EP2250136A1 - Liant anorganique/organique, procédé de fabrication et utilisation - Google Patents

Liant anorganique/organique, procédé de fabrication et utilisation

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Publication number
EP2250136A1
EP2250136A1 EP08859879A EP08859879A EP2250136A1 EP 2250136 A1 EP2250136 A1 EP 2250136A1 EP 08859879 A EP08859879 A EP 08859879A EP 08859879 A EP08859879 A EP 08859879A EP 2250136 A1 EP2250136 A1 EP 2250136A1
Authority
EP
European Patent Office
Prior art keywords
binder
organic
metal
hydrolyzable
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
EP08859879A
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German (de)
English (en)
Inventor
Christian Schmidt
Helmut Schmidt
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.)
EPG Engineered Nanoproducts Germany AG
Original Assignee
EPG ENG NANOPROD GERMANY GmbH
EPG Engineered Nanoproducts Germany AG
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Filing date
Publication date
Application filed by EPG ENG NANOPROD GERMANY GmbH, EPG Engineered Nanoproducts Germany AG filed Critical EPG ENG NANOPROD GERMANY GmbH
Publication of EP2250136A1 publication Critical patent/EP2250136A1/fr
Withdrawn legal-status Critical Current

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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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • 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
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
    • 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
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/30—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Other silicon-containing organic compounds; Boron-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/56—Boron-containing linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00284—Materials permeable to liquids
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • Inorganic-organic binder process for its preparation and its use
  • the invention relates to a process for the preparation of a binder, the binder obtainable therefrom, its use and the cured molded articles produced therefrom.
  • Binders are materials which are usually applied to surfaces in viscous or liquid form or introduced or mixed into finely divided, powdery or granular materials, and which are converted into a solid form from their viscous or liquid form by a generally chemical process become. They connect the substrates firmly together.
  • gaps such as e.g. occur in grains and fillings, be fully filled or remain open in whole or in part. If they are to remain completely or partially open, then the binder must undergo a strong volume contraction during curing, and the remaining binder volume as possible retreat to the contact points of the grains.
  • Such behavior is also referred to as the syneresis effect, and occurs particularly with inorganic gels when using the sol-gel process.
  • Typical examples of inorganic binders are cements, gypsum or lime.
  • Typical examples of organic or polymeric binders are organic adhesives, bitumen, glue or similar materials.
  • inorganic binders can usually cure with water (hydraulic binders); this can also be associated with a hydrothermal process. Sometimes a simple drying process is sufficient for the curing, for example when a binder is suspended in an organic solvent or in water. Other mechanisms may be used, such as one radical crosslinking (this can be initiated by light or thermal), polyaddition or polycondensation. In certain inorganic binders, in particular those in which sol-gel processes play a role, it is also possible to use inorganic polycondensation processes, such as crosslinking of SiOH groups.
  • binders in which various mechanisms are used, e.g. a condensation in a sol-gel process in conjunction with an organic crosslinking reaction, e.g. a radical polymerization.
  • organic crosslinking reaction e.g. a radical polymerization.
  • binders and methods have already been described.
  • WO 2007/121972 and WO 2007/121975 describe inorganic-organic binders which are obtained from condensates of orthosilicic esters, alkoxysilanes, functionalized silanes which carry polymehsierbare groups, and metal or boron compounds and polymerizable organic compounds, especially monomers. It is characteristic of these binders that a covalent bond between the inorganic part and the organic part of the binder takes place via the nonhydrolyzable polymerisable group on the functionalized silane.
  • the disadvantage of the chemical structure resulting from this approach is that the combination of the three-dimensionally crosslinking inorganic building block (the polymerizable group-carrying silane) generally produces very inflexible products which are prone to embrittlement and whose mechanical strength is thereby limited. To avoid such embrittlement, it is therefore necessary that the proportion of the organic component in the binder is relatively high. Moreover, with such a structure, an inhibition of the inorganic polycondensation can also occur, which in turn impairs the chemical resistance or the ecological resistance, especially at high pressures and temperatures.
  • the three-dimensionally crosslinking inorganic building block the polymerizable group-carrying silane
  • IPN Interpenetrating networks, see eg Römpp Chemie Lexikon, 9th edition, p. 2007
  • the invention therefore provides a process for preparing a binder comprising a) a heterocondensate of at least one hydrolyzable silicon compound having at least one non-hydrolyzable organic radical, and at least one metal or boron compound, wherein the metal is selected from Al, Ga, In, Tl, Ge, Sn, Pb, Ti, Zr, Hf, Sc, Y and La, and optionally b) at least one organic binder component ready, wherein
  • A) the silicon compound is mixed with water for hydrolysis and
  • the metal or boron compound is added to the resulting reaction mixture when the added water in the reaction mixture has been substantially consumed, and optionally
  • the organic binder component is added to the resulting heterocondensate or a precursor thereof, wherein the one or more non-hydrolyzable organic radicals of the hydrolysable silicon compounds used have no polymehsierbare group.
  • the process according to the invention surprisingly provides binders which have improved flexibility and less brittleness than binder materials according to the prior art described above with a corresponding proportion of organic component.
