Highly reactive geopolymer foam formulation for rapid curing process

Abstract

A rapidly expanding and rapidly solidifying geopolymer formulation including a liquid aqueous phase having silicate, aluminate and / or aluminosilicate precursors, an inorganic base, a monosaccharide and / or disaccharide, and a water-soluble peroxygen compound. The saccharide and peroxygen compound spontaneously and rapidly react under strongly basic conditions to produce an expanding gas and a reaction exotherm that drives at least the initial solidification of the geopolymer formulation. The resulting foamed geopolymer formulation can be used in a variety of construction and construction applications, and other applications.

Description

Background Technology

[0001] This invention relates to geopolymers and methods for manufacturing geopolymers.

[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. A specific class of inorganic materials (called "geopolymers") has potential in these applications because they can be produced from inexpensive, readily available raw materials that form slurries or pastes and can be cast or molded into any arbitrary geometry.

[0003] Geopolymers are produced by the condensation of aluminosilicate starting materials in the presence of water and a strong base. This results in an amorphous polymeric Si-O-Al framework with tetrahedral aluminosilicate units containing alkali metal ions that balance the charge associated with tetrahedral Al. Geopolymers and methods for their manufacture are described, for example, in U.S. Patent Nos. 4,349,386 and 4,509,985 and many other patents.

[0004] Their adoption in construction and other applications is limited, partly because they require a long time to cure to a non-sticky, self-supporting state at ambient temperatures (such as those typically encountered on-site) (e.g., -10°C to 37°C). This requirement makes geopolymers unsuitable for many on-site applications that require faster curing. For example, adhesive and sealant applications often require materials that rapidly develop bond strength, viscosity, and / or "green strength" within minutes or hours rather than days.

[0005] Even when manufacturing precast products from geopolymers (such as walls, roofs, floors, or insulation panels), shorter initial curing times are desirable to reduce manufacturing cycle times and increase productivity. Rapid initial curing allows the material to be processed shortly after it has been formed into the desired product. While curing can be accelerated by applying heat to the geopolymer formulation during curing, this increases costs due to the additional energy requirements and specialized heating equipment, and supplying heat or maintaining high curing conditions for extended periods in field applications is often impractical.

[0006] Geopolymers, like most other inorganic cementing materials, have a density much higher than that of the organic materials they might replace. This higher density results in a significant increase in weight. Therefore, attempts have been made to produce geopolymers with lower densities. For example, U.S. Patent Application Publication No. 2022 / 0017410A describes incorporating chemical foaming agents (including carbonates, bicarbonates, hydrazides, and peroxides such as hydrogen peroxide and organic peroxides) into geopolymer formulations. This patent application reports densities as low as 127 kg / m³. 3 The density is [not specified], but the curing time is three days in a high humidity and ambient temperature atmosphere, followed by a drying step at 70°C.

[0007] EP 3728159 B describes a process of atomizing air or an inert gas into a water-surfactant mixture to produce an aqueous foam, which is then combined with inorganic raw materials to produce a foamed geopolymer. This patent reports foaming rates as low as 47 kg / m³. 3 The geopolymer density. Unfortunately, this method still requires a long curing time to reach a non-sticky state and has the additional disadvantage of requiring specialized equipment for handling the gas and incorporating it into the water-surfactant mixture. Therefore, the method described in EP 3728159 B has limited applicability, especially for field applications.

[0008] The desired materials and methods are for producing low-density geopolymers that cure rapidly even at ambient temperatures. Geopolymer foam formulations should primarily require inexpensive raw materials and preferably do not require specialized equipment for producing, processing, and curing the foam formulations to generate geopolymer products. Summary of the Invention

[0009] This invention relates to a method for manufacturing a foamed geopolymer, the method comprising the following steps:

[0010] (I) An alkaline aqueous slurry having a water-containing liquid phase is formed by combining components, said components comprising (i) one or more inorganic aluminate and / or silicate precursor materials, wherein said 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 metal hydroxides and alkaline earth metal oxides, (iii) one or more sugars selected from monosaccharides and disaccharides, (iv) at least three moles of a water-soluble peroxide compound per mole of said sugar, and (v) water, which disperses and / or dissolves components (i), (ii), (iii) and (iv) into said liquid phase to produce said alkaline aqueous slurry, wherein said one or more sugars constitute 1% to 10% by weight of the combined weight of components (i), (ii), (iii), (iv) and (v), and water constitutes a percentage of components (i), (ii), (iii), and (iv). The combined weight of (v) is 20% to 75%, and

[0011] (II) The alkaline aqueous slurry is cured to produce the foamed geopolymer.

[0012] The present invention also relates to an expandable geopolymer obtained by curing an alkaline aqueous slurry having a liquid phase containing water, the alkaline aqueous slurry 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 metal hydroxides and alkaline earth metal oxides, (iii) one or more sugars selected from monosaccharides and disaccharides, and (iv) at least three moles of one or more water-soluble peroxides per mole of sugar, wherein components (i)-(iv) are dispersed and / or dissolved in the liquid phase, the one or more sugars constitute 1% to 10% by weight of the combined weight of components (i), (ii), (iii), (iv) and water, and water constitutes 20% to 75% by weight of the combined weight of components (i), (ii), (iii), (iv) and water.

