High temperature low emission mineral wool products

Abstract

The present invention relates to a high temperature, low emission mineral fiber product suitable for use as a thermal insulation material.

Description

Field of the Invention

[0001] The present invention relates to mineral fiber products and uses of mineral fiber products. Background of the Invention

[0003] Mineral fiber products (also known as mineral wool products) typically contain mineral fibers (also known as man-made vitreous fibers (MMVF)), such as glass fibers, ceramic fibers, basalt fibers, slag fibers, and stone fibers (rock fibers), bonded together by a cured thermosetting polymer binder material. For use as thermal or acoustic insulation products, bonded mineral fiber mats are typically produced by converting a melt made from suitable raw materials into fibers in a conventional manner, for example, by a spinning rotor process or a cascade rotor process. The fibers are blown into a forming chamber and, while pneumatically powered and still hot, sprayed with a binder solution and randomly deposited onto a moving conveyor belt in the form of a mat or web. The fiber mat is then transferred to a curing oven, where heated air is blown through the mat to cure the binder and firmly bond the mineral fibers together.

[0004] In the past, the binder resin of choice was phenolic resin, which can be produced economically and can be extended with urea before use as a binder. However, existing and proposed legislation aimed at reducing or eliminating formaldehyde emissions has led to the development of formaldehyde-free binders such as binder compositions based on polycarboxy polymers and polyols or polyamines (for example, the binder compositions disclosed in EP-A-583086, EP-A-990727, EP-A-1741726, US-A-5,318,990 and US-A-2007 / 0173588).

[0005] Another group of non-phenolic binders are addition / elimination reaction products of aliphatic and / or aromatic anhydrides with alkanolamines, as disclosed, for example, in WO 99 / 36368, WO 01 / 05725, WO 01 / 96460, WO 02 / 06178, WO 2004 / 007615, and WO 2006 / 061249. These binder compositions are water-soluble and exhibit excellent bonding properties in terms of cure speed and cure density. WO 2008 / 023032 discloses urea-modified binders of the type that provide mineral wool products with reduced hygroscopicity.

[0006] Since some of the starting materials used to produce these binders are relatively expensive chemicals, there is an ongoing need to provide formaldehyde-free binders that can be produced economically.

[0007] Another effect associated with previously known aqueous binder compositions for mineral fibers is that at least a large portion of the starting materials used to produce these binders originates from fossil fuels. There is a growing trend among consumers towards products that are produced entirely or at least partially from renewable materials, and there is a need to provide binders for mineral wool that are produced at least partially from renewable materials.

[0008] In high-temperature applications, mineral fiber products may release organic components originating from the binder when used at such high temperatures, particularly when used at such temperatures for the first time and / or when used at such temperatures for a short period of time. A high-temperature application is, for example, when mineral fiber products are used as insulation for pipes and equipment in power plants, where temperatures of 400°C to 500°C are not uncommon. Another high-temperature application is the use of mineral fiber products as insulation for furnaces, where the products may be used at their maximum operating temperatures of, for example, 600°C, 650°C, or even 700°C.

[0009] A particular problem in this regard is the release of harmful isocyanic acid (ICA) from mineral fiber products, particularly those containing urea-extended phenolic or other resins or urea-containing binders. Adding urea or other nitrogen-containing compounds is a conventional method for achieving better fire resistance and high-temperature thermal stability in mineral wool products.

[0010] The chemical formula for isocyanic acid is HNCO. A significant portion of ICA emissions from mineral fiber products may be due to the use of urea or urea derivatives in the binder composition. ICA emissions can cause health problems, and legislation exists or has been proposed to reduce or eliminate ICA emissions from mineral fiber products during installation and use, as well as from their production processes.

[0011] Other interesting chemical components from the thermal release may be hydrogen cyanide (HCN), ammonia (NH3) and NOx, but also other nitrous substances.

[0012] The present invention will be described below by means of two alternatives, namely Alternative A and Alternative B.

[0013] Alternative A (First to Fourth Aspects of the Invention) SUMMARY OF THE INVENTION

[0015] It was therefore an object of the present invention to provide a mineral fiber product which has improved high-temperature applications, can be produced economically, and uses renewable materials as starting products for the preparation of aqueous binder compositions.

[0016] Another object of the present invention is to provide uses of such mineral fiber products.

[0017] Another object of the present invention is to provide a method for transporting a medium through a pipeline at a high temperature.

[0018] According to a first aspect of the present invention there is provided a mineral fibre product comprising mineral fibres bonded by a cured binder composition, the uncured binder composition comprising one or more oxidised lignins, wherein heating the mineral fibre product to a temperature of 600°C releases less than 1500 ppm isocyanic acid (ICA) per gram solids content per second.

[0019] According to a second aspect of the present invention, there is provided the use of a mineral fibre product comprising mineral fibres bonded by a cured binder composition at a temperature of at least 300°C, preferably as a thermal insulation product, the uncured binder composition comprising one or more oxidised lignins, wherein optionally, heating the mineral fibre product to a temperature of 600°C releases less than 1500 ppm isocyanic acid (ICA) / g solids content / second.

[0020] According to a third aspect of the present invention, there is provided a method for conveying a medium, the method comprising the following steps:

[0021] a) covering the pipes with mineral fiber products as thermal pipe insulation, and

[0022] b) transporting the medium through the pipeline,

[0023] The mineral fiber product as a thermal pipe insulation material comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein optionally, heating the mineral fiber product to a temperature of 600° C. releases less than 1500 ppm of isocyanate (ICA) per gram of solids content per second.

[0024] According to a fourth aspect of the present invention, there is provided a pipe covered with a mineral fiber product as thermal insulation material, wherein the mineral fiber product comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein optionally, heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanic acid (ICA) / gram solids content / second.

[0025] The present inventors have surprisingly found that when using a binder composition based on oxidized lignin for mineral fiber products, it is possible to use mineral fiber products with low or even no ICA emission in high temperature applications.

[0026] DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The mineral fiber product of the present invention comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanic acid (ICA) / g solids / second, preferably less than 1000 ppm isocyanic acid (ICA) / g solids / second, more preferably less than 750 ppm isocyanic acid (ICA) / g solids / second.

[0028] The heated mineral fiber product contains a cured binder composition. With respect to "gram solids content," the solids content (LOI) refers to the amount of organic material in the mineral fiber product (loss on ignition). This solids content generally refers to the cured binder composition and any hydrophobizing agent and / or impregnating oil contained in the mineral fiber product.

[0029] When a mineral fiber product containing a cured binder composition is heated at a certain temperature and the exhaust gas is quantitatively analyzed for isocyanic acid (ICA) by Fourier transform infrared spectroscopy (FTIR), the result is a measurement of the amount of ICA released. This measurement is considered to be the amount of ICA released in relation to the amount of cured binder composition in the mineral fiber product tested.