  • the organic constituents for example in the form of monomers, oligomers or, where appropriate, provided that sufficient solubility of the polymer in a given solvent, even in the form of polymers.
  • the inorganic constituents for example via the sol-gel process, can be prepared separately.
  • the metal- or boron-containing binder at least one silicon compound and at least one metal- or boron-containing, preferably one titanium-containing component are used.
  • an organic matrix former may also be added to the binder.
  • homogeneous metal- or boron-containing binders which, when used for the production of a shaped article, markedly improve the corrosion resistance of the shaped article obtained are obtained by the process according to the invention.
  • poly (alkoxysilanes) or polyalkyl siloxanes, with reactive end groups can be improved, wherein the elasticity of the molding results by forming a long-chain inorganic network.
  • a heterocondensate of silicon compounds and metal or boron compounds is formed.
  • At least one hydrolyzable silicon compound having at least one non-hydrolyzable organic radical is used as the Si component, with the organic radical (s) of the Si compounds used not carrying any polymerizable groups. Two or more of these compounds may be used together.
  • the at least one hydrolyzable silicon compound having at least one nonhydrolyzable organic group which does not comprise polymerizable groups is e.g. a compound or an organosilane of the general formula (I)
  • hydrolytically removable or hydrolyzable groups X are hydrogen, halogen (F, Cl, Br or I, in particular Cl or Br), alkoxy (eg. Ci-6-alkoxy, such as. Methoxy, ethoxy, n-propoxy, i-propoxy and n-, i-, sec- or tert.-butoxy), aryloxy (preferably C 6 io aryloxy, such as., Phenoxy), alkaryloxy, for example, benzoyloxy, acyloxy (.., for example, Ci-6-acyloxy, preferably Ci -4 acyloxy, such as acetoxy or propionyloxy), alkylcarbonyl and (.
  • halogen F, Cl, Br or I, in particular Cl or Br
  • alkoxy eg. Ci-6-alkoxy, such as. Methoxy, ethoxy, n-propoxy, i-propoxy and n-, i-, sec- or tert.-butoxy
  • C 2 - 7 alkyl-carbonyl such as acetyl
  • NH 2 amino mono- or disubstituted with alkyl, aryl and / or aralkyl, examples of the alkyl, aryl and / or aralkyl radicals given below for R, amido such as benzamido or aldoxime or ketoxime groups.
  • Two or three groups X may also be linked together, e.g. For example, in Si-polyol complexes with glycol, glycerol or pyrocatechol.
  • the groups mentioned may optionally contain substituents such as halogen, hydroxy or alkoxy.
  • Preferred hydrolyzable radicals X are halogen, alkoxy groups and acyloxy groups. Particularly preferred hydrolysable radicals are alkoxy groups, more preferably Ci -4 alkoxy groups, especially methoxy and ethoxy.
  • the hydrolytically non-removable radicals R are z. B. alkyl z.
  • radicals R can have customary substituents, for example halogen, such as chlorine or fluorine, and alkoxy.
  • the radical R has no polymehsierbare group.
  • Preferred radicals R are alkyl groups having preferably 1 to 4 carbon atoms, in particular methyl and ethyl, and also aryl radicals such as phenyl.
  • organosilanes of the general formula (I) are compounds of the following formulas:
  • silanes of the formula (I) are alkylsilanes, in particular alkyltrialkoxysilanes, methylthemethoxysilane and in particular methylthethoxysilane (MTEOS) being particularly preferred.
  • At least one hydrolyzable silane without nonhydrolyzable organic groups may be added. If such silanes are used without nonhydrolyzable groups, they are preferably mixed together with the hydrolyzable silicon compound for hydrolysis with water and together form the Si component. If such silanes are used without nonhydrolyzable groups, they are also used e.g. with regard to the added water or the ratio of Si to metal or boron to be adjusted as Si component.
  • silanes of the general formula (II) SiX 4 , in which the radicals X have the abovementioned meaning, including the preferred meaning, for X in formula (I).
  • the radicals X have the abovementioned meaning, including the preferred meaning, for X in formula (I).
  • Concrete examples are Si (OCH 3 ) 4 , Si (OC 2 Hs) 4 , Si (OC 3 H 7 ) 4 , SiCl 4 , HSiCl 3 , Si (OOCCH 3 ) 4 .
  • TEOS tetraethoxysilane
  • Silanes and polysiloxanes described below can be prepared by known methods; see. W. NoII, "Chemistry and Technology of Silicones", Verlag Chemie GmbH, Weinheim / Bergstrasse (1968).
  • heterocondensate As a further component for the heterocondensate is an additional compound, in particular a hydrolyzable compound, of an element selected from III. Main Group, IV. Main Group, III. Subgroup and IV. Subgroup used. These are B and a metal from these groups, in particular Al, Ga, In, Tl, Ge, Sn, Pb, Ti, Zr, Hf, Sc, Y and La. Through this component, the corrosion resistance and hydrolysis resistance of hardened binder increased. Hydrolyzable compounds of titanium, aluminum, zirconium, tin and boron are particularly preferred, with titanium compounds being most preferred. The compounds may be used singly or as a mixture of two or more of these elements.