[0013] The present invention further relates to a two-component reaction system for generating geopolymers, the system comprising:

[0014] (A) A first alkaline aqueous premix having a pH greater than 10, the 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 metal hydroxides and alkaline earth metal oxides, and...

[0015] (B) A second aqueous premix comprising water and a water-soluble peroxide compound, wherein the second aqueous premix has a pH of 3 to 10 at 25°C, wherein:

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

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

[0018] (3) 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.

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

[0020] (5) Each mole of the one or more sugars contains at least three moles of the one or more water-soluble peroxide compounds, and

[0021] (6) Water accounts for 20% to 75% of the combined weight of (A) and (B). Detailed Implementation

[0022] This invention relates to a method for manufacturing foamed geopolymers, comprising the following steps:

[0023] (I) An alkaline aqueous slurry having a water-containing liquid phase is formed by combining components, which include (i) one or more inorganic aluminate and / or silicate precursor materials, wherein these 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 metal hydroxides and alkaline earth metal oxides, (iii) one or more sugars selected from monosaccharides and disaccharides, (iv) at least three moles of a water-soluble peroxide per mole of sugar, and (v) water, which disperses and / or dissolves components (i), (ii), (iii) and (iv) into a liquid phase to produce an alkaline aqueous slurry, wherein one or more sugars constitute 1% to 10% by weight of the combined weight of components (i), (ii), (iii), (iv) and (v), and water constitutes a percentage of components (i), (ii), (iii), and (iv). The combined weight of (v) is 20% to 75%, and

[0024] (II) The alkaline aqueous slurry is cured to produce the foamed geopolymer.

[0025] This method offers significant advantages. It requires only inexpensive and readily available raw materials, which are formulated to produce a flowable slurry that can be poured, pumped, extruded, sprayed, coated, or otherwise applied and processed. The initial reaction between the sugars and peroxides begins rapidly after the reactants are combined, quickly generating gases that expand the slurry, even when combined at or below room temperature. The reaction between the sugars and peroxides is highly exothermic. This exothermic heat drives the polymerization reaction. Consequently, the reactants expand and solidify very rapidly to produce a self-supporting, expanded geopolymer. Further solidification can be carried out at approximately room temperature, or accelerated by heating, such as to temperatures between 50°C and 100°C, if desired. The cured product is a rigid, non-flammable geopolymer containing gas-filled voids.

[0026] Due to these and other properties, this method can be used in a variety of construction applications where the alkaline aqueous slurry can be produced on-site and is easy to apply and cure. Examples of such construction applications include filling and sealing gaps, cracks, and penetrating holes in building structures, as well as applying coatings to building components such as slabs, joists, and trusses. Such coatings can, for example, improve the flammability and / or acoustic properties of the surfaces they are applied to.

[0027] This method can also be used in manufacturing environments for products such as geopolymer foam insulation boards and composites; ceramic tiles, refractory articles, decorative stone-like artifacts, thermal shock resistant refractory materials, and components for vehicles such as aircraft and automobiles. This method can also be used to generate geopolymers for the sequestration of radioactive and toxic waste, as well as for certain medical applications.

[0028] Another advantage of this invention is that the raw materials can be formulated as a two-component reactive system, wherein each component is non-reactive and exhibits long-term shelf stability when stored individually at temperatures typically encountered during transport and storage (e.g., up to 40°C). This provides significant advantages in terms of packaging, transport, storage, and use of the materials. Therefore, in another aspect, this invention is a two-component reactive system for producing geopolymers, comprising:

[0029] (A) A first alkaline aqueous premix having a pH greater than 10, the 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 metal hydroxides and alkaline earth metal oxides, and...

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

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

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

[0033] (3) 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.

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

[0035] (5) Each mole of one or more sugars contains at least three moles of one or more water-soluble peroxide compounds, and

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

[0037] The present invention is also an expandable geopolymer obtained by curing an alkaline aqueous slurry having a liquid phase containing water, the alkaline aqueous slurry 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 metal hydroxides and alkaline earth metal oxides, (iii) one or more sugars selected from monosaccharides and disaccharides, and (iv) at least three moles of at least one water-soluble peroxide per mole of at least one sugar, wherein components (i)-(iv) are dispersed and / or dissolved in the liquid phase, the one or more sugars constitute 1% to 10% by weight of the combined weight of components (i), (ii), (iii), (iv) and water, and water constitutes 20% to 75% by weight of the combined weight of components (i), (ii), (iii), (iv) and water.

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

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

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

[0041] Inorganic aluminosilicate precursors comprise silicon and aluminum, each bonded to oxygen. These include, for example, various clays, especially kaolin; various industrial wastes, such as blast furnace slag and steel slag; fly ash, such as lignite fly ash and hard coal fly ash; aluminosilicate glasses; natural volcanic ash materials, such as tuff, trachytic tuff, and volcanic ash; and metakaolin. Metakaolin, in its anhydrous calcined form having an approximate empirical formula Al₂O₇Si₂ (sometimes represented by the symbol Al₂O₃·2SiO₂), is a particularly preferred aluminosilicate precursor.

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

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

[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 < 5% by weight) solid particles or in the form of an aqueous solution. Typically, sufficient component (ii) is provided such that the aqueous alkaline slurry has a pH of at least 10, preferably at least 11. The pH can be measured in any convenient manner capable of determining such a high pH value, including wetting pH test paper with the aqueous alkaline slurry.

