Highly reactive geopolymer foam formulation for rapid curing process

Abstract

Rapid-expanding and curing geopolymer formulations comprise a liquid aqueous phase having silicates, aluminates and / or silico-aluminate precursors, inorganic bases, monosaccharides and / or disaccharides, and water-soluble peroxy compounds. The sugars and peroxy compounds react spontaneously and rapidly under strongly alkaline conditions to generate exothermic reaction heat and expanding gases that induce at least initial curing of the geopolymer formulation. The resulting foamed geopolymer formulation can be used in various building and construction applications as well as other applications.

Description

Background Technology

[0001] The present invention relates to a geopolymer and a method for manufacturing a geopolymer.

[0002] There is a need to develop non-combustible materials for the construction industry to replace or supplement combustible organic materials such as wood and organic polymers. Inorganic materials are potential alternatives. One specific class of inorganic materials known as "geopolymers" has potential in these applications because they can be produced from inexpensive and readily available raw materials to form slurries or pastes, and can be cast or molded into any arbitrary geometric structure.

[0003] Geopolymers are produced by the condensation of aluminosilicate starting materials in the presence of water and a strong base. This produces an amorphous polymeric Si-O-Al framework having tetrahedral aluminosilicate units having alkali metal ions that balance the charge associated with tetrahedral Al. Geopolymers and methods for producing the same are described, for example, particularly in U.S. Patents No. 4,349,386 and No. 4,509,985.

[0004] Its adoption in construction and other application areas has been partially limited because it requires a long time to cure in a non-stick, self-supporting state at ambient temperatures (e.g., -10°C to 37°C) typically encountered on construction sites. Due to this requirement, geopolymers are unsuitable for many field applications that require faster curing. For example, adhesive and sealant applications generally require materials that rapidly develop adhesive strength, viscosity, and / or "green strength" within minutes or hours rather than days.

[0005] Even when manufacturing prefabricated products (e.g., walls, roof or floor panels, or insulation panels) from geopolymers, a shorter initial curing time is desirable to reduce manufacturing cycle times and increase production rates. Rapid initial curing will enable the material to be handled immediately after being formed into the desired product. While curing can be accelerated by applying heat as the geopolymer formulation cures, this increases costs due to added energy requirements and specialized heating equipment, and supplying heat or maintaining elevated curing conditions for extended periods is often impractical in field applications.

[0006] Geopolymers, like most other inorganic cementitious materials, have a much higher density than the organic materials they can replace. Higher density leads to a significant increase in weight. Therefore, there have been attempts to produce low-density geopolymers. U.S. Patent Application Publication No. 2022 / 0017410A describes incorporating chemical blowing agents, such as carbonates, bicarbonates, hydrazides, and peroxides like hydrogen peroxide and organic peroxides, into geopolymer-forming formulations. The density is 127 kg / m³. 3 Although it is reported to be as low as 3 days in a high humidity, ambient temperature atmosphere, a drying step follows at 70°C.

[0007] EP 3728159B describes a method of producing an aqueous foam by bubbling air or an inert gas into a water-surfactant mixture, and then combining this with an inorganic material to produce a foamed geopolymer. The density of the geopolymer is 47 kg / m³. 3It has been reported to be as low as possible. Unfortunately, this process still has the additional disadvantage of requiring a long curing time to reach a non-stick state and requiring special equipment to handle the gas and incorporate it into the water-surfactant mixture. As such, the process described in EP 3728159B has limited suitability, particularly for field applications.

[0008] Materials and methods are desired for producing low-density geopolymers that cure rapidly even at ambient temperatures. The materials required for the geopolymer foam formulation should primarily be inexpensive, and it is desirable that special equipment is not required to produce, handle, and cure the foam formulation to create the geopolymer product.

[0009] The present invention relates to a method for manufacturing a foamed geopolymer, and the method

[0010] (I) a step of forming an alkaline aqueous slurry having a liquid phase containing water by combining components comprising: (i) one or more inorganic aluminate and / or silicate precursor materials—the one or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1:1 to 4:1—, (ii) one or more inorganic bases selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth hydroxides and alkaline earth oxides, (iii) one or more sugars selected from monosaccharides and disaccharides, (iv) at least 3 moles of a water-soluble peroxy compound per 1 mole of sugar, and (v) water, which disperses and / or dissolves components (i), (ii), (iii), and (iv) in a liquid phase to produce an alkaline aqueous slurry, wherein one or more sugars constitute 1 to 10 weight% of the sum of components (i), (ii), (iii), (iv), and (v), and water comprises components (i), (ii), (iii), Steps constituting 20 to 75% of the combined weight of (iv) and (v), and

[0011] (II) The method includes the step of curing an alkaline aqueous slurry to produce a foamed geopolymer.

[0012] The present invention also relates to an expanded geopolymer obtained by curing an alkaline aqueous slurry having a liquid phase containing water, wherein the alkaline aqueous slurry comprises (i) one or more inorganic aluminate and / or silicate precursor materials—the one or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1:1 to 4:1—(ii) one or more inorganic bases selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth hydroxides and alkaline earth oxides, (iii) one or more sugars selected from monosaccharides and disaccharides and (iv) one or more water-soluble peroxy compounds in an amount of at least 3 moles per mole of sugar, wherein components (i) to (iv) are dispersed and / or dissolved in the liquid phase, and one or more sugars constitute 1 to 10 weight percent of the combined weight of components (i), (ii), (iii), (iv) and water, and water is composed of components (i), (ii), (iii), (iv) It constitutes 20 to 75% of the combined weight of water.