  • the metal or boron compound may be a compound of formula (III)
  • MX 3 (III) wherein MB, Al, Ga, In, Tl, Ge, Sn, Pb, Ti, Zr, Hf, Sc, Y and La, X is as defined in formula (I), including the preferred examples, where two groups X can be replaced by an oxo group, and a corresponds to the valency of the element, wherein when complex ligands a are also larger or, in the case of multidentate ligands, they can also be less than the valence of M.
  • the valence of M is usually 2, 3 or 4.
  • the compound of formula (III) also includes a counterion.
  • X may also be sulfate, nitrate, a complexing agent such as a ⁇ -diketone, a saturated or unsaturated carboxylic acid or the salt thereof, an inorganic acid or a salt thereof and an aminoalcohol.
  • the metal or boron compound is in particular a hydrolyzable compound. Preference is given to using metal or boron alkoxides.
  • metal or boron compounds comprising complexing ligands or a combination of metal or boron compounds and a complexing ligand are employed.
  • a combination of metal or boron compounds and a complex ligand in situ results in a binding of the complex ligand to the metal or boron of the metal or boron compound used.
  • a complexing agent is chosen, which can make such a connection.
  • Suitable combinations can readily be selected by the person skilled in the art. The combination may e.g. can be obtained by simply mixing the two components.
  • the complexing agent comprises a polymerizable radical.
  • the binders obtained therewith show a surprising amount of example, an increased pressure resistance.
  • the polymerisable organic group may be any conventional group known to those skilled in the art which is capable of undergoing polymerization with itself or with one or more other corresponding polymerizable groups.
  • the polymerizable group should be able to undergo a polymerization reaction, in particular under the given conditions (temperature, other optional corresponding groups, catalyst, etc.), for example during preparation or, in particular, curing. Polymerization also includes polycondensation and polyaddition in the description in addition to free-radical polymerization.
  • the polymerisable group of the complexing agent is preferably reactive with the polymerizable group of an organic binder component used, if used, so that it is assumed that a connection between organic and inorganic network is achieved by complexing the metal or boron compound with the complexing agent.
  • complexing agents including those having a polymerizable group are acetylacetonate, ethylacetoacetate, vinylacetoacetate, methacrylic acid, di-alkyldithiophosphate, dodecylbenzenesulfonic acid, vinylpyridine, vinylbenzenesulfonic acid, oleic acid, palmitic acid, and more preferably 2- (methacryloyloxy) ethylacetoacetate.
  • polymerizable groups or groups wherein thermally polymerizable groups are preferred, which may have the complexing agent and the organic binder component explained below, are epoxide, such as.
  • epoxide such as.
  • glycidyl or glycidyloxy hydroxy, amino, monoalkylamino, dialkylamino, optionally substituted anilino, amide, carboxy, alkenyl, acrylic, acryloxy, methacrylic, methacryloxy, mercapto, cyano, isocyanato, aldehyde, keto, alkylcarbonyl, acid anhydride and phosphoric acid.
  • Preferred polymerizable groups are acrylic or acryloxy, methacrylic or methacryloxy.
  • metal compounds the alkoxides of Ti, Zr and Al, in particular Ti, are preferred.
  • Suitable metal or boron compounds, including those with a complexing agent are, for example, Ti (OC 2 H 5 ) 4 , Ti (on or iC 3 H 7 ) 4 , Ti (OC 4 Hg) 4 , TiCl 4 , Ti (O).
  • a combination of the metal or boron compound with the desired complexing agent can be used.
  • the molar ratio of Si atoms of all the Si compounds used to the metal atoms and boron atoms of all the aforementioned metal and boron compounds used can be selected in a wide range, but is preferably from 10: 1 to 1: 3, and more preferably from 5: 1 to 1: 1 ,
  • metal compounds can be used.
  • metal compounds are compounds of other glass or ceramic-forming metals, in particular compounds of at least one metal from the main group V and / or the subgroups II and V to VIII of the Periodic Table of the Elements. These are preferably hydrolyzable compounds of Mn, Cr, Fe, Ni and in particular V or Zn. Also usable are, for example, hydrolyzable compounds of elements of the main groups I and II of the Periodic Table z. B. Na, K, Ca and Mg. Also hydrolyzable compounds of lanthanides such as Ce can be used.
  • metal compounds of the general formula M 1 X 3 in which M 'is a metal of main groups I, II or V or subgroups II and V to VIII of the Periodic Table of the Elements or a lanthanide, X and a are as in formula (III) are defined.
  • a purely organic component is added, so that an additional organic matrix can be built.
  • an organic binder component By additionally using such an organic binder component, even further improved mechanical strength and flexibility can be achieved.
  • two interpenetrating polymers namely the heterocondensate and a purely organic polymer, are formed to form IPN polymers, which have been generally described above.
  • the interpenetrating polymers can be purely physically mixed. Without wishing to be bound by theory, some binding of heterocondensate and purely organic component can be achieved via the above-described use of complexing agents having a polymerizable group.
  • connection via complexation a connection via ionic interactions, dipolar interactions, hydrogen bonds, or van der Waals interactions is conceivable. If, for example, vinylpyridine is used as the monomer for the organic component, the pyridine nitrogen with Si-OH groups of the inorganic component can facilitate attachment via ionic bonding via acid / base reactions.
