (en) 2013-06-18
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KR20100032869A (en) 2010-03-26

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