[0030] For standardization purposes, the release rates for ICA and other given exhaust gases were determined according to Procedure I, described below, to obtain comparable data for different products tested at different temperatures. Please note that the data obtained are not quantitatively comparable to the release rates of these products determined under specific site conditions when implemented by end customers in industrial insulation systems. For example, in actual end customer installations, the products are not crushed as in Procedure I, described below, and the binder in the mineral fiber products is not completely burned off. In fact, the values ​​obtained using this Procedure I correspond to a worst-case scenario, both in terms of quantity and release time. Therefore, releases from these products are expected to be lower and at a slower rate (reaching steady-state in 2-48 hours), with this Procedure I reaching steady-state in less than 2 hours after actual installation compared to the values ​​obtained in this study. However, it is easy to assume that mineral fiber products that exhibit lower release rates compared to other products according to Procedure I will also have lower release rates in actual end customer installations.

[0031] Emission measurements of different mineral wool products are usually performed by comprehensive tests at external institutes such as RISE in Sweden using a combination of different material tests with different thicknesses to determine the dependence of the insulation thickness on the emission curve by quantification via FID signals and infrared measurements of released gases such as CO, NH3, HCN, NOx and ICA.

[0032] For Alternative A of the present application, the amount of ICA released was measured according to Procedure I described below. Different ground mineral wool products have been measured in-house according to Procedure I to eliminate discussions about thickness and porosity. These experiments were conducted in a custom-built release chamber (a tube furnace) that heated the material to a specific temperature set point for a specific time. During these experiments, air was passed through the chamber at a specified rate and sampled to quantify the different compounds. Four different temperatures were tested (250°C, 350°C, 450°C, and 600°C), and the released gases were quantified using Fourier transform infrared spectroscopy. Details on Procedure I are given below in the Experimental section.

[0033] Preferably, the mineral fibre product of the present invention also exhibits low emissions of other waste gases such as NH3, HCN and / or NOx when the mineral fibre product containing the cured binder composition is subjected to heating.

[0034] In a preferred embodiment, heating the mineral fiber product of the present invention to a temperature of 600°C releases less than 2500 ppm NH3 / g solid content / second, for example less than 2000 ppm NH3 / g solid content / second, for example less than 1500 ppm NH3 / g solid content / second, and / or heating the mineral fiber product to a temperature of 600°C releases less than 2000 ppm HCN / g solid content / second, for example less than 1500 ppm HCN / g solid content / second, for example less than 1000 ppm HCN / g solid content / second.

[0035] For the purposes of the present application, the amount of NH3, HCN and / or NOx released can be measured according to the same procedure I described below. Of course, the gas analysis by FTIR will then be targeted to the compounds to be determined.

[0036] The mineral fiber products of the present invention are suitable for high-temperature applications and also relate to thermal stability. In particular, the mineral fiber products of the present invention can be used in applications with a maximum operating temperature of at least 600°C, preferably at least 650°C. Therefore, according to the maximum service temperature panel test according to EN 14706:2012, the mineral fiber products of the present invention typically meet the maximum service temperature (MST) requirement of at least 600°C, preferably at least 650°C. MST is not related to thermal degradation or off-gassing, but rather to mechanical strength.

[0037] Typically, the uncured cement composition is an aqueous cement composition. In a preferred embodiment, the cement of the present invention does not contain formaldehyde.

[0038] For the purposes of this application, the term "formaldehyde-free" is defined as a term characterizing a mineral wool product wherein the formaldehyde released from the mineral wool product is less than 5 μg / m 2 / h, preferably less than 3 μg / m2 / h of mineral wool product. Preferably, the test is performed according to ISO 16000 for testing aldehyde emission.

[0039] The uncured binder composition used to prepare the mineral fibre product of the present invention comprises one or more oxidised lignins as component (i).

[0040] Component (i)

[0041] Component (i) is in the form of one or more oxidized lignins.

[0042] Lignin, cellulose, and hemicellulose are the three main organic compounds in plant cell walls. Lignin can be thought of as the glue that holds cellulose fibers together. Lignin contains both hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, after cellulose, and is estimated to account for as much as 20-30% of the total carbon contained in biomass, exceeding 1 billion tons globally.

[0043] Figure 1 A portion of a possible lignin structure is shown.

[0044] There are at least four groups of industrial lignins available on the market. These four groups are shown in Figure 3 A possible fifth group, biorefined lignin, is somewhat different in that it is not described by extraction method but by process source, such as biorefining, and therefore can be similar or different to any of the other groups mentioned. Each group is different from the others, and each is suitable for different applications. Lignin is a complex, heterogeneous material composed of up to three different phenylpropane monomers, depending on the source. Softwood lignin is primarily composed of coniferyl alcohol units (see Figure 2 ), and therefore they are more homogeneous than hardwood lignins, which have a higher syringol content (cf. Figure 2 ). The appearance and consistency of lignin varies greatly and depends largely on the process.

[0045] A summary of the properties of these industrial lignins is shown in Figure 4 middle.

[0046] Lignosulfonates derived from the sulfite pulping process remain the largest commercially available source of lignin, with a production capacity of 1.4 million tons. However, aside from these, the kraft process is currently the most widely used pulping process and is gradually replacing the sulfite process. An estimated 78 million tons of lignin are produced annually through the kraft pulping process globally, but much of this is burned to produce steam and energy. Current kraft recycling capacity is estimated at 160,000 tons, but sources indicate that only approximately 75,000 tons are currently recycled. Kraft lignin is developed from black liquor, the waste liquor from the kraft or kraft processes. Currently, three well-known processes are used to produce kraft lignin: LignoBoost, LignoForce, and SLRP. These three processes are similar in that they involve the addition of CO2 to lower the pH to 9-10, followed by acidification to further reduce the pH to approximately 2. The final step involves some combination of washing, leaching, and filtration to remove ash and other contaminants. These three processes are at varying stages of commercialization worldwide.

[0047] The sulfate process introduces thiol groups and stilbene, while retaining some carbohydrates. Since the lignin is precipitated from the liquor with sulfuric acid, sodium sulfate is also present as an impurity, but this could potentially be avoided by modifying the method used to isolate the lignin. The sulfate process results in a high concentration of phenolic hydroxyl groups, and when these groups are ionized (at a pH above about 10), the lignin becomes soluble in water.

[0048] Commercial kraft lignin is generally purer than lignin sulfonate and has a molecular weight of 1000-3000 g / mol.

[0049] Alkali lignin is derived from the sodium hydroxide pulping process used primarily for wheat straw, bagasse, and flax. g In terms of alkali lignin, the properties of alkali lignin are similar to those of kraft lignin. This process does not use sulfur, nor does it contain covalently bound sulfur. Ash levels are very low. Alkali lignin has low solubility in neutral and acidic media, but is fully soluble at pH 12 and above.