  • organic binder component one or more organic monomers, oligomers or polymers are used which, in a preferred embodiment, each have one or more polymerizable groups, in particular thermally polymerizable groups. It is also possible to use a mixture of two or more monomers, oligomers or polymers. In an alternative embodiment, organic oligomers or polymers can be used which have no polymerizable groups, i. non-reactive oligomers or polymers. The respective advantages of the alternatives are described below.
  • the organic binder component comprises polymerizable groups
  • the presence of at least two polymerizable groups is preferred.
  • the polymerizable groups are used for the polymerization or linking of the organic nischen component, which may be a polymehsierbare group or corresponding polymehsierbare groups. It is preferably selected so as to be reactive with the polymerizable group of the chelating agent, if employed.
  • Organic monomers, oligomers or polymers as a binder component are well known to those skilled in the art and can readily be selected as appropriate according to need.
  • the organic component used may be defined individual compounds or mixtures of compounds with different degrees of polymerization.
  • polymers are z.
  • polyisocyanates melamine resins, polyesters and epoxy resins.
  • Mono-, bi- or polyfunctional acrylates and methacrylates are preferably used as binder component.
  • Further examples of the organic binder component are diethylene glycol dimethacrylate (DEGMA), triethylene glycol dimethacrylate (TEGDMA), bisphenol A glycidyl methacrylate (BisGMA), bisphenol A diacrylate, butyl acrylate (AB), diurethane dimethacrylate, urethane dimethacrylate (UDMA), styrene, styrene derivatives, vinylpyridine, vinylbenzenesulfonic acid, Laromer ® -Acry- late BASF, Ebecryl ®, pentaerythritol triacrylate (PETIA), hexanediol diacrylate, Th- methylolpropanthacrylat, trimethylolpropane trimeth
  • polysiloxanes for example poly (alkoxysilanes) or polyalkylsiloxanes or corresponding polyarylsiloxanes and copolymers thereof. It can be used polysiloxanes which carry no reactive groups. However, preference is given to using polysiloxanes which have at least one reactive group, in particular a reactive end group. It can thereby obtain IPN polymers with covalent bonds between the interpenetrating polymers. However, it is also possible to form IPN polymers which are purely physically mixed.
  • polysiloxanes there is a wide variety of poly (alkoxysilanes), polyalkylsiloxanes and polyarylsilanes and copolymers thereof with reactive end groups.
  • polysiloxanes in particular polyalkylsiloxanes, having commercially available reactive groups or end groups, for example from Gelest, Inc., Philadelphia.
  • the reactive group or end group are vinyl, hydride, silanol, alkoxy, amines, epoxy, carbinol, methacrylate / acrylate, mercapto, acetoxy, chloride and dimethylamine.
  • the polysiloxanes can be incorporated or crosslinked into the inorganic network and optionally into the organic matrix via the reactive groups or end groups.
  • silanol-terminated polysiloxanes when silanol-terminated polysiloxanes are used, the silanol group will react with hydroxy groups of the hydrolyzed silanes or the metal or boron compounds. As a result, the elasticity or compressive strength of the molding is surprisingly increased even further.
  • the polysiloxanes may be cyclic, branched or preferably linear.
  • the reactive group may be present on the main chain or a side chain, but is preferably an end group. Of course, more than one reactive group may be present, e.g. 2 or more reactive groups.
  • a linear polysiloxane contains e.g. preferably 2 reactive end groups.
  • polysiloxanes having reactive groups or end groups polysiloxanes having silanol and alkoxy groups are preferably used, in particular silanol-terminated polysiloxanes.
  • poly (alkoxysilanes), polyalkyl or polyarylsiloxanes and copolymers thereof are polydimethylsiloxanes, polydiethylsiloxanes, polymethylethylsiloxanes, polydiphenylsiloxanes and corresponding copolymers which each contain at least one reactive group.
  • Specific examples are silanol-terminated or alkoxy-terminated polydimethylsiloxanes, poly (diethoxysiloxanes) and polydimethoxysiloxanes.
  • the molecular weight of the polysiloxanes used can be selected from a wide range, for example in the range from 100 to 10,000 g / mol. Preference is given to polysiloxanes having a molecular weight of from 100 to 3500 g / mol and more preferably from 300 to 3000 g / mol, for example from 400 to 2000 g / mol. It is also possible to use relatively high molecular weight polysiloxanes, for example having a molecular weight of up to 50,000 g / mol or more. By molecular weight is meant here the number average molecular weight.
  • the reaction between polysiloxanes and silicon compounds or metal or boron compounds can take place in the presence of a catalyst, for example hexachloro-platinic acid, dibutyltin diacetate, tin 2-ethylhexanoate, or at elevated temperature, for example 8O 0 C, without first the silicon compounds and / or metal - or to have to hydrolyze boron compounds.
  • a catalyst for example hexachloro-platinic acid, dibutyltin diacetate, tin 2-ethylhexanoate, or at elevated temperature, for example 8O 0 C, without first the silicon compounds and / or metal - or to have to hydrolyze boron compounds.