[0013] In addition, the present invention relates to a two-component reactive system for producing a geopolymer, and the system

[0014] (A) a first alkaline aqueous premix having a pH greater than 10, comprising water and one or more inorganic bases selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth hydroxides and alkaline earth oxides, and

[0015] (B) A second aqueous premix comprising water and a water-soluble peroxy compound, comprising a second aqueous premix having a pH of 3 to 10 at 25°C, and

[0016] (1) At least one of (A) and (B) contains one or more inorganic aluminate and / or silicate precursor materials, and

[0017] (2) At least one of (A) and (B) contains one or more sugars selected from monosaccharides and disaccharides, and

[0018] (3) One or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1:1 to 4:1, and

[0019] (4) One or more sugars constitute 1 to 10% of the combined weight of (A) and (B);

[0020] (5) At least 3 moles of one or more water-soluble peroxy compounds are present per 1 mole of one or more sugars, and

[0021] (6) Water makes up 20 to 75% of the combined weight of (A) and (B). Specific details for implementing the invention

[0022] The present invention is a method for manufacturing a foamed geopolymer, and the method

[0023] (I) a step of forming an alkaline aqueous slurry having a liquid phase containing water by combining components comprising: (i) one or more inorganic aluminate and / or silicate precursor materials—the one or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1:1 to 4:1—, (ii) one or more inorganic bases selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth hydroxides and alkaline earth oxides, (iii) one or more sugars selected from monosaccharides and disaccharides, (iv) at least 3 moles of a water-soluble peroxy compound per 1 mole of sugar, and (v) water, which disperses and / or dissolves components (i), (ii), (iii), and (iv) in a liquid phase to produce an alkaline aqueous slurry, wherein one or more sugars constitute 1 to 10 weight% of the sum of components (i), (ii), (iii), (iv), and (v), and water comprises components (i), (ii), (iii), Steps constituting 20 to 75% of the combined weight of (iv) and (v), and

[0024] (II) The method includes the step of curing an alkaline aqueous slurry to produce a foamed geopolymer.

[0025] This method has significant advantages. It requires only inexpensive and readily available raw materials formulated to produce a fluid slurry that can be applied and worked with by pouring, pumping, extruding, spraying, plastering, or other methods. Even when combined at room temperature or below, the initial reaction between the sugars and the peroxy compounds begins rapidly after the reactants are combined, quickly generating gas that expands the slurry. The reaction between the sugars and the peroxy compounds is highly exothermic. The heat of this exothermic reaction eventually induces a polymerization reaction. Consequently, the reactants expand and harden very rapidly to produce a self-supporting expanded geopolymer. Further hardening can be performed at approximately room temperature if desired, or accelerated by heating to, for example, a temperature of 50 to 100°C. The hardened product is a rigid, non-flammable geopolymer containing gas-filled pores.

[0026] Due to these and other properties, the present method is useful in various construction applications where an alkaline aqueous slurry can be generated on-site, easily applied, and cured. Examples of such construction applications include filling and sealing gaps, cracks, and penetrations within building structures, and applied coatings for building components such as panels, joists, and trusses. Such coatings can, for example, improve the flammability and / or acoustic performance of the surfaces to which they are applied.

[0027] This method is also useful in production environments for manufacturing processed products such as geopolymer foam insulation boards and composites; ceramic tiles, refractory articles, decorative stone-like artifacts, thermal shock refractories, and components for vehicles such as aircraft and automobiles. This method may also be used to produce geopolymers for radioactive and toxic waste containment, and may be used to produce geopolymers for specific medical applications.

[0028] Another advantage of the present invention is that the raw material can be formulated into a two-component reactive system, wherein each component is non-reactive and has long-term storage stability when maintained separately at temperatures typically encountered during transport and storage (e.g., up to 40°C). This provides significant advantages in the packaging, transport, storage, and use of the material. Accordingly, in another aspect, the present invention is a two-component reactive system for producing a geopolymer, wherein the system

[0029] (A) a first alkaline aqueous premix having a pH greater than 10, comprising water and one or more inorganic bases selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth hydroxides and alkaline earth oxides, and

[0030] (B) A second aqueous premix comprising water and one or more water-soluble peroxy compounds, wherein the second aqueous premix has a pH of less than 10 at 25°C, and

[0031] (1) At least one of (A) and (B) contains one or more inorganic aluminate and / or silicate precursor materials, and

[0032] (2) At least one of (A) and (B) contains one or more sugars selected from monosaccharides and disaccharides, and

[0033] (3) One or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1:1 to 4:1, and

[0034] (4) One or more sugars constitute 1 to 10% of the combined weight of (A) and (B);

[0035] (5) At least 3 moles of one or more water-soluble peroxy compounds are present per 1 mole of one or more sugars, and

[0036] (6) Water makes up 20 to 75% of the combined weight of (A) and (B).

[0037] The present invention also relates to an expanded geopolymer obtained by curing an alkaline aqueous slurry having a liquid phase containing water, wherein the alkaline aqueous slurry comprises (i) one or more inorganic aluminate and / or silicate precursor materials—the one or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1:1 to 4:1—(ii) one or more inorganic bases selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth hydroxides and alkaline earth oxides, (iii) one or more sugars selected from monosaccharides and disaccharides, and (iv) at least one water-soluble peroxy compound in an amount of at least 3 moles per 1 mole of at least one sugar, wherein components (i) to (iv) are dispersed and / or dissolved in the liquid phase, and one or more sugars constitute 1 to 10 weight% of the combined weight of components (i), (ii), (iii), (iv) and water, and water is composed of components (i), (ii), (iii), (iv) It constitutes 20 to 75% of the combined weight of water.

[0038] Component (i) is one or more inorganic aluminates, silicates, or aluminosilicates. These materials, alone or in combination, provide silicon and aluminum in a molar ratio of 1:1 to 4:1. Such ratios may be at least 1.25:1, at least 1.5:1, or at least 1.75:1, and at most 3:1, at most 2.5:1, or at most 2.25:1.

[0039] Inorganic aluminate precursor materials include, for example, alumina (Al2O3) and alkali metal aluminates, particularly sodium and / or potassium aluminates, aluminum, and oxygen bonded to aluminum.

[0040] Inorganic silicate precursor materials comprise silicon and oxygen bonded to silicon, and include, for example, silica in amorphous forms, such as microsilica and fumed silica, ground glass, sand, and alkali metal silicates, in particular sodium and / or potassium silicates. Particularly useful inorganic silicate precursor materials are water-soluble alkali metal silicates, in particular potassium silicate and most preferably sodium silicate. The term "alkali metal silicate" is of the formula M 2x Si y O (2y+x) or (SiO2) y · (M2O) x It includes various compounds represented by, where M is sodium and / or potassium, and y and x are positive numbers having a ratio of 1 to 2.85, specifically 1 to 2.5 or 1 to 2.0. Thus, "sodium silicate" typically refers to sodium metasilicate (Na2SiO3), sodium orthosilicate (Na4SiO4), and sodium pyrosilicate (Na6Si2O7) and optionally general formula M 2x Si y O (2y+x) It is a mixture of other species represented as. Alkali metal silicates are conveniently provided in the form of aqueous solutions.