[0050] The ligninsulfonate process introduces a large number of sulfonate groups, making lignin soluble in water but also in acidic aqueous solutions. Lignosulfonates contain up to 8% sulfur in the form of sulfonates, while kraft lignin has 1-2% sulfur, primarily bound to the lignin. Lignosulfonates have a molecular weight of 15,000-50,000 g / mol. Compared to other types of lignin, this type of lignin contains more residual carbohydrates and has a higher average molecular weight. Lignin's characteristic hydrophobic core, combined with the large number of ionized sulfonate groups, makes this type of lignin attractive as a surfactant, and it is often used in applications such as dispersing cement.

[0051] Another group of lignins that is becoming available is lignin produced by biorefining processes, in which carbohydrates are separated from lignin by chemical or biochemical processes to produce a carbohydrate-rich fraction. This remaining lignin is called biorefining lignin. Biorefineries focus on producing energy and alternatives to products obtained from fossil fuels and petrochemicals, as well as lignin. Lignin from this process is generally considered a low-value product or even a waste that is primarily used for thermal combustion or as a low-grade feed or disposed of in other ways.

[0052] The availability of organosolv lignin is still being considered on a pilot scale. This process involves extracting lignin using water and various organic solvents (most commonly ethanol) and some organic acids. One advantage of this method is that the lignin obtained is relatively pure, but it is much more expensive than other industrial lignins and has solubility in organic solvents but not in water.

[0053] Previous attempts to use lignin as a base compound in binder compositions for mineral fibers failed because it proved difficult to find suitable crosslinkers capable of achieving the desired mechanical properties of the cured mineral wool product while avoiding harmful and / or corrosive components. Currently, lignin is used to replace petroleum-derived chemicals, such as phenol in binder applications or phenolic resins in asphalt. It is also used as a cement and concrete additive and, in some applications, as a dispersant.

[0054] The crosslinking of polymer will provide improved performance usually, as mechanical, chemical and thermal tolerance etc.Lignin has abundant phenolic hydroxyl group and aliphatic hydroxyl group especially, and they can react, and cause the crosslinked structure of lignin.Different lignins also will have other available functional groups, and they can be utilized potentially.The existence of these other groups depends on the mode (sulfonate radical in the mercaptan in the sulfate lignin, the lignin sulfonate etc.) of lignin and Mierocrystalline cellulose and hemicellulose separation to a great extent, depends on source.

[0055] It has been found that by using oxidized lignin, a binder composition for mineral fibers can be prepared which allows the mineral fiber products produced therefrom to have excellent properties, while not requiring other components to be included in the binder composition, enabling the mineral fiber products of the present invention to be used in high temperature applications with low levels of ICA emissions or even no ICA emissions.

[0056] In one embodiment, the component (i) is in the form of one or more oxidized kraft lignins.

[0057] In one embodiment, the component (i) is in the form of one or more oxidized alkali lignins.

[0058] In one embodiment, the component (i) is in the form of one or more ammonia-oxidized lignins. For the purposes of the present invention, the term "ammonia-oxidized lignin" is understood to mean lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.

[0059] In an alternative embodiment, the ammonia is partially or completely replaced by an alkali metal hydroxide, in particular sodium hydroxide and / or potassium hydroxide.

[0060] A typical oxidizing agent used to prepare the oxidized lignin is hydrogen peroxide.

[0061] In one embodiment, the ammonia-oxidized lignin comprises one or more compounds selected from ammonia, amines, hydroxides or any salts thereof.

[0062] In one embodiment, the component (i) has a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i).

[0063] In the binder composition, preferably an aqueous binder composition, used according to the present invention, component (i), i.e. the one or more oxidized lignins, may be present in an amount of 25-95% by weight, such as 30-90% by weight, such as 35-85% by weight, based on the dry weight of the binder composition.

[0064] In one embodiment, the component (i) has an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups per macromolecule of component (i), such as more than 2.5 groups per macromolecule of component (i).

[0065] It is believed that the carboxylic acid group content of the oxidized lignin plays an important role in the surprising advantages of the aqueous binder composition for mineral fibers of the present invention. In particular, it is believed that the carboxylic acid groups of the oxidized lignin improve the crosslinking properties and thus allow the cured mineral fiber product to have better mechanical properties.

[0066] In a preferred embodiment, the uncured binder composition, preferably an aqueous binder composition, used to prepare the mineral fiber product of the present invention comprises:

[0067] - component (i) in the form of one or more oxidized lignins;

[0068] - component (ii) in the form of one or more crosslinking agents;

[0069] - Optionally, component (iii) in the form of one or more plasticizers.

[0070] Component (ii)

[0071] Optional component (ii) is in the form of one or more cross-linking agents.

[0072] In one embodiment, component (ii) comprises one or more crosslinkers selected from β-hydroxyalkylamide crosslinkers and / or oxazoline crosslinkers.

[0073] β-Hydroxyalkylamide crosslinkers are curing agents for acid-functional macromolecules. They provide a hard, durable, corrosion-resistant, and solvent-resistant crosslinked polymer network. β-Hydroxyalkylamide crosslinkers are believed to cure via an esterification reaction to form multiple ester bonds. The hydroxyl functionality of the β-Hydroxyalkylamide crosslinker should average at least 2, preferably greater than 2, and more preferably between 2 and 4, for optimal curing response.

[0074] The oxazoline-containing crosslinking agent is a polymer containing one or more oxazoline groups in each molecule, and can generally be easily obtained by polymerizing oxazoline derivatives. Patent US6818699B2 discloses such a method.

[0075] In one embodiment, the component (ii) is an epoxidized oil based on fatty acid triglycerides.

[0076] It is noted that epoxidized oils based on fatty acid triglycerides are not considered hazardous and therefore the use of these compounds in the cement compositions of the present invention does not render these compositions unsafe to handle.

[0077] In one embodiment, the component (ii) is a molecule having three or more epoxy groups.

[0078] In one embodiment, the component (ii) is one or more flexible oligomers or polymers, such as low Tg acrylic polymers, such as low Tg vinyl polymers, such as low Tg polyethers, which contain reactive functional groups, such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

[0079] In one embodiment, component (ii) is selected from the group consisting of crosslinking agents that participate in the curing reaction, such as hydroxyalkylamides, alkanolamines, and reaction products of alkanolamines and polycarboxylic acids. Reaction products of alkanolamines and polycarboxylic acids can be found in US Pat. No. 6,706,853 B1.

[0080] Without wishing to be bound by any particular theory, it is believed that the very advantageous properties of the binder composition, preferably an aqueous binder composition, of the present invention are due to the interaction of the oxidized lignin used as component (i) and the crosslinking agent mentioned above. It is believed that the presence of carboxylic acid groups in the oxidized lignin enables the oxidized lignin to crosslink very effectively.

[0081] In one embodiment, the component (ii) is one or more crosslinking agents selected from the group consisting of polyfunctional organic amines, such as alkanolamines, diamines such as 1,6-hexanediamine, and triamines.