[0045] Component (iii) is preferably a monosaccharide. Component (iii) can be a reducing sugar and can be an aldose, but in each case it is preferably a monosaccharide. In some embodiments, preferred monosaccharides have six carbon atoms; examples of these include, but are not limited to, glucose, mannose, galactose, allose, azurose, and tarose. In other embodiments, preferred monosaccharides have five carbon atoms, such as xylose, arabinose, lythose, and ribose. Xylose is a preferred monosaccharide due to its reactivity with hydrogen peroxide in the presence of a base and its availability. The monosaccharide can be an L-isomer or a D-isomer, or a mixture of both. Examples of disaccharides include sucrose, lactose, trehalose, and maltose. If desired, component (iii) can be provided in an aqueous solution. One or more sugars may constitute 1% to 10% by weight, preferably 2% to 10% or 2% to 7.5% of the combined weight of components (i), (ii), (iii), (iv), and (v).

[0046] Component (iv) is a peroxide compound, i.e., a compound having at least one -OO- bond. Water-soluble peroxides, peroxide esters, percarbonates, etc., are suitable. The peroxide compound can be organic, provided it is soluble in water, but is more preferably inorganic. Inorganic peroxide compounds include hydrogen peroxide, alkali metal peroxides (such as sodium peroxide and potassium peroxide), and alkali metal percarbonates (such as sodium percarbonate and potassium percarbonate). Hydrogen peroxide is most preferred. The water-soluble peroxide compound is preferably provided in an aqueous solution. At least 3 moles of water-soluble peroxide compound are provided per mole of sugar; at least 5 moles are preferred when the sugar is a C5 monosaccharide, and at least 6 moles are preferred when the sugar is a C6 monosaccharide. Larger amounts of water-soluble peroxide compound can be used, such as up to 10 moles or up to 20 moles per mole of sugar, or even more.

[0047] Water (component v) typically 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 with controllable rheological properties. The preferred amount of water is at least 30% or at least 40% based on the foregoing, and also up to 65% or up to 60% based on the foregoing.

[0048] Alkaline aqueous slurries are prepared by mixing the above-mentioned components. The components can be combined using a simple mixing method sufficient to wet any solid starting material and obtain a uniform distribution. This can be carried out at temperatures, for example, -10°C to 40°C, especially 0°C to 37°C or 10°C to 37°C. If desired, the components can be combined at higher temperatures, but this is not necessary, and at such high temperatures, the reaction of one or more sugars with one or more water-soluble peroxides may be more difficult to control.

[0049] Since the sugar / peroxide reaction occurs spontaneously when sugars and peroxides combine in an alkaline environment, it is preferable to keep at least one of these components (sugars, peroxides, and any alkaline material) separate from the other components until the other components are combined or have already been combined.

[0050] It is generally convenient to formulate alkaline aqueous slurries as two-component reactive systems, especially for field applications. The two components are kept separate until they are combined to form an alkaline aqueous slurry that cures to produce a geopolymer. This reduces the need for on-site storage, measurement, and assembly of materials, minimizes formulation errors, and improves overall ease of use. To prevent premature reaction and improve shelf stability, the two-component reactive system is formulated to keep at least one of the sugars, hydrogen peroxide, and alkaline materials separate from the other materials until both components are combined and cured to produce an expanding geopolymer.

[0051] In such embodiments, 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 metal hydroxides, and alkaline earth metal oxides. Alkaline aluminate and / or silicate precursor materials (such as alkali metal silicates, if used) are 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 can be up to 18 or up to 17. The other component is a second aqueous premix comprising water and a water-soluble peroxide compound. The second aqueous premix has a pH less than 10, preferably 3 to 9, 3 to 8, or 4 to 8. Other components (such as the non-alkaline inorganic aluminate and / or silicate precursor materials, sugars, and optional components described below) may be freely distributed between the first and second components (including by distributing any one of them between the first and second components), provided that the alkaline component is contained in the first alkaline aqueous premix, and thus the second aqueous premix containing the water-soluble peroxide compound has a pH of up to 10 as described above.

[0052] In a specific embodiment, the first component comprises one or more inorganic bases, alkali metal silicates, and at least one aluminosilicate, preferably metakaolin, as described above; and the second component comprises hydrogen peroxide, a monosaccharide, and optionally at least one aluminosilicate (preferably metakaolin), as described above. In such embodiments, if desired, the aluminosilicate may be distributed between the first and second components, with a portion present in each of the components. This can be beneficial in producing first and second components with similar viscosities (which facilitates easier mixing) and allows the first and second components to be combined in convenient mixing ratios (e.g., 3:1 to 1:3 by volume, 2:1 to 1:2 by volume, or 1:1 by volume) when used to form geopolymers. The alkaline aqueous slurry produced by mixing the first and second components should have a pH greater than 10, preferably at least 11 or at least 12.