[0041] Inorganic aluminosilicate precursors include silicon and aluminum, each of which is bonded to oxygen. These include, for example, various clays, particularly kaolin; various industrial slags, such as blast furnace slag and steelmaking slag; fly ash, such as lignite fly ash and light coal fly ash; aluminosilicate glass; natural pozzolans, such as tuff, thres, and volcanic ash; and metakaolin. Metakaolin, which is the anhydrous calcined form of kaolin having the approximate empirical formula Al2O7Si2 (sometimes expressed using the notation Al2O3·2SiO2), is a particularly preferred aluminosilicate precursor.

[0042] In a particularly preferred embodiment, component (i) comprises a mixture of sodium silicate and metakaolin providing a silicon:aluminum molar ratio of 1.5:1 to 2.5:1, particularly 1.75:1 to 2.25:1.

[0043] Component (i) may constitute, for example, at least 20%, at least 30%, or at least 35% of the combined weight of components (i), (ii), (iii), (iv), and (v), and may constitute, for example, up to 70%, up to 60%, or up to 50% of the total weight.

[0044] Component (ii) is preferably an alkali metal hydroxide, more preferably potassium hydroxide, sodium hydroxide, or a mixture thereof, and most preferably sodium hydroxide. Component (ii) may be provided in the form of substantially anhydrous (e.g., water content of less than 5 weight%) solid particles or in the form of an aqueous solution. Generally, sufficient component (ii) is provided so that the aqueous alkaline slurry has a pH of at least 10, preferably at least 11. The pH may be measured in any convenient way to determine such high pH values, including using wet pH test paper with the aqueous alkaline slurry.

[0045] Component (iii) is preferably a monosaccharide. Component (iii) may be a reducing sugar or an aldose sugar, and in each case, is preferably a monosaccharide. In some embodiments, the preferred monosaccharide has six carbon atoms; examples of these include, but are not limited to, glucose, mannose, galactose, allose, altrose, and talose. In other embodiments, the preferred monosaccharide has five carbon atoms, such as xylose, arabinose, lixose, and ribose. Xylose is a preferred monosaccharide based on its reactivity with hydrogen peroxide in the presence of alkali and its easy availability. The monosaccharide may be an L- or D-isomer, or a mixture of both isomers. Examples of disaccharides include sucrose, lactose, trehalose, and maltose. Component (iii) may be provided as an aqueous solution if desired. One or more sugar(s) may constitute 1 to 10 weight%, preferably 2 to 10 weight% or 2 to 7.5 weight% of the combined weight of components (i), (ii), (iii), (iv) and (v).

[0046] Component (iv) is a peroxy compound, that is, a compound having at least one -OO- link. Suitable compounds include water-soluble peroxides, peroxy esters, peroxycarbonates, etc. The peroxy compound may be organic as long as it is soluble in water, but more preferably inorganic. Inorganic peroxy compounds include hydrogen peroxide, alkali metal peroxides, such as sodium peroxide and potassium peroxide, and alkali metal peroxycarbonates, such as sodium carbonate and potassium carbonate peroxide. Hydrogen peroxide is most preferred. The water-soluble peroxy compound is preferably provided as a solution in water. At least 3 moles of the water-soluble peroxy compound are provided per mole of sugar; at least 5 moles are preferred if the sugar is a C5 monosaccharide, and at least 6 moles are preferred if the sugar is a C6 monosaccharide. A larger amount of the water-soluble peroxy compound per mole of sugar, such as up to 10 or up to 20 moles of the water-soluble peroxy compound, or even more, may be used.

[0047] Water (component v) generally constitutes 20 to 75% of the combined weight of components (i), (ii), (iii), (iv) and (v). This amount includes water from all sources, including water introduced together with aqueous solutions and / or dispersions of other components. This amount of water is generally sufficient to dissolve the water-soluble components and produce a slurry having manageable rheological properties. The preferred amount of water is at least 30% or at least 40% of the aforementioned criteria, and again up to 65% or up to 60% of the aforementioned criteria.

[0048] An alkaline aqueous slurry is prepared by mixing the aforementioned components. The components can be combined using a simple mixing method suitable for wetting any solid starting material and obtaining a uniform distribution. This can be carried out, for example, at a temperature of -10°C to 40°C, particularly 0°C to 37°C or 10°C to 37°C. The components can be combined at higher temperatures if desired, but this is not essential, and the reaction of the sugar(s) and the water-soluble peroxy compound(s) may be more difficult to control at these higher temperatures.

[0049] Since the sugar / peroxy compound reaction occurs spontaneously when sugars and peroxy compounds are combined in an alkaline environment, it is desirable to keep at least one of these components (sugars, peroxy compounds, and any alkaline substance) separated from the other components until the other components are combined or the combination of the other components is completed.

[0050] Particularly for use in field applications, it is often convenient to formulate an alkaline aqueous slurry into a two-component reactive system. The two components remain separated until they combine to form an alkaline aqueous slurry, which then cures to produce a geopolymer. This can reduce the need to store, measure, and combine materials in the field, reduce formulation errors, and generally improve ease of use. To prevent premature reactions and promote storage stability, the two-component reactive system is formulated to keep at least one of the sugars, hydrogen peroxide, and alkaline substances separated from the others until the two components of the two-component reactive system combine and cure to produce an expanded geopolymer.

[0051] In such an embodiment, one component is a first alkaline aqueous premix comprising water and one or more inorganic bases selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth hydroxides, and alkaline earth oxides. An alkaline aluminate and / or silicate precursor material, such as an alkali metal silicate (if used), is also present in the first component. The first alkaline aqueous premix typically has a pH greater than 10, preferably at least 11 or at least 12. The pH may be up to 18 or up to 17. The other component is a second aqueous premix comprising water and a water-soluble peroxy compound. The second aqueous premix has a pH less than 10, preferably 3 to 9, 3 to 8, or 4 to 8. Other components (non-alkaline inorganic aluminate and / or silicate precursor materials as described below, sugars and optional components) may be freely distributed between the first component and the second component (e.g., by dividing any of these between the first component and the second component), but the single alkaline component is included in the first alkaline aqueous premix, and accordingly, the second aqueous premix containing a water-soluble peroxy compound has a pH of up to 10 as described above.