[0082] In one embodiment, the component (ii) is one or more crosslinking agents selected from the group consisting of polyethyleneimine, polyvinylamine, and fatty amine.

[0083] In one embodiment, the component (ii) is one or more fatty amides.

[0084] In one embodiment, the component (ii) is one or more cross-linking agents selected from the group consisting of dimethoxyacetaldehyde, glycolaldehyde, and glyoxylic acid.

[0085] In one embodiment, the component (ii) is one or more crosslinking agents selected from polyester polyols such as polycaprolactone.

[0086] In one embodiment, the component (ii) is one or more cross-linking agents selected from the group consisting of starch, modified starch, and CMC.

[0087] In one embodiment, the component (ii) is one or more crosslinking agents in the form of aliphatic polyfunctional carbodiimides.

[0088] In one embodiment, the component (ii) is one or more crosslinking agents selected from melamine-based crosslinking agents such as hexa(methylmethoxy)melamine (HMMM)-based crosslinking agents.

[0089] Examples of such compounds are Picassian XL 701, 702, 725 (Stahl Polymers), e.g. XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).

[0090] In one embodiment, component (ii) is Primid XL552, which has the following structure:

[0091]

[0092] Component (ii) may also be any mixture of the above-mentioned compounds.

[0093] In one embodiment, the cement composition of the present invention comprises component (ii) in an amount of 1 to 40 wt%, such as 4 to 20 wt%, such as 6 to 12 wt%, based on the dry weight of component (i).

[0094] Component (iii)

[0095] Optional component (iii) is in the form of one or more plasticizers.

[0096] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids, such as adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides such as urea / urea, or any mixtures thereof.

[0097] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of carbonates, for example ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with a structure similar to lignin, such as vanillin, acetosyringone, solvents used as coalescents, such as alcohol ethers, polyvinyl alcohol.

[0098] In one embodiment, component (iii) is in the form of one or more non-reactive plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or other esters, solvents used as coalescing agents such as alcohol ethers, acrylic polymers, polyvinyl alcohol.

[0099] In one embodiment, component (iii) is one or more reactive plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tricarboxylic acids, such as adipic acid, or lactic acid, and / or vanillic acid and / or ferulic acid, polyurethane dispersions, acrylic acid-based polymers with free carboxyl groups, compounds with a structure similar to lignin, such as vanillin, acetosyringone.

[0100] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of fatty alcohols, monohydric alcohols such as amyl alcohol, stearyl alcohol.

[0101] In one embodiment, component (iii) comprises one or more plasticizers selected from the group consisting of polyethylene glycol, polyethylene glycol ethers.

[0102] Another particularly surprising aspect of the present invention is that the use of plasticizers with a boiling point above 100°C, in particular with a boiling point between 140 and 250°C, significantly improves the mechanical properties of the mineral fiber products of the present invention, even though, given their boiling point, these plasticizers are likely to at least partially evaporate during the curing of the binder, preferably an aqueous binder, in contact with the mineral fibers.

[0103] In one embodiment, component (iii) comprises one or more plasticizers having a boiling point above 100°C, for example from 110 to 280°C, more preferably from 120 to 260°C, more preferably from 140 to 250°C.

[0104] It is believed that the effectiveness of these plasticizers in the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention is related to the effect of increasing the mobility of the oxidized lignin during the curing process. It is believed that the increased mobility of the lignin or oxidized lignin during the curing process promotes effective crosslinking.

[0105] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, in particular 150 to 4,000 g / mol, more particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, more preferably 200 to 400 g / mol.

[0106] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4000 to 25000 g / mol, in particular 4000 to 15000 g / mol, more particularly 8000 to 12000 g / mol.

[0107] In one embodiment, component (iii) is capable of forming a covalent bond with component (i) and / or component (ii) during the curing process. Such a component will not evaporate and remain as part of the composition, but will be effectively modified so as not to introduce unwanted side effects such as water absorption of the cured product. Non-limiting examples of such components are caprolactone and acrylic acid-based polymers with free carboxyl groups.

[0108] In one embodiment, component (iii) is selected from the group consisting of fatty alcohols, monohydric alcohols, such as amyl alcohol, stearyl alcohol.

[0109] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxides, such as ethoxides, for example butanol ethoxides such as butoxytriglycol.

[0110] In one embodiment, component (iii) is selected from one or more propylene glycols.

[0111] In one embodiment, component (iii) is selected from one or more glycol esters.

[0112] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates.

[0113] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of phenol derivatives, such as alkyl or aryl substituted phenols.

[0114] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of silanols, siloxanes.

[0115] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkylarylsulfonates, for example alkylsulfonates, phosphates such as tripolyphosphates; for example tributyl phosphate.

[0116] In one embodiment, component (iii) is selected from one or more hydroxy acids.

[0117] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of monomeric amides, such as acetamide, benzamide, fatty acid amides, such as tall oil amide.

[0118] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of quaternary ammonium compounds, such as trimethylglycine, distearyldimethylammonium chloride.

[0119] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of vegetable oils, such as castor oil, palm oil, linseed oil, tall oil, soybean oil.

[0120] In one embodiment, component (iii) is in the form of tall oil.

[0121] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils.

[0122] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0123] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucosides, glucamides, aminoglucamides, sucrose esters, sorbitan esters.

[0124] It has surprisingly been found that the inclusion of a plasticizer in the binder composition, preferably an aqueous binder composition, used according to the invention greatly improves the mechanical properties of the mineral fiber product of the invention.

[0125] The term "plasticizer" refers to a substance added to a material to make the material softer, more flexible (by lowering the glass transition temperature, Tg), and easier to process.

[0126] Component (iii) may also be any mixture of the compounds mentioned above.

[0127] In one embodiment, component (iii) is present in an amount of 0.5 to 50 wt%, preferably 2.5 to 25 wt%, more preferably 3 to 15 wt%, based on the dry weight of component (i).

[0128] A binder composition for mineral fibers, preferably an aqueous binder composition, comprising components (i) and (iia)

[0129] In one embodiment, the present invention relates to a binder composition for mineral fibers, preferably an aqueous binder composition, comprising:

[0130] - component (i) in the form of one or more oxidized lignins;

[0131] - component (iia) in the form of one or more modifiers.

[0132] The inventors have found that the excellent binder properties can also be achieved by a two-component system comprising component (i) in the form of one or more oxidized lignins and component (iia) in the form of one or more modifiers, and optionally any other components mentioned above and below.

[0133] In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from the group consisting of epoxidized oils based on fatty acid triglycerides.

[0134] In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from the group consisting of molecules having three or more epoxy groups.

[0135] In one embodiment, component (iia) is a modifier in the form of one or more of the following: a flexible oligomer or polymer, such as a low Tg acrylic polymer, such as a low Tg vinyl polymer, such as a low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

[0136] In one embodiment, component (iia) is one or more modifiers selected from the group consisting of polyethyleneimine, polyvinylamine, and fatty amine.