[0053] Various optional ingredients can also be provided in alkaline aqueous slurries. 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] For example, surfactants can be provided to stabilize the cellular structure of the expanding reaction mixture as it grows and solidifies, and / or as wetting agents for components that are insoluble or poorly dispersible in water. Surfactants can 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, alkylbenzene sulfonates, fatty carboxylates, alkyl ether phosphates, and alkyl-aryl ether phosphates. Examples of cationic surfactants include, but are not limited to, various quaternary ammonium compounds having C8-24 alkyl groups, such as hexadecyltrimethylammonium bromide, hexadecylpyridinium chloride, benzalkonium chloride, benzyl chloride, dimethyl dioctadecyl ammonium chloride, and dioctadecyl dimethyl ammonium bromide. Suitable amphiphilic surfactants are described in US2020 / 0017410 A. Such surfactants, if present, may be present in amounts ranging from 0.1% to 5% by weight, particularly from 0.25% to 2%, of one or more surfactants and the combination of components (i), (ii), (iii), (iv) and (v).

[0055] Water-soluble and / or water-dispersible polymers may be present. They can perform a variety of 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, carboxymethyl cellulose, alginate and its salts; acrylic 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 marketed by Dow Chemical Company under the trade name Acrysol®. Such water-soluble and / or water-dispersible polymers (if present) may comprise 0.1% to 5% by weight of one or more polymers and the combination of components (i), (ii), (iii), (iv) and (v), particularly 0.25% to 2%.

[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, with examples being ferrous sulfate, MnO2, and KMnO4.

[0057] The composition of the alkaline aqueous slurry may further include (viii) one or more fillers. For the purposes of this invention, the filler is a particulate material having an aspect ratio of 3 or less that does not react, melt, dissolve, decompose, or degrade under the conditions of a geopolymer formation reaction. The filler does not participate in one or more geopolymer formation reactions. The filler may include, for example, thermosetting polymer particles, metal particles, and mineral fillers. Mineral fillers may be naturally occurring and / or synthetic materials. 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 composition of the alkaline aqueous slurry may further include (ix) one or more fibers. For the purposes of this 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 degrade under the conditions of geopolymer formation reaction. The fibers do not participate in one or more geopolymer formation reactions. Examples of suitable fibers may include, for example, thermosetting polymer fibers, thermoplastic polymer fibers (such as nylon, aromatic polyamide, polypropylene, polyvinyl alcohol, and polyester fibers), various plant fibers (including cellulose fibers), alkali-resistant glass fibers, metal fibers and fibrous mineral whiskers and fibers, and carbon fibers.

[0059] Inorganic calcium sources can be present in alkaline aqueous slurries. Some calcium (most typically in the form of oxides) can be present in one or more aluminate and / or silicate precursors, such as certain slags. Generally preferred, the alkaline aqueous slurry contains no more than 0.5 mol of calcium per mole of silicon, and more preferably no more than 0.25 mol or 0.1 mol of calcium per mole of silicon.

[0060] After the formation of the alkaline aqueous slurry, sugars and water-soluble peroxides undergo an exothermic reaction to produce water and formic acid. This reaction typically occurs spontaneously even at temperatures ranging from -10°C to 37°C, but some sugars (such as xylose) react faster than others (such as glucose). Gas evolution is typically observed within 10 seconds to 20 minutes after the formation of the alkaline aqueous slurry. Gas evolution is observed more rapidly with monosaccharides than with disaccharides, and more rapidly with more reactive monosaccharides (such as xylose) than with less reactive monosaccharides (such as glucose). Therefore, the choice of sugar can be used to adjust reactivity, the time until gas production begins, and the time to non-viscous conditions, as needed. 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, if desired.

[0061] The expanding gas is generated by one or more mechanisms. The exothermic reaction of sugars with water-soluble peroxides produces formic acid, which can be neutralized to alkali metal formate and further decomposed to produce carbon monoxide, carbon dioxide, and water. The exothermic heat of these reactions can further volatilize water, producing vapors that expand the geopolymer. Catalytic or thermal decomposition of water-soluble peroxides produces oxygen and water; however, unlike cases where sugars are absent, gas generation in this invention occurs spontaneously and rapidly, even when the alkaline aqueous slurry is formed at low temperatures (e.g., approximately room temperature). The applied heat is not necessary for generating the expanding gas using this invention.

[0062] The exothermic heat generated by the reaction of sugars / water-soluble peroxides also provides energy for driving the reaction of aluminate and / or silicate precursors to produce geopolymers. Geopolymer formation reactions are well known and described, for example, in U.S. Patent Nos. 4,349,386 and 4,509,985, and other patents. An advantage of this invention is the rapid occurrence of initial curing; even when the alkaline aqueous slurry is formed at temperatures ranging from -10°C to 37°C and allows the reaction to occur without the application of additional heat, the geopolymer typically expands and cures to a self-supporting state within a very short timeframe (often one hour or less, or even 30 minutes or less). "Self-supporting" means that the partially cured geopolymer retains its shape and size without lateral support, i.e., when supported only from below. The exothermic reaction of sugars is primarily and typically completed rapidly within minutes. Therefore, unless heat is subsequently applied, the temperature of the reactants tends to reach its maximum shortly after the formation of the alkaline aqueous slurry, followed by a subsequent temperature drop to ambient temperature. Curing can continue even at ambient temperature. If necessary, heat can be applied to accelerate the formation of the geopolymer and the development of its physical properties. Heating (if applied) can reach temperatures, for example, 60°C to 200°C, particularly 60°C to 100°C, for a period of 15 minutes to 6 hours or longer. Heating can be applied before or after the geopolymer has fully cured to the point of expansion and self-support. In a particularly preferred embodiment, the alkaline aqueous slurry is produced at temperatures of -10°C to 37°C, particularly 10°C to 35°C, and partially cured without the application of additional heat until an expanded, self-supporting, partially cured geopolymer is obtained. Further curing can then be carried out by heating the partially cured geopolymer to temperatures of 60°C to 200°C, particularly 60°C to 100°C, for a period of 15 minutes to 6 hours or longer.