  • the weight ratio of all the inorganic components used, including the organic groups contained therein, to the purely organic components used, if used, can be chosen in wide ranges and, based on the cured binder, e.g. 95: 5 to 5:95 and preferably 80:20 to 20:80.
  • IPN polymers can be built up from interpenetrating polymers, namely the heterocondensate and the purely organic polymer.
  • hydrolyzable silanes and the metal or boron compound by a two-stage process according to the invention by means of hydrolysis and partial condensation (precondensation) heterocondensates as a soluble to viscous system, which then preferably with the above-mentioned organic binder component is mixed with or without a solvent, wherein the organic binder component is preferably added after a maturation of the prepared heterocondensate.
  • an organic binder component it may be advantageous to obtain a sufficiently low viscosity mass by using the organic portion in the form of monomers or short-chain oligomers each having at least one polymerizable group. These are then polymethylated during curing. Not yet completely hydrolyzed or polycondensed Inorganic components can be further reacted, for example, during curing by diffusion of moisture, so that a stable inorganic network is formed.
  • Another variant is the use of non-reactive oligomers or polymers as organic binder component.
  • the advantage of such systems without a polymerizable group in the organic binder component is that polymerization shrinkage no longer occurs.
  • the hydrolyzable silanes used, which carry a high proportion of non-polymerizable organic groups it is thus possible to prepare binders which virtually no longer show any shrinkage during gel formation or solidification (curing) and are thus suitable in particular for sealing.
  • amphiphilic binders which have good adhesion to both hydrophilic and hydrophobic surfaces.
  • the advantage of this property is that e.g. loose or loose substrates such as beds can be bound or filled, regardless of whether they have a hydrophilic or a hydrophobic surface.
  • the chemical resistance of the systems is adjusted by the nature of the organic components, in particular depending on their polymerizable groups, but also by the appropriate choice or synthesis of the inorganic constituent. For example, it has been found that composites containing exclusively Si-containing components as an inorganic constituent, which are converted into corresponding silicate networks by hydrolysis and condensation, re-dissolve very rapidly under hydrothermal conditions.
  • the hydrolyzable silanes are first prehydrolyzed by the addition of water until practically complete consumption of water, that is to say the hydrolysis of the hydrolyzable silanes. until the free water in the mixture is substantially consumed by conversion of SiOR to SiOH groups so that substantially no free water is left.
  • the fast-reacting metal or boron compound such as an alkoxide, e.g. a titanium alkoxide, aluminum alkoxide, zirconium alkoxide, an immediate linkage of the metal or boron of the metal or boron compound with the SiOH group is achieved.
  • an alkoxide e.g. a titanium alkoxide, aluminum alkoxide, zirconium alkoxide
  • an immediate linkage of the metal or boron of the metal or boron compound with the SiOH group is achieved.
  • additional water
  • the hydrolyzable silicon compound is first subjected to hydrolysis in the first stage by mixing with water.
  • the hydrolyzable compounds are generally hydrolyzed with water, if appropriate in the presence of acidic or basic catalysts.
  • the hydrolysis is carried out in the presence of acidic catalysts, for. Hydrochloric acid, phosphoric acid or formic acid, at a pH of preferably 1 to 3. Details of the sol-gel process are, for example, at CJ.
  • hydrolysis stoichiometric amounts of water, but also smaller or larger amounts can be used, for example, up to 1, 2 moles of water per mole of the hydrolyzable groups present. Preference is given to using a substoichiometric amount of water, based on the hydrolyzable groups present.
  • the amount of water used for the hydrolysis and condensation of the hydrolyzable compounds is preferably from 0.1 to 0.9 mol, and more preferably from 0.25 to 0.75 mol of water per mole of hydrolyzable groups present.
  • hydrolyzable groups are here all hydrolyzable groups of the total added starting compounds understood, including those of the later added metal or boron compounds.
  • the process according to the invention is a two-stage process, whereby a very homogeneous heterocondensate with markedly improved properties can be obtained.
  • hydrolysis of the silanes takes place first.
  • the hydrolysis consumes the added free water.
  • the hydrolyzed silanes can then undergo condensation reactions, in which water is released again.
  • condensation reactions may optionally begin even before the silanes have been completely hydrolyzed, the content or concentration of free water in the mixture after addition of the water will be reduced to a minimum over time and then increase again due to condensation reactions.
  • the water used is first completely or substantially completely consumed before water is released again by the condensation, i. At a minimum, there is virtually no water or only little water in the mixture.
  • the metal or boron compound is added to the mixture of the hydrolyzable silicon compound and water when the Water in the reaction mixture has been substantially consumed by the hydrolysis, ie at the time of addition of the metal or boron compound, no water or only a small amount of water is present in the reaction mixture, preferably less than 15%, more preferably less than 10%, and especially preferably less than 5% of the amount of water added for hydrolysis.
  • the metal or boron compound is also particularly added before the condensation reactions again form a higher level of free water in the reaction mixture.
  • the appropriate period of time for the addition of the metal or boron compound can also be determined empirically eg in preliminary tests in which the metal or boron compound is added at certain times to the mixture hydrolyzable silicon compound / water and then tested, for example by photocorrelation spectroscopy (PCS) whether particles are formed which are the oxides of the metal or boron compound, such as TiO 2 particles. If such particles form, the addition is too early or too late. The appropriate time for addition in which these particles are not formed can be easily determined in this way.