[0137] In one embodiment, component (iia) is one or more modifying agents selected from the group consisting of aliphatic multifunctional carbodiimides.

[0138] Component (iia) may also be any mixture of the above-mentioned compounds.

[0139] Without wishing to be bound by any particular theory, the present inventors believe that the excellent binder properties achieved by the binder composition for mineral fibres comprising components (i) and (iia) and optionally further components are at least partly due to the effect of the modifier acting as component (iia) functioning at least partly as a plasticiser and a cross-linking agent.

[0140] In one embodiment, the cement composition, preferably an aqueous cement composition, comprises component (iia) in an amount of 1 to 40 wt%, such as 4 to 20 wt%, such as 6 to 12 wt%, based on the dry weight of component (i).

[0141] Additional components

[0142] In some embodiments, the cement composition, preferably an aqueous cement composition, used according to the present invention comprises additional components.

[0143] In one embodiment, the binder composition used according to the present invention, preferably an aqueous binder composition, contains a catalyst selected from the group consisting of: inorganic acids, such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid and / or phosphoric acid, and / or any salts thereof, such as sodium hypophosphite, and / or ammonium salts such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid and / or phosphoric acid, and / or sodium polyphosphate (STTP), and / or sodium metaphosphate (STMP), and / or phosphorus oxychloride. The presence of such a catalyst can improve the curing properties of the binder composition used according to the present invention, preferably an aqueous binder composition.

[0144] In one embodiment, the binder composition used according to the present invention, preferably an aqueous binder composition, comprises a catalyst selected from Lewis acids that can accept an electron pair from a donor compound forming a Lewis adduct, such as ZnCl2, Mg(ClO4)2, Sn[N(SO2-n-C8F 17 )2]4.

[0145] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the present invention comprises a catalyst selected from metal chlorides, such as KCl, MgCl2, ZnCl2, FeCl3 and SnCl2.

[0146] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises a catalyst selected from metal organic compounds, such as titanate-based catalysts and tin-based catalysts.

[0147] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention comprises a catalyst selected from chelating agents, such as transition metals, for example iron ions, chromium ions, manganese ions, copper ions.

[0148] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention further comprises a further component (iv) in the form of one or more silanes.

[0149] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention comprises a further component (iv) in the form of one or more coupling agents, such as organofunctional silanes.

[0150] In one embodiment, component (iv) is selected from the group consisting of organofunctional silanes, such as primary or secondary amino-functionalized silanes, epoxy-functionalized silanes, such as polymeric or oligomeric epoxy-functionalized silanes, methacrylate-functionalized silanes, alkyl- and aryl-functionalized silanes, urea-functionalized silanes, or vinyl-functionalized silanes.

[0151] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the present invention further comprises component (v) in the form of one or more components selected from ammonia, amines or any salts thereof.

[0152] It has been found that when oxidized lignin which has not been oxidized in the presence of ammonia is used in component (i), it may be particularly useful to include ammonia, an amine or any salt thereof as a further component.

[0153] In one embodiment, the binder composition used according to the invention, preferably an aqueous binder composition, further comprises a further component in the form of urea, in particular in an amount of 5 to 40% by weight, for example 10 to 30% by weight, 15 to 25% by weight, based on the dry weight of component (i).

[0154] In one embodiment, the binder composition used according to the present invention, preferably an aqueous binder composition, further comprises an additional component, which is in the form of one or more carbohydrates selected from the group consisting of sucrose, reducing sugars, in particular dextrose, polysaccharides, and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, more preferably glucose syrup with a dextrose equivalent value DE of 30 to less than 100, for example DE of 60 to less than 100, for example DE=60-99, for example DE=85-99, for example DE=95-99.

[0155] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the present invention further comprises an additional component in the form of one or more carbohydrates selected from sucrose and reducing sugars in an amount of 5 to 50% by weight, such as 5 to less than 50% by weight, such as 10-40% by weight, such as 15-30% by weight, based on the dry weight of component (i).

[0156] In the context of the present invention, a binder composition having a sugar content of 50% by weight or more based on the total dry weight of the binder components is considered to be a sugar-based binder. In the context of the present invention, a binder composition having a sugar content of less than 50% by weight based on the total dry weight of the binder components is considered to be a non-sugar-based binder.

[0157] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, further comprises an additional component in the form of one or more surfactants in the form of nonionic and / or ionic emulsifiers, such as polyoxyethylene (4) lauryl ether, soy lecithin, sodium lauryl sulfate.

[0158] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0159] - component (i) in the form of one or more ammonia-oxidized lignins having a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0160] - component (ii) in the form of one or more crosslinking agents selected from β-hydroxyalkylamide crosslinkers and / or oxazoline crosslinkers and / or one or more crosslinking agents selected from the group consisting of polyfunctional organic amines, for example alkanolamines, diamines such as 1,6-hexanediamine, triamines;

[0161] - component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, in particular 150 to 4,000 g / mol, more particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, more preferably 150 to 300 g / mol, or having an average molecular weight of 4,000 to 25,000 g / mol, in particular 4,000 to 15,000 g / mol, more particularly 8,000 to 12,000 g / mol; wherein preferably the binder composition, preferably an aqueous binder composition, comprises 1 to 40% by weight, for example 4 to 20% by weight, 6 to 12% by weight, based on the dry weight of component (i), of component (ii), and component (iii) is present in an amount of 0.5 to 50% by weight, preferably 2.5 to 25% by weight, more preferably 3 to 15% by weight, based on the dry weight of component (i).

[0162] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0163] - component (i) in the form of one or more ammonia-oxidized lignins having a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0164] - component (iia) in the form of one or more modifiers chosen from epoxidized oils based on fatty acid triglycerides.

[0165] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0166] - component (i) in the form of one or more ammonia-oxidized lignins having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups per macromolecule of component (i), for example more than 2.5 groups per macromolecule of component (i);

[0167] - component (ii) in the form of one or more crosslinking agents selected from β-hydroxyalkylamide crosslinkers and / or oxazoline crosslinkers and / or one or more crosslinking agents selected from the group consisting of polyfunctional organic amines, for example alkanolamines, diamines such as 1,6-hexanediamine, triamines;

[0168] - component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, in particular 150 to 4,000 g / mol, more particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, more preferably 150 to 300 g / mol, or having an average molecular weight of 4,000 to 25,000 g / mol, in particular 4,000 to 15,000 g / mol, more particularly 8,000 to 12,000 g / mol; wherein preferably the binder composition, preferably an aqueous binder composition, comprises 1 to 40% by weight, for example 4 to 20% by weight, 6 to 12% by weight, based on the dry weight of component (i), of component (ii), and component (iii) is present in an amount of 0.5 to 50% by weight, preferably 2.5 to 25% by weight, more preferably 3 to 15% by weight, based on the dry weight of component (i).