[0063] The methods and compositions of this invention can be used in a variety of construction and other applications.

[0064] One important construction application is the use of sealants to fill and seal gaps, cracks, and perforations in building structures. The two-component reactive system of this invention is particularly suitable for such applications because it allows the starting materials to be formulated and packaged into individual components, which can be easily combined on-site to produce an expanding geopolymer. For example, each of the components can be packaged into a separate tube (which can be mounted on a twin-barrel dispensing gun), mixed using an in-line static mixer, and discharged as a homogeneous reactive system.

[0065] Another construction application is the use of adhesives for temporarily or permanently attaching building components to each other. Similar to sealants, the two-component reactive system of the present invention is particularly suitable for adhesive applications (such as these adhesive applications) and can be dispensed and applied in a manner similar to that described for sealants, if desired. Furthermore, alkaline aqueous slurries can be applied in adhesive applications by other methods (such as spraying) that allow for immediate dispensing of the slurry after its formation. Suitable spraying apparatus includes a mixing head for combining the components (or sub-combinations thereof, such as the two-component reactive system of the present invention) to form an alkaline aqueous slurry, and a spraying device for immediately dispensing the slurry as an aerosolized suspension of reactive droplets in a carrier gas. As these droplets deposit on the substrate, they adhere to the surface, and overlapping droplets merge and coalesce into a film of the alkaline aqueous slurry, which continues to react as described above to form an expanded geopolymer coating.

[0066] Another application is coating of building components such as slabs, beams, and trusses. Spraying is particularly suitable for applying such coatings, but other methods such as dip coating, roller coating, and / or brush coating can also be used. Such coatings can be applied conveniently at the work site and / or at the manufacturing facility where the building components are produced, depending on the circumstances.

[0067] Another application is in the application of geopolymers for building components such as walls and floors. Spraying is particularly useful for this application, but other methods can be used to apply the geopolymer if convenient.

[0068] Another construction application is wall panels, insulation boards, laminates, and other boards. These can be produced by: forming an alkaline aqueous slurry, distributing the alkaline aqueous slurry onto a substrate, measuring the expansion of the geopolymer to produce a geopolymer layer of a predetermined thickness, and then curing the geopolymer. Such products can be produced continuously by: distributing the alkaline aqueous slurry onto the substrate while it moves, and at least partially curing the alkaline aqueous slurry onto the moving substrate to form a self-supporting, expanding geopolymer layer on the substrate. The partial curing step can be carried out without heat until the self-supporting, expanding geopolymer is formed, after which heat can be applied, if necessary, to complete the curing and establish the physical properties. Heat can be applied continuously to the substrate with the partially cured geopolymer layer 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 measure the thickness of the board or sheet); alternatively, heat can be applied discontinuously. Boards and sheets manufactured in this way can be easily cut to length and trimmed if necessary. A substrate can adhere to the cured geopolymer layer, and in such cases, a layer of the final product can be formed. During or after curing, another substrate layer can be laid on the geopolymer layer to create a top layer, which can be retained with the final product and become part of it. For example, a paper layer can be used as a top and / or bottom substrate for producing wall panels or similar board products. Other substrates include metal sheets or foils, wood, thermoplastic and / or thermosetting resins, various felts, various mineral wools, and reinforcing sparse fabrics (such as polymers, alkali-resistant glass, metal or cellulose sparse fabrics, etc.), which can be used for the intended application.

[0069] Another application is in flame-retardant particleboard, as described, for example, in US 4,028,454.

[0070] Ceramic tiles (in which expanded geopolymers can form the tiles or the layers that form the tiles) (such as the substrate layer) represent yet another application.

[0071] Molded articles are conveniently manufactured by introducing an alkaline aqueous slurry into a mold cavity to partially fill the cavity, and at least partially curing the alkaline aqueous slurry within the mold cavity, causing the alkaline aqueous slurry to expand to fill the mold cavity and at least partially cure, thereby creating a self-supporting, expanded geopolymer within the mold cavity. Further curing, if desired, can be performed within the mold or after demolding the partially cured, self-supporting, expanded geopolymer. As previously described, curing within the mold can be carried out by applying heat. In a particularly preferred method, the alkaline aqueous slurry is prepared at a temperature of -10°C to 37°C and introduced into the mold at this temperature, and then at least partially cured within the mold without applying additional heat. In such embodiments, curing can be completed within the mold, optionally 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 with or without heat and further cured outside the mold. Example

[0072] In the following examples, all parts and percentages are by weight unless otherwise specified. All solutions are aqueous solutions unless otherwise specified.

[0073] Examples 1-4 and comparative samples A and B

[0074] The geopolymer is made from the formulations listed in Table 1. The formulations are divided into two parts, designated as Part A and Part B in Table 1.

[0075] Table 1

[0076]

[0077] This is not an example of the present invention.

[0078] Combine and stir component A to dissolve the NaOH and disperse the metakaolin powder. Combine component B separately and agitate until the xylose dissolves. Component A has a pH greater than 12; component B has a pH of approximately 5 to 8. Then combine components A and B at room temperature (approximately 23°C). Place a thermocouple in the resulting reaction mixture and start a timer.