[0052] In certain embodiments, the first component comprises one or more inorganic bases, alkali metal silicates, and at least one aluminosilicate such as the one described above, preferably metakaolin; and the second component comprises hydrogen peroxide, monosaccharides, and optionally at least one aluminosilicate such as the one described above (preferably metakaolin). In such embodiments, the aluminosilicate may be divided between the first component and the second component if desired, with a portion present in each component. This may have the advantage of producing a first component and a second component having similar viscosity (which facilitates easier mixing) and allowing the first component and the second component to be combined in a simple mixing ratio, for example, 3:1 to 1:3 by volume, 2:1 to 1:2 by volume, or 1:1 by volume, when used to form a geopolymer. The alkaline aqueous slurry produced by mixing the first component and the second component must have a pH greater than 10, preferably at least 11 or at least 12.

[0053] Various optional components may also be provided in the alkaline aqueous slurry. These include various types of surfactants, various water-soluble and / or water-dispersible organic polymers, catalysts for the reaction of hydrogen peroxide with monosaccharides, colorants, and various fillers.

[0054] Surfactants may be provided, for example, to stabilize the cell structure of a reaction mixture that expands as it increases in volume and hardens, and / or as a wetting agent for such components that are not soluble in water or not easily disperseable. Surfactants may be nonionic, anionic, cationic, or amphiphilic. Examples of nonionic surfactants include, but are not limited to, polyether block copolymers, such as poly(propylene oxide)-poly(ethylene oxide) block copolymers, alkylphenol ethoxylates, ethoxylated fatty acids, ethoxylated fatty alcohols, and various silicone surfactants. Examples of anionic surfactants include, but are not limited to, alkyl sulfates, alkyl-ether sulfates, alkyl-aryl ether sulfates, alkyl benzene sulfonates, fatty acid salts, alkyl ether phosphates, and alkyl-aryl ether phosphates. Examples of cationic surfactants include, but are not limited to, various quaternary ammonium compounds having a C8-24 alkyl group, such as cetrimonium bromide, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, dimethyldioctadecyl ammonium chloride, and dioctadecyldimethylammonium bromide. Suitable amphiphilic surfactants are described in US 2020 / 0017410A. Such surfactants may constitute 0.1 to 5%, particularly 0.25 to 2%, of the combined weight of the surfactant(s) and components (i), (ii), (iii), (iv) and (v), where present.

[0055] Water-soluble and / or water-dispersible polymers may be present. These may provide various useful functions, including thickening, imparting thixotropic properties, or other rheological modifications. Examples of such water-soluble and / or water-dispersible polymers include, but are not limited to, hydrophobically modified ethylene oxide urethane rheology modifiers, nonionic urethane rheology modifiers, starch, modified starch, cellulose, cellulose ethers, such as methylcellulose and hydroxymethylcellulose, xanthan gum, carboxymethylcellulose, alginic acid, and salts thereof; acrylic acid homopolymers and copolymers (which may be partially or completely neutralized) and polystyrene sulfonates. Useful hydrophobically modified ethylene oxide urethane rheology modifiers and nonionic urethane rheology modifiers include those sold by The Dow Chemical Company under the trade name Acrysol®. Such water-soluble and / or water-dispersible polymers may constitute 0.1 to 5%, particularly 0.25 to 2%, of the combined weight of the polymer(s) and components (i), (ii), (iii), (iv) and (v), where present.

[0056] Another optional component is a catalyst for the reaction of hydrogen peroxide with one or more monosaccharides. Examples of such catalysts include, but are not limited to, transition metal compounds, such as iron and / or manganese salts, examples of which are ferrous sulfate, MnO2 and KMnO4.

[0057] The components of the alkaline aqueous slurry may further include (viii) one or more fillers. For the purposes of the present invention, the filler is a particulate material having a length-to-diameter ratio of 3 or less that does not react, melt, dissolve, decompose, or degrade under the conditions of a geopolymer-forming reaction. The filler does not participate in the geopolymer-forming reaction(s). The filler may include, for example, thermosetting polymer particles, metal particles, and mineral fillers. The mineral filler may be a naturally occurring and / or synthetic material. Examples of fillers include basalt, limestone, calcium carbonate, magnesium carbonate, spinel, zirconium oxide, magnesium oxide, tin oxide, titanium dioxide, and cerium oxide, boron nitride, silicon nitride, boron carbide, silicon nitride, alkali-resistant glass, carbon, etc.

[0058] The components of the alkaline aqueous slurry may further include (ix) one or more fibers. For the purposes of the present invention, the fibers are particulate materials having an aspect ratio greater than 3, preferably greater than 10, which do not react, melt, dissolve, decompose, or deteriorate under the conditions of a geopolymer-forming reaction. The fibers do not participate in the geopolymer-forming reaction(s). Examples of suitable fibers may include, for example, thermosetting polymer fibers, thermoplastic polymer fibers such as nylon, aramid, polypropylene, polyvinyl alcohol, and polyester fibers, cellulose fibers, alkali-resistant glass fibers, metal fibers, and various plant fibers including fibrous mineral whiskers and fibers, carbon fibers.

[0059] Inorganic calcium sources may be present in the alkaline aqueous slurry. Some calcium (most typically in oxide form) may be present in one or more of aluminate and / or silicate precursors, such as certain slags. It is generally desirable for the alkaline aqueous slurry to contain 0.5 moles or less of calcium per mole of silicon, and more preferably 0.25 moles or less or 0.1 moles or less of calcium per mole of silicon.

[0060] Upon the formation of an alkaline aqueous slurry, sugars and water-soluble peroxy compounds react exothermically to produce water and formic acid. While this reaction typically occurs spontaneously at temperatures ranging from -10°C to 37°C, some sugars, such as xylose, react more rapidly than others, such as glucose. Gas generation is typically observed within 10 seconds to 20 minutes after the formation of the alkaline aqueous slurry. Gas generation is found more rapidly in monosaccharides than in disaccharides, and in more highly reactive monosaccharides, such as xylose, than in less reactive monosaccharides, such as glucose. Therefore, the selection of sugars can serve as a means to adjust reactivity, the time to gas generation, and the non-sticking time as desired. Similarly, the presence or absence of a catalyst, and if present, its concentration and type, can be manipulated to adjust the reactivity of the system as desired.

[0061] Expanding gas is generated by one or more mechanisms. The exothermic reaction of sugars and water-soluble peroxy compounds produces formic acid, which can be neutralized to become alkali metal formates and further decomposed to produce carbon monoxide, carbon dioxide, and water. This exothermic heat of condensation can further volatilize water, generating vapor that expands the geopolymer. Catalytic or thermal decomposition of water-soluble peroxy compounds yields oxygen gas and water; however, unlike in the absence of sugars, gas generation in the present invention occurs spontaneously and rapidly even when the alkaline aqueous slurry is formed at low temperatures, such as approximately room temperature. It is not necessary to apply heat to generate expanding gas using the present invention.