[0169] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0170] - component (i) in the form of one or more ammonia-oxidized lignins having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups per macromolecule of component (i), for example more than 2.5 groups per macromolecule of component (i);

[0171] - component (iia) in the form of one or more modifiers chosen from epoxidized oils based on fatty acid triglycerides.

[0172] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention consists essentially of the following components:

[0173] - component (i) in the form of one or more oxidized lignins;

[0174] - component (ii) in the form of one or more cross-linking agents;

[0175] - component (iii) in the form of one or more plasticizers;

[0176] - component (iv) in the form of one or more coupling agents such as organofunctional silanes;

[0177] - optional components in the form of one or more compounds selected from ammonia, amines or any salts thereof;

[0178] - optional components in the form of urea;

[0179] - optional components in the form of more reactive or non-reactive silicones;

[0180] - optionally a hydrocarbon oil;

[0181] - optionally one or more surfactants;

[0182] -water.

[0183] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention consists essentially of the following components:

[0184] - component (i) in the form of one or more oxidized lignins;

[0185] - component (iia) in the form of one or more modifiers chosen from epoxidized oils based on fatty acid triglycerides;

[0186] - component (iv) in the form of one or more coupling agents such as organofunctional silanes;

[0187] - optional components in the form of one or more compounds selected from ammonia, amines or any salts thereof;

[0188] - optional components in the form of urea;

[0189] - optional components in the form of more reactive or non-reactive silicones;

[0190] - optionally a hydrocarbon oil;

[0191] - optionally one or more surfactants;

[0192] -water.

[0193] Method for producing mineral fiber products

[0194] The mineral fiber product of the present invention can be prepared by conventional methods for producing mineral fiber products by binding mineral fibers with a binder composition. Therefore, the mineral fiber product of the present invention is preferably prepared by a method comprising the steps of contacting mineral fibers with an uncured, preferably aqueous, binder composition comprising one or more oxidized lignins.

[0195] In a preferred embodiment, the uncured, preferably aqueous, cement composition comprises:

[0196] - component (i) in the form of one or more oxidized lignins;

[0197] - component (ii) in the form of one or more crosslinking agents;

[0198] - optional component (iii) in the form of one or more plasticizers.

[0199] Curing

[0200] The uncured binder composition in a mineral fiber product precursor, such as a web in which the mineral fibers are in contact with the binder composition, is cured by chemical and / or physical reaction of the binder components.

[0201] In one embodiment, the curing is carried out in a curing apparatus.

[0202] In one embodiment, the curing is carried out at a temperature of 100-300°C, such as 170-270°C, such as 180-250°C, such as 190-230°C.

[0203] In one embodiment the curing is carried out in a conventional curing oven used for mineral wool production, operating at a temperature of 150 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.

[0204] In one embodiment, the curing is performed for a period of 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes.

[0205] In a typical embodiment, curing is performed at a temperature of 150 to 250° C. for a time period of 30 seconds to 20 minutes.

[0206] The curing process may begin immediately after the binder is applied to the fibers. Curing is defined as the process by which a binder composition undergoes a physical and / or chemical reaction (curing typically increases the molecular weight of compounds in the binder composition in the case of a chemical reaction) and thereby increases the viscosity of the binder composition, typically until the binder composition reaches a solid state.

[0207] In one embodiment, the curing process comprises drying by pressure.Pressure may be applied by blowing air or gas through / over the mixture of mineral fibres and binder.

[0208] Mineral fiber products of the present invention

[0209] The present invention relates to a mineral fibre product comprising mineral fibres in contact with a cured binder composition as described above, ie in contact with a cured binder resulting from the curing of a binder composition, preferably an aqueous binder composition, as described above.

[0210] The mineral fibers used can be any one of man-made vitreous fibers (MMVF), glass fibers, ceramic fibers, basalt fibers, slag fibers, rock fibers, stone fibers, etc. These fibers can be in the form of velvet products such as asbestos products.

[0211] Fiber / melt composition

[0212] Man-made vitreous fibers (MMVF) can have any suitable oxide composition. The fibers can be glass fibers, ceramic fibers, basalt fibers, slag fibers, or rock or stone fibers. The fibers are preferably of the type commonly referred to as rock fibers, stone fibers, or slag fibers, most preferably stone fibers.

[0213] Stone fiber usually contains the following oxides, expressed in weight percentage:

[0214] SiO2:30-51

[0215] CaO: 8-30

[0216] MgO: 2-25

[0217] FeO (including Fe2O3): 2-15

[0218] Na2O+K2O: no more than 10

[0219] CaO+MgO: 10-30

[0220] In some preferred embodiments, the MMVF has the following elemental levels, calculated as oxides and expressed in weight %:

[0221] SiO2: at least 30, 32, 35 or 37; not more than 51, 48, 45 or 43

[0222] Al2O3: at least 12, 16 or 17; not more than 30, 27 or 25

[0223] CaO: at least 8 or 10; no more than 30, 25 or 20

[0224] MgO: at least 2 or 5; no more than 25, 20 or 15

[0225] FeO (including Fe2O3): at least 4 or 5; not more than 15, 12 or 10

[0226] FeO+MgO: at least 10, 12 or 15; not more than 30, 25 or 20

[0227] Na2O+K2O: 0 or at least 1; not more than 10

[0228] CaO+MgO: at least 10 or 15; not more than 30 or 25

[0229] TiO2: 0 or at least 1; no more than 6, 4 or 2

[0230] TiO2+FeO: at least 4 or 6; not more than 18 or 12

[0231] B2O3: 0 or at least 1; no more than 5 or 3

[0232] P2O5: 0 or at least 1; not more than 8 or 5

[0233] Other: 0 or at least 1; no more than 8 or 5

[0234] The MMVF prepared by the method of the present invention preferably has the following composition (expressed in wt%):

[0235] SiO2: 35-50

[0236] Al2O3: 12-30

[0237] TiO2: up to 2

[0238] Fe2O3: 3-12

[0239] CaO: 5-30

[0240] MgO: up to 15

[0241] Na2O: 0-15

[0242] K2O: 0-15

[0243] P2O5: up to 3

[0244] MnO: up to 3

[0245] B2O3: up to 3

[0246] Another preferred composition of MMVF is as follows (expressed in wt%):

[0247] SiO2: 39-55%, preferably 39-52%

[0248] Al2O3: 16-27%, preferably 16-26%

[0249] CaO: 6-20%, preferably 8-18%

[0250] MgO: 1-5%, preferably 1-4.9%

[0251] Na2O: 0-15%, preferably 2-12%

[0252] K2O: 0-15%, preferably 2-12%

[0253] R2O (Na2O + K2O): 10-14.7%, preferably 10-13.5%

[0254] P2O5: 0-3%, preferably 0-2%

[0255] Fe2O3 (total iron): 3-15%, preferably 3.2-8%

[0256] B2O3: 0-2%, preferably 0-1%

[0257] TiO2: 0-2%, preferably 0.4-1%

[0258] Others: 0-2.0%

[0259] Glass fibers typically contain the following oxides (expressed in wt%):

[0260] SiO2:50-70

[0261] Al2O3: 10-30

[0262] CaO: no more than 27

[0263] MgO: not more than 12

[0264] Glass fibers may also contain the following oxides (expressed in wt%):

[0265] Na2O+K2O: 8-18, especially Na2O+K2O is greater than CaO+MgO

[0266] B2O3:3-12

[0267] Certain glass fiber compositions may contain less than 2% Al2O3.