  • PCS photocorrelation spectroscopy
  • Another easy method to determine the time of addition is to determine the clear point.
  • Addition of water to the hydrolyzable silicon compound results in an aqueous and an organic phase. This is indicated by turbidity of the stirred reaction mixture. At the clear point, these two phases merge and the reaction mixture clears up. Even if the reaction mixture remains cloudy, for example because of existing polysiloxanes, this clear point is recognizable. Since the clearing usually occurs approximately when the added water has been substantially consumed or the water content is minimal, the metal or boron compound can be added when the clearing point has been reached. This includes, of course, an addition just before or after the clearing.
  • the resulting binder can be used as is.
  • the forming SoI can be determined by suitable parameters, for. For example, degree of condensation, solvent or pH, are set to the desired viscosity for the binder.
  • the binder is allowed to age by simply standing, e.g. for at least 1 h and preferably at least 5 h. After that it can be used for the intended application.
  • the intended amount of water can be completely added in step A). In one embodiment, part of the intended amount may be added only after the addition of the metal or boron compound. In this case, not 100% of the intended amount of water as described above in step A) can be used for the hydrolysis, but for example 90 to 20% and preferably 70 to 30% of the intended amount of water as described above. The remainder of the intended amount is then, for example, directly after the addition of the hydrolyzable Metal or boron compound or preferably added after maturation. In another embodiment, 100% of the intended amount of water as described above in step A) may be used for hydrolysis and an additional amount of water may be added after the addition of the metal or boron compound. Appropriate amounts for the additional water then correspond to the amounts given above for step A). It can also be added more water, especially after maturation.
  • the above-described optional and preferably used organic binder component is, as stated, preferably added after preparation of the heterocondenstate, but it can also be added beforehand.
  • the binder component is added to a precursor of the heterocondensate, e.g. to the hydrolyzable or hydrolyzed silicon compounds or to the metal or boron compound.
  • the polysiloxane component is preferably introduced together with the other Si components before the water is added. If necessary, it can also be added at a later date.
  • the additional metal compounds described above are preferably added together with the metal or boron compound of the formula (III).
  • solvents may also be added after the preparation of the binder, e.g. for adjusting the viscosity. If appropriate, additional water may also be used for this purpose, but preferably only after ripening.
  • the binder produced may also contain conventional additives as required.
  • Thermal or photolytic catalysts for the polymerization are preferably also added to the binder, preferably thermal initiators. It may be, for example, ionic starter or radical starter.
  • the catalyst initiates the polymerization, whereby the binder is cured or crosslinked.
  • thermal initiators may be, for example, ionic starter or radical starter.
  • the catalyst initiates the polymerization, whereby the binder is cured or crosslinked.
  • free-radical thermo-initiators are organic peroxides, for example diacyl peroxides, peroxydicarbonates, alkyl peresters, alkyl peroxides, perketals, ketone peroxides and alkyl hydroperoxides, and azo compounds.
  • dibenzoyl peroxide Trigonox ® 121
  • tert-butyl perbenzoate amyl peroxy-2-ethylhexanoate
  • azobisisobutyronitrile An example of an ionic initiator suitable for thermal initiation is 1-methyl in idazole. These starters are used in the customary amounts known to the person skilled in the art, for example from 0.01 to 5% by weight, based on the total solids content of the binder.
  • Examples of usable further solvents are alcohols, preferably lower aliphatic alcohols (C 1 -C 8 -alcohols), ketones, ethers, monoethers of diols, such as ethylene glycol or propylene glycol, with C 1 -C 4 -alcohols, amides, tetrahydrofuran, dioxane, sulfoxides, sulfones or butyl glycol and their mixtures.
  • alcohols are used. It can also be used high boiling solvents. In some cases, other solvents are also used, for example light paraffins.
  • the resulting binder according to the invention is usually free of particles as a solution or emulsion, it is in particular free of crystalline products or particles. In particular, it is a binder sol.
  • PCS photocorrelation spectroscopy
  • a binder comprising a heterocondensate which is a metallo or borosiloxane and heteroatom units of heteroatoms selected from B, Al, Ga, In, Tl, Ge, Sn, Pb, Ti, Zr, Hf, Sc , Y and La, which are incorporated via oxygen bridges in the siloxane skeleton, and Siloxane units in which the silicon atom has a non-hydrolyzable organic radical, wherein the organic radical does not comprise a polymerizable group.
  • the heteroatom is incorporated into the siloxane skeleton via 2, 3 or 4 oxygen bridges.
  • B, Al, Sn, Ti or Zr are preferably used as heteroatoms, so that boro-, alumino-, stanno-, titano- or zirconosiloxanes are formed, titanium siloxanes being particularly preferred.
  • the heterocondensate also comprises the corresponding siloxane units.
  • heterocondensate can be schematically illustrated without regard to proportions or distribution as follows, wherein the radicals R represent the nonhydrolyzable organic group and X represent the hydrolyzable group as defined in the above formulas:
  • the undefined valences in the scheme may mean substituents according to the above formulas, OH groups or oxygen bridges.