[0062] The exothermic reaction generated by the reaction of sugars / water-soluble peroxy compounds also provides the energy to induce the reaction of aluminate and / or silicate precursors to produce geopolymers. Geopolymer-forming reactions are widely known and are described, for example, particularly in U.S. Patents No. 4,349,386 and No. 4,509,985. An advantage of the present invention is that initial curing occurs rapidly; even when an alkaline aqueous slurry is formed at a temperature of -10°C to 37°C and reacts without the application of additional heat, the geopolymer usually expands and cures to a self-supporting state in a very short period, often less than one hour, or even within 30 minutes. "Self-supporting" means that the partially cured geopolymer maintains its shape and dimensions without lateral support; that is, when supported only from below. The exothermic reaction of sugars is mainly rapid, generally completed within minutes. Therefore, unless heat is subsequently applied, the temperature of the reactants reaches a maximum immediately after the alkaline aqueous slurry is formed, and then tends to decrease toward ambient temperature. Curing can continue at ambient temperature. If desired, heat can be applied to accelerate geopolymer formation and develop physical properties. When applied, heating may be carried out for a period of 15 minutes to 6 hours or more, for example, to temperatures of 60°C to 200°C, particularly 60°C to 100°C. Heating may be applied before or after the geopolymer has cured sufficiently to expand and become self-supporting. In a particularly preferred embodiment, the alkaline aqueous slurry is produced at a temperature of -10°C to 37°C, particularly 10°C to 35°C, and partially cured without additional heat until an expanded, self-supporting, partially cured geopolymer is obtained. Subsequently, additional curing may be performed by heating the partially cured geopolymer to a temperature of 60°C to 200°C, particularly 60°C to 100°C, for a period of 15 minutes to 6 hours or more.

[0063] The method and composition of the present invention are useful in various construction and other applications.

[0064] One important construction application is a sealant for filling and sealing gaps, cracks, and penetrations within building structures. The two-component reactive system of the present invention is particularly suitable for such applications because the starting materials can be formulated and packaged as separate components that can be easily combined on-site to produce an expanded geopolymer. For example, each component can be packaged in a separate tube, mounted on a dual-cartridge dispensing gun, mixed using an inline static mixer, and discharged as a homogeneous reactive system.

[0065] Another construction application is an adhesive for temporarily or permanently bonding building elements to one another. Similar to sealants, the two-component reactive system of the present invention is particularly suitable for such adhesive applications and, if desired, can be dispensed and applied in a manner similar to that described for sealants. Additionally, the alkaline aqueous slurry can be applied to adhesive applications by other methods that allow the slurry to be dispensed immediately after formation, such as spraying. A suitable spraying device comprises a mix head for combining components (or subcombinations thereof, e.g., the two-component reactive system of the present invention) to form an alkaline aqueous slurry, and a spraying device for immediately dispensing the slurry in the form of an aerosolized suspension of reactive droplets in a carrier gas. When these droplets are deposited on a substrate, they adhere to the surface, and overlapping droplets merge and coalesce to form a film of the alkaline aqueous slurry, which continues to react as described above to form an expanded geopolymer coating.

[0066] Another construction application is coatings for building components such as panels, joists, and trusses. Spraying methods are particularly suitable for applying these coatings, but other methods such as immersion coating, rolling, and / or brushing may be used. Depending on convenience, these coatings can be applied at the work site and / or at manufacturing facilities producing building components.

[0067] Another construction application is insulation for building components such as walls and floors. Additionally, while spraying methods are particularly useful in these applications, other methods may be used to apply geopolymers depending on convenience.

[0068] Other construction applications include wallboards, insulation panels, laminated panels, and other boardstocks. These can be produced by forming an alkaline aqueous slurry, dispensing it onto a substrate, controlling the dimensions of the geopolymer as it expands to create a geopolymer layer of a predetermined thickness, and subsequently curing the geopolymer. Such products can be produced continuously by dispensing an alkaline aqueous slurry onto a substrate as the substrate moves, and at least partially curing the alkaline aqueous slurry on the moving substrate to form a self-supporting expanded geopolymer layer on the substrate. The partial curing step can be performed without applying heat until the self-supporting expanded geopolymer is formed, after which heat may be applied if desired to complete the curing and develop physical properties. Heat can be applied to a substrate with a partially cured geopolymer layer in a continuous process by passing the material through an oven, between the belts of a double-belt laminator, or between a series of heated rollers (which can also control the thickness of the board or panel); alternatively, heat can be applied discontinuously. Boards and panels manufactured in this manner are easily cut and trimmed to length if necessary. The substrate can be attached to the cured geopolymer layer, in which case it can form a layer of the final product. Another layer of the substrate can be placed on the geopolymer layer during or after curing to create a top layer that can remain with the final product and become part of the final product. For example, a paper layer can be used as a top and / or bottom substrate in producing a wallboard or similar panel product. Other substrates include metal sheets or foils useful for the intended application, wood, thermoplastic and / or thermosetting resins, various felts, various mineral wools, and reinforcing scrims, particularly polymeric alkali-resistant glass, metal, or cellulose scrims.

[0069] Another application is flame-retardant chip-board panels, such as those described in US Patent No. 4,028,454.

[0070] Ceramic tiles in which expanded geopolymers can constitute tiles or form a layer such as a substrate layer are another application.

[0071] Molded articles are easily manufactured by introducing an alkaline aqueous slurry into the mold cavity to partially fill the mold cavity, and by at least partially curing the alkaline aqueous slurry within the mold cavity so that the alkaline aqueous slurry expands to fill the mold cavity and at least partially cures to produce a self-supporting expanded geopolymer within the mold cavity. If desired, additional curing may be performed within the mold or after demolding the partially cured self-supporting expanded geopolymer. As before, curing within the mold may be performed by applying heat. In a particularly preferred process, the alkaline aqueous slurry is prepared at a temperature of -10°C to 37°C, introduced into the mold at this temperature, and then at least partially cured within the mold without applying additional heat. In such an embodiment, curing may optionally be completed within the mold by heating the mold and its contents to a temperature of 60°C to 200°C, preferably 60°C to 100°C; Alternatively, the partially cured geopolymer can be demolded outside the mold with or without heat and further cured.