[0079] Due to the exothermic decomposition of xylose, the reaction mixture in Example 1 began to heat almost immediately, reaching approximately 102°C after about 100 seconds. At this point, bubbles began to form in the reaction mixture and expanded rapidly as gas (mainly vapor) was released. Over the next 20 minutes, an open-cell, porous solid geopolymer foam was formed. After cooling, a portion of the geopolymer foam from Example 1 was placed in water; a portion of the foam floated, indicating a pH well below 1.0 g / cm³. 3 The density.

[0080] The reaction mixtures in Examples 2-4 reacted similarly, exhibiting exothermic temperature rises to over 100°C and rapid solidification to form a density far below 1.0 g / cm³. 3 Self-supporting open-cell solid geopolymer foam.

[0081] When samples A and B were combined, control samples A and B showed almost no increase in exothermic temperature, with peak temperatures reaching only about 28°C. No foaming or gas generation was observed, and the reaction mixture remained in ointment form after one day.

[0082] Examples 5-6 and comparative samples C and D

[0083] Geopolymers are made from the formulations listed in Table 2 in the same general manner as described in the previous example group.

[0084] Table 2

[0085]

[0086] This is not an example of the present invention.

[0087] Part A has a pH exceeding 12; part B has a pH of approximately 6-8. Examples 5 and 6 exhibit an exothermic temperature rise and begin to expand and solidify within 2 minutes of the combination of parts A and B, forming a gel with a concentration of less than 1 g / cm³ in each case. 3 The density of the foamed geopolymer is [not specified]. Example 6, containing cellulose, has greater mechanical strength than Examples 1-4. The presence of starch in Example 5 causes some foam shrinkage.

[0088] As previously mentioned, comparative samples C and D showed almost no exothermic reaction and remained uncured after one day.

[0089] Examples 7 and 8

[0090] Geopolymers are made from the formulations listed in Table 3 in the same general manner as described with respect to Examples 1-4.

[0091] Table 3

[0092]

[0093] 1 Vorasurf 504, from Dow Chemical Company.

[0094] Part A has a pH exceeding 12; part B has a pH of approximately 6-8. In each case, the reaction mixture undergoes an exothermic reaction and begins to expand and solidify after approximately 90 seconds, producing a solid geopolymer foam after 20-30 minutes. Example 8 exhibits a finer pore structure due to the presence of the surfactant.

[0095] Examples 9 and 10 and comparative sample E

[0096] Geopolymers were prepared by mixing the ingredients shown in Table 4. All ingredients were combined at room temperature to form a single-component formulation with a pH greater than 11. Examples 9 and 10 began foaming immediately after material mixing and produced self-supporting expanded materials within one hour. Examples 9 and 10 were then cured overnight at 80°C and 60°C, respectively. Control sample E did not foam or expand until it was heated to 80°C and held at that temperature overnight. Density measurements were performed on each product. For Example 9 and Control sample E, thermal conductivity was measured according to ASTM C518-21 (Standard Test Method for Steady-State Thermal Transmission Properties by Means of the Heat Flow Meter Apparatus) and compressive strength was measured according to ASTM C165-23 (Standard Test Method for Measuring Compressive Properties of Thermal Insulations). The results are shown in Table 4.

[0097] Table 4

[0098]

[0099] Comparison sample. ND indicates incomplete.

[0100] Example 11

[0101] Geopolymer Example 11 was prepared by mixing the ingredients shown in Table 5. Part A had an estimated pH greater than 12; Part B had a pH of approximately 6-8. Parts A and B were combined at room temperature, and foaming began immediately thereafter. The reaction mixture expanded and became self-supporting within one hour. Further curing was carried out overnight at 60°C to produce a rigid, porous geopolymer.

[0102] Table 5

[0103]

[0104] Examples 12 and 13

[0105] Geopolymers are made from the formulations listed in Table 6 in the same general manner as described with respect to Examples 1-4.

[0106] Table 6

[0107]

[0108] In each case, portions A and B are combined at room temperature. The reaction mixture expands and partially solidifies without the application of heat, although the reaction rate with these hexoses is much slower than that seen in previous examples with pentoses (xylose).

Claims

1. A method for manufacturing a foamed geopolymer, the method comprising the following steps: (I) An alkaline aqueous slurry having a water-containing liquid phase is formed by combining components, said components comprising (i) one or more inorganic aluminate and / or silicate precursor materials, wherein said 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 metal hydroxides and alkaline earth metal oxides, (iii) one or more sugars selected from monosaccharides and disaccharides, (iv) at least three moles of a water-soluble peroxide compound per mole of said sugar, and (v) water, which disperses and / or dissolves components (i), (ii), (iii) and (iv) into said liquid phase to produce said alkaline aqueous slurry, wherein said one or more sugars constitute 1% to 10% by weight of the combined weight of components (i), (ii), (iii), (iv) and (v), and water constitutes a percentage of components (i), (ii), (iii), and (iv). The combined weight of (v) is 20% to 75%, and (II) The alkaline aqueous slurry is cured to produce the foamed geopolymer.

2. The method as described in claim 1, wherein, The 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.

3. The method as described in claim 1 or 2, wherein, The one or more inorganic aluminate and / or silicate precursor materials comprise 30% to 60% of the combined weight of components (i), (ii), (iii), (iv), and (v).