[0268] Suitable fiber formation methods and subsequent production steps for producing mineral fiber products are those conventional in the art. Typically, the binder is sprayed onto the airborne mineral fibers immediately after fibrillation of the mineral melt. The amount of uncured, preferably aqueous, binder composition applied is typically 0.1 to 18% by weight, preferably 0.2 to 8% by weight, of the mineral fiber product being bonded, calculated on a dry basis.

[0269] The sprayed mineral fiber web is usually cured in a curing oven using a stream of hot air, which can be introduced into the mineral fiber web from below or above or from alternating directions in different zones along the length of the curing oven.

[0270] Typically, the curing oven operates at a temperature of about 150° C. to about 300° C., such as 170 to 270° C., such as 180 to 250° C., such as 190 to 230° C. Typically, the curing oven residence time is 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes, depending on, for example, product density.

[0271] In a typical embodiment, the mineral fiber product of the invention is cured at a temperature of from 150°C to 250°C for a period of from 30 seconds to 20 minutes.

[0272] If desired, the mineral fiber web may be subjected to a shaping process before curing. The bonded mineral fiber product emerging from the curing oven may be cut into the desired form, for example in the form of a batt.

[0273] In a preferred embodiment, the mineral fiber product of the present invention is a thermal insulation product. The mineral fiber product is preferably in the form of preformed pipe sections, mats or slabs.

[0274] In a preferred embodiment, the mineral fiber product of the present invention has a thickness in the range of 20 mm to 500 mm, preferably 30 mm to 300 mm, such as 50 mm to 150 mm, wherein typically the mineral fiber product is in the form of a sheet.

[0275] The mineral fiber products of the present invention generally have a mass fraction of 6-250 kg / m 3 , preferably 20-200kg / m 3 The mineral fiber product typically has a loss on ignition (LOI) in the range of 0.25-18.0% or 0.3-18.0%, preferably 0.5-8.0%. In a preferred embodiment, the mineral fiber product has a loss on ignition (LOI) of 0.25-8.0% or 0.3-8.0%, more preferably 0.25-6.0%.

[0276] Use of the mineral fiber product of the invention

[0277] The inventive use of the mineral fiber product relates to high temperature applications. High temperature applications here mean using the mineral fiber product at temperatures of at least 300°C, preferably at least 400°C, for example at least 450°C and / or up to 700°C.

[0278] The present invention therefore also relates to the use of a mineral fiber product comprising mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, at a temperature of at least 300° C., preferably at least 400° C., for example at least 450° C. Typically, the use according to the invention is at a temperature not exceeding 700° C., preferably not exceeding 650° C.

[0279] Generally, it is preferred that heating the mineral fiber product to a temperature of 600° C. releases less than 1500 ppm isocyanic acid (ICA) / g solids / second, more preferably less than 1000 ppm isocyanic acid (ICA) / g solids / second, still more preferably less than 750 ppm isocyanic acid (ICA) / g solids / second. The method for determining the ICA release rate is described below.

[0280] In a preferred embodiment of the use according to the invention, the mineral fiber product is used as a thermal insulation product, more preferably as a thermal pipe insulation material.

[0281] For use according to the invention, the pipe is preferably operated at a high use temperature of at least 300° C., preferably at least 400° C., for example at least 450° C. Typically, the temperature does not exceed 700° C., preferably does not exceed 650° C.

[0282] The pipeline is preferably a metal pipeline. In particular, the pipeline is used to transport a medium, such as gas, steam or fluid. The medium transported by the pipeline is usually a high-temperature medium with the above-mentioned minimum operating temperature.

[0283] The mineral fibre product for the use according to the invention may have all the features described above for the mineral fibre product according to the invention, to which description reference is therefore made.

[0284] Method for conveying medium of the present invention

[0285] The present invention also relates to a method for conveying a medium, comprising the following steps:

[0286] a) covering the pipes with mineral fiber products as thermal pipe insulation, and

[0287] b) transporting the medium through the pipeline,

[0288] The mineral fiber product comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins.

[0289] Generally, it is preferred that heating the mineral fiber product to a temperature of 600° C. releases less than 1500 ppm isocyanic acid (ICA) / g solids / second, for example less than 1000 ppm isocyanic acid (ICA) / g solids / second, preferably less than 750 ppm isocyanic acid (ICA) / g solids / second. The method for determining the ICA release rate is described below.

[0290] In a preferred embodiment, the conveyed medium has a temperature of at least 300° C., preferably at least 400° C., for example at least 450° C. Preferably, the temperature does not exceed 700° C., preferably does not exceed 650° C.

[0291] The medium transported through the pipes may be, for example, gas, steam or fluid.

[0292] The mineral fibre product used in the process according to the invention may have all the features described above for the mineral fibre product according to the invention, to which description reference is therefore made.

[0293] Pipe with thermal insulation material of the present invention

[0294] The present invention also relates to a pipe covered or wrapped with a mineral fiber product as thermal insulation material, wherein the mineral fiber product comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins.

[0295] Generally, it is preferred that heating the mineral fiber product to a temperature of 600° C. releases less than 1500 ppm isocyanic acid (ICA) / g solids / second, preferably less than 1000 ppm isocyanic acid (ICA) / g solids / second, more preferably less than 750 ppm isocyanic acid (ICA) / g solids / second. The method for determining the ICA release rate is described below.

[0296] The mineral fibre product for covering the pipe according to the invention may have all the features described above for the mineral fibre product according to the invention, to which reference is therefore made.

[0297] Alternative B (Fifth to Eighth Aspects of the Invention) SUMMARY OF THE INVENTION

[0299] As indicated above, one object of the present invention is to provide a mineral fiber product which has improved high temperature applications, can be produced economically, and uses renewable materials as starting products for the preparation of aqueous binder compositions.

[0300] Another object of the present invention is to provide uses of such mineral fiber products.

[0301] Another object of the present invention is to provide a method for transporting a medium through a pipeline at a high temperature.

[0302] According to a fifth aspect of the present invention, there is provided a mineral fiber product comprising mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1000 μg isocyanic acid (ICA) / gram sample, for example less than 750 μg isocyanic acid (ICA) / gram sample, for example less than 500 μg isocyanic acid (ICA) / gram sample, for example less than 250 μg isocyanic acid (ICA) / gram sample, for example less than 100 μg isocyanic acid (ICA) / gram sample.