[0072] Examples

[0073] In the following examples, all parts and percentages are by weight unless otherwise specified. Unless otherwise specified, all solutions are in water.

[0074] Examples 1 to 4 and Comparative Samples A and B

[0075] Geopolymers are prepared from the formulations presented in Table 1. The formulations are divided into two parts designated as Part A and Part B in Table 1.

[0076] [Table 1]

[0077]

[0078] * Not an embodiment of the present invention.

[0079] Combine the components of Part A and stir to dissolve the NaOH and disperse the metakaolin powder. Separately, combine the components of Part B and shake until the xylose is dissolved. The pH of Part A is greater than 12; and the pH of Part B is approximately 5 to 8. Afterward, combine Parts A and B at room temperature (approx. 23°C). Insert a thermocouple into the resulting reaction mixture and start a timer.

[0080] The reaction mixture of Example 1 begins to heat up almost immediately due to the exothermic decomposition of xylose, reaching approximately 102°C after about 100 seconds. At that time, the reaction mixture begins to form bubbles and expands rapidly with the generation of gas, primarily steam. Over the next 20 minutes, a continuous-bubble porous solid geopolymer foam is formed. After cooling, when a portion of the geopolymer foam of Example 1 is placed in water, it floats, and the concentration is 1.0 g / cm³. 3 It indicates that it has a much lower density.

[0081] The reaction mixtures of Examples 2 to 4 react similarly, exhibit an exothermic temperature rise to over 100°C in each case, and cure rapidly to 1.0 g / cm³ 3 It forms a self-supporting continuous cellular solid geopolymer foam with a much lower density.

[0082] When parts A and B are combined, comparison samples A and B show almost no exothermic temperature rise, and the peak temperature is limited to about 28°C. No foaming or gas generation is observed, and the reaction mixture remains in the form of a soft paste after one day.

[0083] Examples 5 and 6 and comparative samples C and D

[0084] Geopolymers are prepared from the formulations presented in Table 2 in the same general manner as described in the previous set of examples.

[0085] [Table 2]

[0086]

[0087] * Not an embodiment of the present invention.

[0088] The pH of Part A is greater than 12; the pH of Part B is approximately 6 to 8. Examples 5 and 6 exhibit an exothermic temperature rise, and expansion and curing begin within 2 minutes after combining Part A and Part B, with 1 g / cm² in each case. 3 It forms a foamed geopolymer having a density of less than . Example 6, containing cellulose, has greater mechanical strength than Examples 1 to 4. In Example 5, the presence of starch causes slight foam shrinkage.

[0089] As before, comparison samples C and D showed almost no reaction exothermic reaction and remained uncured after 1 day.

[0090] Examples 7 and 8

[0091] Geopolymers are prepared from the formulations presented in Table 3 in the same general manner as described in relation to Examples 1 to 4.

[0092] [Table 3]

[0093]

[0094] 1 Dow Chemical's Vorasurf 504.

[0095] The pH of Part A is greater than 12; the pH of Part B is approximately 6 to 8. In each case, the reaction mixture reacts exothermically, begins to expand and harden after about 90 seconds, and produces a solid geopolymer foam after 20 to 30 minutes. Example 8 has a finer cell structure due to the presence of a surfactant.

[0096] Examples 9 and 10 and Comparative Sample E

[0097] Geopolymers are prepared by mixing the components listed in Table 4. All components are combined at room temperature in a one-component formulation with a pH greater than 11. Examples 9 and 10 begin to foam immediately upon mixing, and self-supporting expanded materials are obtained within one hour. Subsequently, Examples 9 and 10 are cured overnight at 80°C and 60°C, respectively. Comparative Sample E does not foam or expand until heated to 80°C and maintained at that temperature overnight. Density is measured for each product. Thermal conductivity is measured according to ASTM C518-21 (Standard Test Method for Steady-State Heat Transfer Characteristics by Heat Flowmeter), and for Example 9 and Comparative Sample E, compressive strength is measured according to ASTM C165-23 (Standard Test Method for Measuring Compressive Characteristics of Insulating Materials). The results are shown in Table 4.

[0098] [Table 4]

[0099]

[0100] *Comparison. ND is not performed.

[0101] Example 11

[0102] Geopolymer Example 11 is prepared by mixing the components shown in Table 5. The pH of Part A is estimated to be greater than 12; the pH of Part B is estimated to be approximately 6 to 8. Part A and Part B are combined at room temperature, and foaming begins immediately thereafter. The reaction mixture expands and becomes self-supporting within one hour. Further curing is performed overnight at 60°C to produce a rigid cellular geopolymer.

[0103] [Table 5]

[0104]

[0105] Examples 12 and 13

[0106] Geopolymers are prepared from the formulations presented in Table 6 in the same general manner as described in relation to Examples 1 to 4.

[0107] [Table 6]

[0108]

[0109] Parts A and B are combined at room temperature in each case. Although the reaction rate when using these hexose sugars is much slower than that seen in the previous example using pentose sugars (xylose), the reaction mixture expands and partially hardens without the application of heat.

Claims

Claim 1 A method for manufacturing a foamed geopolymer comprising: (I) a step of forming an alkaline aqueous slurry having a liquid phase containing water by combining components comprising: (i) one or more inorganic aluminate and / or silicate precursor materials, wherein the one or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1:1 to 4:1; (ii) one or more inorganic bases selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth hydroxides and alkaline earth oxides; (iii) one or more sugars selected from monosaccharides and disaccharides; (iv) at least 3 moles of a water-soluble peroxy compound per 1 mole of sugar; and (v) water, which disperses and / or dissolves components (i), (ii), (iii), and (iv) in a liquid phase to produce an alkaline aqueous slurry, wherein the one or more sugars constitute 1 to 10 weight% of the sum of components (i), (ii), (iii), (iv), and (v). A method comprising the steps of: (1) water constituting 20 to 75% of the combined weight of components (i), (ii), (iii), (iv) and (v); and (2) curing an alkaline aqueous slurry to produce a foamed geopolymer. Claim 2 The method of claim 1, wherein one or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1.25:1 to 2.5:

1. Claim 3 A method according to claim 1 or 2, wherein one or more inorganic aluminate and / or silicate precursor materials constitute 30 to 60% of the combined weight of components (i), (ii), (iii), (iv) and (v). Claim 4 A method according to any one of claims 1 to 3, wherein one or more inorganic aluminate and / or silicate precursor materials (i) comprise aluminosilicate and alkali metal silicate. Claim 5 In paragraph 4, the aluminosilicate is metakaolin, method. Claim 6 A method according to any one of claims 1 to 5, wherein the inorganic base comprises sodium hydroxide, sodium oxide, potassium hydroxide, potassium oxide, or any two or more of these. Claim 7 A method according to any one of claims 1 to 6, wherein the sugar (iv) is a reducing monosaccharide. Claim 8 In claim 7, the reducing monosaccharide is one or more of glucose, mannose, galactose, allose, altrose, and talose. Claim 9 In claim 7, the reducing monosaccharide is one or more of xylose, arabinose, lixose, and ribose. Claim 10 In paragraph 7, the reducing monosaccharide is xylose. Claim 11 A method according to any one of claims 1 to 10, wherein the component comprises at least 5 moles of a water-soluble peroxy compound per 1 mole of sugar. Claim 12 A method according to any one of claims 1 to 11, wherein the water-soluble peroxy compound is hydrogen peroxide, an alkali metal peroxide, or an alkali metal percarbonate. Claim 13 In paragraph 12, the water-soluble peroxy compound is hydrogen peroxide. Claim 14 A method according to any one of claims 1 to 13, wherein the component of the aqueous alkaline slurry further comprises (vi) at least one material selected from the group consisting of a) organic and / or silicone surfactants and b) water-soluble and / or water-dispersible organic polymers. Claim 15 In claim 14, the method wherein component (vi) is selected from the group consisting of a polyether block copolymer surfactant; a silicone surfactant, a hydrophobically modified ethylene oxide urethane rheology modifier, a nonionic urethane rheology modifier, an acrylic acid homopolymer, an acrylic acid copolymer, and a polystyrene sulfonate. Claim 16 A method according to any one of claims 1 to 15, wherein the component of the aqueous alkaline slurry further comprises (vii) a catalytic amount of a transition metal catalyst for the reaction of a water-soluble peroxy compound with one or more monosaccharides. Claim 17 In paragraph 16, the transition metal catalyst is an iron or manganese compound. Claim 18 A method according to any one of claims 1 to 17, wherein the component of the alkaline aqueous slurry further comprises (viii) one or more fillers. Claim 19 A method according to any one of claims 1 to 18, wherein the component of the alkaline aqueous slurry further comprises (ix) one or more fibers. Claim 20 A method according to any one of claims 1 to 19, wherein the alkaline aqueous slurry is formed by the steps of: (A) producing a first alkaline aqueous premix comprising water and (ii) one or more inorganic bases; and (B) separately producing a second aqueous premix comprising hydrogen peroxide, wherein the second aqueous premix has a pH of 3 to 10 at 25°C; - one or more inorganic aluminate and / or silicate precursor materials and one or more sugars are independently present in the first alkaline aqueous premix and the second aqueous premix, or are divided between the first alkaline aqueous premix and the second aqueous premix -, and then (C) combining the first alkaline aqueous premix with the second aqueous premix. Claim 21 A method according to claim 20, wherein the first alkaline aqueous premix contains one or more inorganic bases, alkali metal silicates, and metakaolin, and the second aqueous premix contains hydrogen peroxide, monosaccharides, and optionally metakaolin. Claim 22 A method according to any one of claims 1 to 21, wherein the step of curing an alkaline aqueous slurry to produce a foamed geopolymer is performed by combining the components at a temperature of 0 to 40°C and allowing the alkaline aqueous slurry to expand and cure without applying heat until at least a partially cured expanded self-supporting geopolymer is produced. Claim 23 A method according to claim 22, further comprising the step of further curing the geopolymer by heating the partially cured expanded self-supporting geopolymer at a temperature of 60 to 200°C for a period of at least 15 minutes. Claim 24 A method according to any one of claims 1 to 23, wherein an alkaline aqueous slurry is introduced into a mold cavity to partially fill the mold cavity, and step II is performed at least partially within the mold cavity so that the alkaline aqueous slurry expands to fill the mold cavity and at least partially hardens to produce a self-supporting expanded geopolymer within the mold cavity. Claim 25 A method according to any one of claims 1 to 23, wherein an alkaline aqueous slurry is distributed onto the surface of a moving substrate and formed into a layer on the moving substrate, and the alkaline aqueous slurry layer on the moving substrate is at least partially cured to form a self-supporting expanded geopolymer layer on the substrate. Claim 26 An expanded geopolymer article manufactured according to the method of any one of claims 1 to 25. Claim 27 An expanded geopolymer obtained by curing an alkaline aqueous slurry having a liquid phase containing water, wherein the alkaline aqueous slurry comprises (i) one or more inorganic aluminate and / or silicate precursor materials—the one or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1:1 to 4:1—(ii) one or more inorganic bases selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth hydroxides, and alkaline earth oxides, (iii) one or more sugars selected from monosaccharides and disaccharides, and (iv) one or more water-soluble peroxy compounds in an amount of at least 3 moles per mole of sugar, wherein components (i) to (iv) are dispersed and / or dissolved in the liquid phase, and one or more sugars constitute 1 to 10 weight% of the combined weight of components (i), (ii), (iii), (iv) and water, and water is the sum of components (i), (ii), (iii), (iv) and water Expanded geopolymer constituting 20 to 75% by weight. Claim 28 In paragraph 27, one or more inorganic aluminate and / or silicate precursor materials are an expanded geopolymer providing silicon and aluminum in a molar ratio of 1.25:1 to 2.5:

1. Claim 29 In claim 27 or 28, an expanded geopolymer in which one or more inorganic aluminate and / or silicate precursor materials constitute 30 to 60% of the combined weight of components (i), (ii), (iii), (iv) and water. Claim 30 In any one of claims 27 to 30, one or more inorganic aluminate and / or silicate precursor materials (i) are expanded geopolymers comprising aluminosilicate and alkali metal silicate. Claim 31 In paragraph 30, the aluminosilicate is an expanded geopolymer that is metakaolin. Claim 32 An expanded geopolymer according to any one of claims 27 to 31, wherein the inorganic base comprises sodium hydroxide, sodium oxide, potassium hydroxide, potassium oxide, or a mixture of any two or more of these. Claim 33 In any one of paragraphs 27 to 32, the expanded geopolymer, wherein the sugars (iv) are reducing monosaccharides. Claim 34 In paragraph 33, the expanding geopolymer, wherein the reducing monosaccharide is one or more of glucose, mannose, galactose, allose, altrose, and talose. Claim 35 In paragraph 33, the expanding geopolymer is one or more of the reducing monosaccharides xylose, arabinose, lixose, and ribose. Claim 36 In paragraph 33, the reducing monosaccharide is xylose, an expanded geopolymer. Claim 37 An expanded geopolymer according to any one of claims 27 to 36, wherein the alkaline aqueous slurry comprises at least 5 moles of a water-soluble peroxy compound per 1 mole of sugar. Claim 38 An expanded geopolymer according to any one of paragraphs 27 to 37, wherein the water-soluble peroxy compound is hydrogen peroxide, an alkali metal peroxide, or an alkali metal percarbonate. Claim 39 An expanded geopolymer according to any one of paragraphs 27 to 38, wherein the water-soluble peroxy compound is hydrogen peroxide. Claim 40 An expanded geopolymer according to any one of claims 27 to 39, wherein the aqueous alkaline slurry further comprises (vi) at least one material selected from the group consisting of a) organic and / or silicone surfactants and b) water-soluble and / or water-dispersible organic polymers. Claim 41 In paragraph 40, component (vi) is an expanded geopolymer selected from the group consisting of a polyether block copolymer surfactant; a silicone surfactant, a hydrophobically modified ethylene oxide urethane rheology modifier, a nonionic urethane rheology modifier, an acrylic acid homopolymer, an acrylic acid copolymer, and a polystyrene sulfonate. Claim 42 In any one of claims 27 to 41, the aqueous alkaline slurry further comprises (vii) a catalytic amount of a transition metal catalyst for the reaction of a water-soluble peroxy compound with one or more monosaccharides, an expanded geopolymer. Claim 43 In paragraph 42, the transition metal catalyst is an expanded geopolymer that is an iron or manganese compound. Claim 44 In any one of paragraphs 27 to 43, the aqueous alkaline slurry is an expanded geopolymer further comprising (viii) one or more fillers. Claim 45 A two-component reactive system for producing a geopolymer comprises: (A) a first alkaline aqueous premix having a pH greater than 10, comprising water and one or more inorganic bases selected from alkali metal hydroxides, alkali metal oxides, alkali metal carbonates, alkaline earth hydroxides, and alkaline earth oxides; and (B) a second aqueous premix comprising water and a water-soluble peroxy compound, wherein the second aqueous premix has a pH of 3 to 10 at 25°C; (1) at least one of (A) and (B) contains one or more inorganic aluminate and / or silicate precursor materials; (2) at least one of (A) and (B) contains one or more sugars selected from monosaccharides and disaccharides; (3) one or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1:1 to 4:1; and (4) one or more sugars are of the combined weight of (A) and (B). A two-component reactive system comprising 1 to 10%; (5) at least 3 moles of one or more water-soluble peroxy compounds per 1 mole of one or more sugars, and (6) water comprising 20 to 75% of the combined weight of (A) and (B). Claim 46 In paragraph 45, a two-component reactive system in which one or more inorganic aluminate and / or silicate precursor materials provide silicon and aluminum in a molar ratio of 1.25:1 to 2.5:

1. Claim 47 A two-component reactive system according to claim 45 or 46, wherein one or more inorganic aluminate and / or silicate precursor materials constitute 30 to 60% of the combined weight of one or more inorganic bases, water-soluble peroxy compounds, one or more inorganic aluminate and / or silicate precursor materials, one or more monosaccharides, and water. Claim 48 A two-component reactive system according to any one of claims 45 to 47, wherein one or more inorganic aluminate and / or silicate precursor materials (i) comprise an aluminosilicate and an alkali metal silicate. Claim 49 In paragraph 48, the alkali metal silicate is a two-component reactive system present in the first alkaline aqueous premix. Claim 50 In paragraph 48, a two-component reactive system in which the aluminosilicate is metakaolin. Claim 51 In paragraph 50, metakaolin is a two-component reactive system present in the first alkaline aqueous premix. Claim 52 In paragraph 50, metakaolin is a two-component reactive system present in the second aqueous premix. Claim 53 A two-component reactive system according to paragraph 50, wherein part of the metakaolin is present in the first alkaline aqueous premix and another part of the metakaolin is present in the second aqueous premix. Claim 54 A two-component reactive system according to any one of claims 45 to 53, wherein the inorganic base comprises sodium hydroxide, sodium oxide, potassium hydroxide, potassium oxide, or a mixture of any two or more of these. Claim 55 A two-component reactive system, wherein, in any one of paragraphs 45 to 54, the sugars are reducing monosaccharides. Claim 56 In paragraph 55, the reducing monosaccharide is xylose, a two-component reactive system. Claim 57 In any one of paragraphs 45 to 56, the sugars are a two-component reactive system present in the first alkaline aqueous premix. Claim 58 In any one of paragraphs 45 to 56, the sugars are a two-component reactive system present in the second aqueous premix. Claim 59 A two-component reactive system according to any one of claims 45 to 56, wherein some of the sugars are present in the first alkaline aqueous premix and other of the sugars are present in the second aqueous premix. Claim 60 A two-component reactive system according to any one of claims 45 to 59, comprising at least 5 moles of a water-soluble peroxy compound per 1 mole of sugar. Claim 61 A two-component reactive system according to any one of claims 45 to 60, wherein the water-soluble peroxy compound is hydrogen peroxide. Claim 62 A two-component reactive system according to any one of claims 45 to 61, wherein at least one of the first alkaline aqueous premix and the second aqueous premix further comprises at least one material selected from the group consisting of a) organic and / or silicone surfactants and b) water-soluble and / or water-dispersible organic polymers. Claim 63 A two-component reactive system according to any one of claims 45 to 62, wherein at least one of the first alkaline aqueous premix and the second aqueous premix further comprises a catalytic amount of a transition metal catalyst for the reaction of a water-soluble peroxy compound with one or more monosaccharides. Claim 64 A two-component reactive system according to any one of claims 45 to 63, wherein at least one of the first alkaline aqueous premix and the second aqueous premix further comprises one or more fillers. Claim 65 A two-component reactive system according to any one of claims 45 to 64, wherein at least one of the first alkaline aqueous premix and the second aqueous premix further comprises (ix) one or more fibers.

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