4. The method according to any one of claims 1 to 3, wherein, The one or more inorganic aluminate and / or silicate precursor materials (i) include aluminosilicates and alkali metal silicates.

5. The method of claim 4, wherein, The aluminosilicate is metakaolin.

6. The method according to any one of claims 1 to 5, wherein, The inorganic base includes sodium hydroxide, sodium oxide, potassium hydroxide, potassium oxide, or a mixture of any two or more thereof.

7. The method according to any one of claims 1 to 6, wherein, The sugars (iv) mentioned are reducing monosaccharides.

8. The method of claim 7, wherein, The reducing monosaccharide is one or more of the following: glucose, mannose, galactose, allose, azoose, and tarose.

9. The method of claim 7, wherein, The reducing monosaccharide is one or more of the following: xylose, arabinose, lysolose, and ribose.

10. The method of claim 7, wherein, The reducing monosaccharide is xylose.

11. The method according to any one of claims 1 to 10, wherein, The ingredient comprises at least 5 moles of the water-soluble peroxide compound per mole of the sugar.

12. The method according to any one of claims 1 to 11, wherein, The water-soluble peroxide is hydrogen peroxide, alkali metal peroxide, or alkali metal percarbonate.

13. The method of claim 12, wherein, The water-soluble peroxide compound is hydrogen peroxide.

14. The method according to any one of claims 1 to 13, 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.

15. The method of claim 14, wherein, Component (vi) is selected from the group consisting of: polyether block copolymer surfactants, silicone surfactants, hydrophobically modified ethylene oxide urethane rheology modifiers, nonionic urethane rheology modifiers, acrylic homopolymers, acrylic copolymers, and polystyrene sulfonates.

16. The method according to any one of claims 1 to 15, wherein, The aqueous alkaline slurry further comprises (vii) a catalytic amount of a transition metal catalyst for the reaction of the water-soluble peroxide with the one or more monosaccharides.

17. The method of claim 16, wherein, The transition metal catalyst is an iron or manganese compound.

18. The method according to any one of claims 1 to 17, wherein, The composition of the alkaline aqueous slurry further includes (viii) one or more fillers.

19. The method according to any one of claims 1 to 18, wherein, The alkaline aqueous slurry further comprises (ix) one or more fibers.

20. The method according to any one of claims 1 to 19, wherein, The alkaline aqueous slurry is formed by the following steps: (A) A first alkaline aqueous premix is ​​produced, the first alkaline aqueous premix comprising water and one or more inorganic bases as described in (ii), and (B) To produce a second aqueous premix containing hydrogen peroxide, wherein the second aqueous premix has a pH of 3 to 10 at 25°C; The 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 distributed between the first alkaline aqueous premix and the second aqueous premix, and then (C) Combine the first alkaline aqueous premix with the second aqueous premix.

21. The method of 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.

22. The method according to any one of claims 1 to 21, wherein, The step of curing the alkaline aqueous slurry to produce the foamed geopolymer is carried out by combining the components at a temperature of 0°C to 40°C and allowing the alkaline aqueous slurry to expand and cure without the application of heat, at least until a partially cured, expanded and self-supporting geopolymer is produced.

23. The method of claim 22, further comprising heating the partially cured, expanded, and self-supporting geopolymer at a temperature of 60°C to 200°C for a period of at least 15 minutes to further cure the geopolymer.

24. The method according to any one of claims 1 to 23, wherein, The alkaline aqueous slurry is introduced into the mold cavity to partially fill the mold cavity, and step II is performed at least partially within the mold cavity, such that the alkaline aqueous slurry expands to fill the mold cavity and at least partially solidifies to produce a self-supporting, expanding geopolymer within the mold cavity.

25. The method according to any one of claims 1 to 23, wherein, The alkaline aqueous slurry is dispensed onto the surface of a mobile substrate and a layer is formed on the mobile substrate, and the alkaline aqueous slurry layer on the mobile substrate is at least partially cured to form a self-supporting, expanding geopolymer layer on the substrate.

26. An expanded geopolymer article manufactured by the method according to any one of claims 1 to 25.

27. An expandable geopolymer obtained by curing an alkaline aqueous slurry having a liquid phase comprising water, said alkaline aqueous slurry comprising (i) one or more inorganic aluminate and / or silicate precursor materials, wherein said 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 metal hydroxides and alkaline earth metal oxides, (iii) one or more sugars selected from monosaccharides and disaccharides, and (iv) at least three moles of one or more water-soluble peroxides per mole of sugar, wherein components (i)-(iv) are dispersed and / or dissolved in said liquid phase, said one or more sugars constituting 1% to 10% by weight of the combined weight of components (i), (ii), (iii), (iv) and said water, and water constituting the weight of components (i), (ii), (iii), and (iv). The combined weight of the water is 20% to 75%.

28. The expanded geopolymer of claim 27, wherein, The 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.

29. The expanded geopolymer as described in claim 27 or 28, wherein, The one or more inorganic aluminate and / or silicate precursor materials comprise 30% to 60% of the combined weight of components (i), (ii), (iii), (iv) and the water.

30. The expanded geopolymer according to any one of claims 27 to 30, wherein, The one or more inorganic aluminate and / or silicate precursor materials (i) include aluminosilicates and alkali metal silicates.