  • very homogeneous heterocondents can advantageously be formed, in which the heteroatoms are homogeneously distributed in the condensate, ie in a molecular dispersion.
  • the heteroatoms condense with common hydrolysis substantially with each other, so that, for example, in the case of Ti essentially Ti ⁇ 2 particles are formed in addition to a Siloxankondensat and no homogeneous heterocondensates are obtained.
  • binders are present even after a longer time than sol or solution and do not form a gel. So the binders gelled only after days.
  • the stability of the binder brine is important because gelled binders are no longer useful, since mixing with the respective material is no longer possible. According to the invention stable and thus storable binders are obtained.
  • the substrate to be bonded may be e.g. from metals, non-metals, glass, ceramics, carbon, oxides, nitrides, carbides, borides, minerals, plastics, plastic fibers, glass fibers, mineral fibers, natural fibers, sand, soil, gravel, concretes, cements and wood-based materials.
  • the substrate may e.g. a geological formation, a grain or bed, soil or rock.
  • the binder of the invention is used to strengthen the substrate, e.g. of inorganic granules, e.g. Sand, used.
  • the substrate e.g. of inorganic granules, e.g. Sand
  • a bed of the substrate mixed with the binder and then cured.
  • the mixture can be carried out in the usual way, e.g. by mixing or infiltrating the binder into the substrate to be consolidated, e.g. by pumping.
  • the curing of the binder or of the shaped body is preferably carried out thermally by supplying heat.
  • suitable catalysts or starters have been mentioned above.
  • Another type of curing is the supply of condensation catalysts, which further cross-linking the inorganic crosslinkable SiOH groups or metal-OH groups to form an inorganic effect a niche network.
  • condensation catalysts are z.
  • bases but also fluoride ions.
  • the properties of substrates bound with a binder also depend on the conditions under which they are cured. Hardening is also referred to as setting. In general, an improved behavior is obtained when the setting process is carried out under approximately the same conditions in which the set substrates are to be used or are present. For applications at elevated pressures and temperatures, it is therefore desirable to also carry out the production under approximately the same conditions.
  • hydrothermal conditions exist in relatively large water depths, ie an elevated temperature and elevated pressure, so that it is expedient for applications in such water depths, the setting also at the corresponding hydrothermal conditions, for example at temperatures above 40 0 C and at least 4 bar , or directly on site of the operation.
  • a particular advantage of the binder according to the invention is that it can be cured or set even under such hydrothermal conditions, so that it is particularly suitable for applications under these conditions, such as under water.
  • the setting is carried out for such applications preferably at elevated temperature and elevated pressure, based on the normal conditions, ie, the pressure is greater than 1 bar and the temperature is higher than 20 0 C.
  • the binder according to the geological conditions of the reservoir in which it is used usually cured at temperatures above 40 ° C and pressures of at least 40 bar.
  • the use of the organic component also achieves improved mechanical strength and good flexibility by formation of the IPN polymer after setting.
  • the binder according to the invention can be converted via a purely inorganic condensation mechanism or via additional polymerization reactions (parallel to the condensation, before the condensation or after condensation). sation).
  • organic polymerizable, polyaddable or polycondensable components can be used.
  • set shrinkage behavior can be done a seal or only a solidification of a bed or a grain.
  • the behavior of the binder of the invention can be controlled so that spaces or channels, e.g. in formations, grits and fillings, are fully filled in or remain open in whole or in part.
  • the consolidation of the bound substrate can thus lead to a seal when filling the gaps or channels or, in the absence of filling, to an at least partial retention of the permeability of the unbound substrate.
  • the binder is e.g. consists mainly or exclusively of the inorganic component
  • the permeability of the substrate can be maintained due to the syneresis effect described above, since the substrate remains porous.
  • the organic binder component rather leads to a filling of the pores or channels and thus to a seal.
  • consolidation and sealing or strengthening and at least partial retention of the permeability can thus be achieved.
  • an organic binder component of non-reactive oligomers or polymers is preferably used, e.g. a complete seal of the substrate is desired.
  • the binder can close pores in large volumes. This may for example preferably by displacing the liquid binder from the pores, for example by blowing a liquid or gaseous medium, such as air or nitrogen, into the material to be bonded, which is mixed with the binder, so that only at the contact points of the grains remains binder, prevented or eliminated the, whereby a porosity can be adjusted in the desired manner.
  • the blowing in takes place in particular before or during setting over a certain period of time.
  • Parameters for the pumping such as duration, time, amount or flow rate of the liquid or gaseous phase can be readily selected by the skilled person in a suitable manner to adjust the desired porosity.
  • the initiation can be carried out, for example, before or after a partial hardening, with complete curing taking place after and / or during the initiation.
  • a liquid or gaseous medium for example, an inert solvent or gas, for. B. N 2 , CO 2 or air, are pumped, whereby the pore volumes are flushed and reaction products are removed.
  • the liquid or gaseous medium may optionally contain catalysts and / or gas-releasing components or solutes.
  • the binder according to the invention can thus be used for the formation or solidification of moldings or formations.
  • the binder can be used for the consolidation of geological formations or of granulate beds, in particular in the field of oil and gas production.