31. The expanded geopolymer of claim 30, wherein, The aluminosilicate is metakaolin.

32. The expanded geopolymer according to any one of claims 27 to 31, wherein, The inorganic base includes sodium hydroxide, sodium oxide, potassium hydroxide, potassium oxide, or a mixture of any two or more thereof.

33. The expanded geopolymer according to any one of claims 27 to 32, wherein, The sugars (iv) mentioned are reducing monosaccharides.

34. The expanded geopolymer of claim 33, wherein, The reducing monosaccharide is one or more of the following: glucose, mannose, galactose, allose, azoose, and tarose.

35. The expanded geopolymer of claim 33, wherein, The reducing monosaccharide is one or more of the following: xylose, arabinose, lysolose, and ribose.

36. The expanded geopolymer of claim 33, wherein, The reducing monosaccharide is xylose.

37. The expanded geopolymer according to any one of claims 27 to 36, wherein, The alkaline aqueous slurry contains at least 5 moles of the water-soluble peroxide compound per mole of the sugar.

38. The expanded geopolymer according to any one of claims 27 to 37, wherein, The water-soluble peroxide is hydrogen peroxide, alkali metal peroxide, or alkali metal percarbonate.

39. The expanded geopolymer according to any one of claims 27 to 38, wherein, The water-soluble peroxide compound is hydrogen peroxide.

40. The 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.

41. The expanded geopolymer of claim 40, wherein, Component (vi) is selected from the group consisting of: polyether block copolymer surfactants, silicone surfactants, hydrophobically modified ethylene oxide urethane rheology modifiers, nonionic urethane rheology modifiers, acrylic homopolymers, acrylic copolymers, and polystyrene sulfonates.

42. The expanded geopolymer according to any one of claims 27 to 41, wherein, The aqueous alkaline slurry further comprises (vii) a catalytic amount of a transition metal catalyst for the reaction of the water-soluble peroxide with the one or more monosaccharides.

43. The expanded geopolymer of claim 42, wherein, The transition metal catalyst is an iron or manganese compound.

44. The expanded geopolymer according to any one of claims 27 to 43, wherein, The aqueous alkaline slurry further comprises (viii) one or more fillers.

45. A two-component reaction system for producing geopolymers, the system comprising: (A) A first alkaline aqueous premix having a pH greater than 10, the 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 metal hydroxides and alkaline earth metal oxides, and... (B) A second aqueous premix comprising water and a water-soluble peroxide compound, wherein the second aqueous premix has a pH of 3 to 10 at 25°C, wherein: (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, said sugars being selected from monosaccharides and disaccharides. (3) 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. (4) The one or more sugars constitute 1% to 10% of the combined weight of (A) and (B); (5) Each mole of the one or more sugars contains at least three moles of the one or more water-soluble peroxide compounds, and (6) Water accounts for 20% to 75% of the combined weight of (A) and (B).

46. ​​The two-component reaction system as described in claim 45, wherein, The 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.

47. The two-component reaction system as described in claim 45 or 46, wherein, The one or more inorganic aluminate and / or silicate precursor materials comprise 30% to 60% of the combined weight of the one or more inorganic bases, water-soluble peroxides, one or more inorganic aluminate and / or silicate precursor materials, one or more monosaccharides, and water.

48. The two-component reaction system according to any one of claims 45 to 47, wherein, The one or more inorganic aluminate and / or silicate precursor materials (i) include aluminosilicates and alkali metal silicates.

49. The two-component reaction system as described in claim 48, wherein, The alkali metal silicate is present in the first alkaline aqueous premix.

50. The two-component reaction system as described in claim 48, wherein, The aluminosilicate is metakaolin.

51. The two-component reaction system as described in claim 50, wherein, The metakaolin is present in the first alkaline aqueous premix.

52. The two-component reaction system as described in claim 50, wherein, The metakaolin is present in the second aqueous premix.

53. The two-component reaction system as described in claim 50, wherein, A portion of the metakaolinite is present in the first alkaline aqueous premix, and another portion of the metakaolinite is present in the second aqueous premix.

54. The two-component reaction system according to any one of claims 45 to 53, wherein, The inorganic base includes sodium hydroxide, sodium oxide, potassium hydroxide, potassium oxide, or a mixture of any two or more thereof.

55. The two-component reaction system according to any one of claims 45 to 54, wherein, The sugars mentioned are reducing monosaccharides.

56. The two-component reaction system as described in claim 55, wherein, The reducing monosaccharide is xylose.

57. The two-component reaction system according to any one of claims 45 to 56, wherein, The sugars are present in the first alkaline aqueous premix.

58. The two-component reaction system according to any one of claims 45 to 56, wherein, The sugars are present in the second aqueous premix.

59. The two-component reaction system according to any one of claims 45 to 56, wherein, A portion of the sugars are present in the first alkaline aqueous premix, and another portion of the sugars are present in the second aqueous premix.

60. The two-component reaction system according to any one of claims 45 to 59, comprising at least 5 moles of the water-soluble peroxide compound per mole of the sugar.

61. The two-component reaction system according to any one of claims 45 to 60, wherein, The water-soluble peroxide compound is hydrogen peroxide.

62. The two-component reaction 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.

63. The two-component reaction 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 the water-soluble peroxide with the one or more monosaccharides.

64. The two-component reaction 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.

65. The two-component reaction 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.

Images