  • the binder is also suitable for consolidating molding sands. Further fields of application for the binder are the consolidation of friable sandstones in architecture or the production of brake linings.
  • the binder according to the invention Due to its chemical constitution, the binder according to the invention, as explained above, enables rapid and effective solidification of oil-bearing or water-bearing, mostly sand-containing, geological formations. It has furthermore been found that the binders are also particularly suitable for contaminated sands, in particular oil-contaminated sands, since the binder can infiltrate and detach dirt, in particular an oil layer, on the inorganic surface. The latter has the additional effect that such systems are also suitable to replace fats and oils of inorganic surfaces and z. B. to improve the discharge of such substances from the interstices of sand fillings or geological formations. It thus succeeds in binding processes in To realize oily sands and to purify such sands of oil. Treatment of contaminated sand with the binder may thus have a tightening or a cleaning function or fulfill both purposes.
  • the heterocondensate can additionally contain a component which is oleophobic and hydrophobic, whereby the wetting behavior of geological formations can be changed.
  • a component which is oleophobic and hydrophobic e.g., silanes of the general formula (V)
  • Rf is a non-hydrolyzable group having from 1 to 30 fluorine atoms attached to aliphatic carbon atoms and b is 0, 1 or 2. These compounds are also referred to below as fluorosilanes.
  • the silane can be used in the process of the invention as additional Si component as well as described above for the other optional Si components.
  • Rf is preferably a fluorinated alkyl group, eg having 3 to 20 C atoms, and examples are CF 3 CH 2 CH 2 , C 2 F 5 CH 2 CH 2 , nC 6 Fi 3 CH 2 CH 2 , i - C 3 F 7 OCH 2 CH 2 CH 2 , nC 8 Fi 7 CH 2 CH 2 and n-CioF 2 rCH 2 CH 2 .
  • Preferred examples of Rf are 1H, 1H, 2H, 2H-perfluorooctyl.
  • the binder may cause a change in the wetting behavior of sands so that it serves as a wetting-regulating agent.
  • it may be expedient to use the binder in high dilution, for example with a maximum solids content of 10% by weight.
  • MEAA was added to TPT at RT and stirred for 30 min.
  • MTEOS was hydrolyzed with 1 M HCl. After the clear point, the solution of MEAA and TPT was added. The mixture was stirred at RT for 1 h and then DEGMA and AB were added. The curing was carried out with 2 wt .-% Trigonox 121 at 60 0 C for 12h.
  • the measured compressive strength depends on whether the samples are measured immediately after removal from the autoclave in the wet state or whether the samples are dried before the pressure resistance test.
  • the "recovery time” was about 30 minutes.
  • Viscosity of the binder at RT about 3 cP
  • solids content theoretical
  • 71, 1% solids content
  • UCS strength uniaxial compressive strength
  • the viscosity of the binder in the rheometer (at 150 psi) is measured with increasing temperature. From one point, the viscosity increases rapidly. This is considered as the start of the polymerization.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un liant contenant un hétérocondensé constitué d'un composé de silicium comprenant au moins un radical organique non-hydrolysable, et d'un composé de métal ou de bore, et éventuellement un constituant de liant organique. Le composé de silicium est mélangé à de l'eau pour l'hydrolyse et le composé de métal ou de bore est additionné au mélange de réaction obtenu lorsque l'eau ajoutée est essentiellement consommée dans le mélange de réaction, et le constituant de liant organique est éventuellement additionné à l'hétérocondensat obtenu ou à un précurseur de celui-ci. Le ou les radicaux non-hydrolysables des composés de silicium hydrolysables employés ne présentent pas de groupe polymérisable. Les hétérocondensats homogènes obtenus peuvent être employés en tant que liant pour la solidification de substrats meubles et lâches.
EP08859879A 2007-12-10 2008-12-09 Liant anorganique/organique, procédé de fabrication et utilisation Withdrawn EP2250136A1 (fr)

Applications Claiming Priority (2)

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DE200710059423 DE102007059423A1 (de) 2007-12-10 2007-12-10 Anorganisch-organisches Bindemittel, Verfahren zu dessen Herstellung und dessen Anwendung
PCT/EP2008/067094 WO2009074567A1 (fr) 2007-12-10 2008-12-09 Liant anorganique/organique, procédé de fabrication et utilisation

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US9033631B2 (en) * 2009-04-17 2015-05-19 United Technologies Corporation High temperature thread locking compound
US10741316B2 (en) * 2010-02-18 2020-08-11 Höganäs Ab (Publ) Ferromagnetic powder composition and method for its production
GB201119824D0 (en) * 2011-11-17 2011-12-28 Dow Corning Silicone resins comprising metallosiloxane
US8881813B2 (en) 2012-03-26 2014-11-11 Halliburton Energy Services, Inc. Methods of forming high-porosity fractures in weakly consolidated or unconsolidated formations
US9260650B2 (en) 2012-08-29 2016-02-16 Halliburton Energy Services, Inc. Methods for hindering settling of proppant aggregates in subterranean operations
DE102012022731A1 (de) 2012-11-21 2014-05-22 Epg (Engineered Nanoproducts Germany) Ag Hochabriebfeste Antikalkschichten mit hoher chemischer Beständigkeit
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