[0303] According to a sixth aspect of the present invention, there is provided the use of a mineral fiber product comprising mineral fibers bonded by a cured binder composition at a temperature of at least 300°C, preferably as an insulation product, the uncured binder composition comprising one or more oxidized lignins, wherein optionally, heating the mineral fiber product to a temperature of 600°C releases less than 1000 μg isocyanic acid (ICA) / gram sample, for example less than 750 μg isocyanic acid (ICA) / gram sample, for example less than 500 μg isocyanic acid (ICA) / gram sample, for example less than 250 μg isocyanic acid (ICA) / gram sample, for example less than 100 μg isocyanic acid (ICA) / gram sample.

[0304] According to a seventh aspect of the present invention, there is provided a method for conveying a medium, the method comprising the steps of:

[0305] a) covering the pipes with mineral fiber products as thermal pipe insulation, and

[0306] b) transporting the medium through the pipeline,

[0307] The mineral fiber product as a thermal pipe insulation material comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein optionally, heating the mineral fiber product to a temperature of 600° C. releases less than 1000 μg of isocyanic acid (ICA) / gram of sample, such as less than 750 μg of isocyanic acid (ICA) / gram of sample, such as less than 500 μg of isocyanic acid (ICA) / gram of sample, such as less than 250 μg of isocyanic acid (ICA) / gram of sample, such as less than 100 μg of isocyanic acid (ICA) / gram of sample.

[0308] According to an eighth aspect of the present invention, there is provided a pipe covered with a mineral fiber product as insulation material, wherein the mineral fiber product comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein optionally, heating the mineral fiber product to a temperature of 600°C releases less than 1000 μg isocyanic acid (ICA) / gram sample, for example less than 750 μg isocyanic acid (ICA) / gram sample, for example less than 500 μg isocyanic acid (ICA) / gram sample, for example less than 250 μg isocyanic acid (ICA) / gram sample, for example less than 100 μg isocyanic acid (ICA) / gram sample.

[0309] The present inventors have surprisingly found that when using a binder composition based on oxidized lignin for mineral fiber products, it is possible to use mineral fiber products with low or even no ICA emission in high temperature applications.

[0310] DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0311] The mineral fiber product of the present invention comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1000 μg isocyanic acid (ICA) / gram sample, preferably less than 750 μg isocyanic acid (ICA) / gram sample, for example less than 500 μg isocyanic acid (ICA) / gram sample, for example less than 250 μg isocyanic acid (ICA) / gram sample, for example less than 100 μg isocyanic acid (ICA) / gram sample.

[0312] The heated mineral fiber product comprises the cured binder composition.By "gram sample," the gram sample refers to the sample weight as defined in Procedure II below.

[0313] When a mineral fiber product containing a cured binder composition is heated at a certain temperature and the exhaust gas is quantitatively analyzed for isocyanic acid (ICA) by Fourier transform infrared spectroscopy (FTIR), the result is a measurement of the amount of ICA released. This measurement is considered to be the amount of ICA released in relation to the amount of cured binder composition in the mineral fiber product tested.

[0314] For standardization purposes, total emissions of ICA and other specified exhaust gases were determined according to Procedure II, described below, to obtain comparable data for different products tested at different temperatures. Please note that the data obtained are not directly comparable in quantity to the emissions of these products determined under site-specific conditions when implemented by end customers in industrial insulation systems. For example, in actual end customer installations, the products are not crushed as in Procedure II, described below, and the binder in the mineral fiber products is not completely burned off. In fact, the values ​​obtained using this Procedure II correspond to worst-case scenarios, both in terms of quantity and release time. Therefore, emissions from these products are expected to be lower and released more slowly (reaching steady-state in 2-48 hours), with this Procedure II reaching steady-state in less than 2 hours after actual installation, compared to the values ​​obtained in this study. However, it is easy to assume that mineral fiber products that exhibit lower total emissions compared to other products according to Procedure II will also have lower total emissions in actual end customer installations.

[0315] Emission measurements of different mineral wool products are usually performed by comprehensive tests at external institutes such as RISE in Sweden using a combination of different material tests with different thicknesses to determine the dependence of the insulation thickness on the emission curve by quantification via FID signals and infrared measurements of released gases such as CO, NH3, HCN, NOx and ICA.

[0316] For Alternative B of the present application, the total amount of ICA released was measured according to Procedure II described below. Different ground mineral wool products have been measured internally according to Procedure II to eliminate discussions about thickness and porosity. These experiments were carried out in a custom-made release chamber (tube furnace) that heated the material to a specific temperature set point for a specific time. During these experiments, air was passed through the chamber at a specified rate and sampled to quantify the different compounds. Four different temperatures were tested (250°C, 350°C, 450°C and 600°C) and the released gases were quantified using Fourier transform infrared spectroscopy. Details on Procedure II are given below in the experimental section.

[0317] Preferably, the mineral fibre product of the present invention also exhibits low emissions of other waste gases such as NH3, HCN and / or NOx when the mineral fibre product containing the cured binder composition is subjected to heating.

[0318] In a preferred embodiment, heating the mineral fibre product to a temperature of 600°C releases less than 500 μg HCN / g sample, such as less than 250 μg HCN / g sample, such as less than 100 μg HCN / g sample, such as less than 50 μg HCN / g sample.

[0319] For the purposes of the present application, the total amount of HCN released can be measured according to the same procedure II described below. Of course, the gas analysis by FTIR will then be targeted to the compound to be determined.

[0320] The mineral fiber products of the present invention are suitable for high-temperature applications and also relate to thermal stability. In particular, the mineral fiber products of the present invention can be used in applications with a maximum operating temperature of at least 600°C, preferably at least 650°C. Therefore, according to the maximum service temperature panel test according to EN 14706:2012, the mineral fiber products of the present invention typically meet the maximum service temperature (MST) requirement of at least 600°C, preferably at least 650°C. MST is not related to thermal degradation or off-gassing, but rather to mechanical strength.

[0321] Typically, the uncured cement composition is an aqueous cement composition. In a preferred embodiment, the cement of the present invention does not contain formaldehyde.

[0322] For the purposes of this application, the term "formaldehyde-free" is defined as a term characterizing a mineral wool product wherein the formaldehyde released from the mineral wool product is less than 5 μg / m 2 / h, preferably less than 3 μg / m 2 / h of mineral wool product. Preferably, the test is performed according to ISO 16000 for testing aldehyde emission.

[0323] The uncured binder composition used to prepare the mineral fibre product of the present invention comprises one or more oxidised lignins as component (i).

[0324] Component (i)

[0325] Component (i) is in the form of one or more oxidized lignins.

[0326] Lignin, cellulose, and hemicellulose are the three main organic compounds in plant cell walls. Lignin can be thought of as the glue that holds cellulose fibers together. Lignin contains both hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, after cellulose, and is estimated to account for as much as 20-30% of the total carbon contained in biomass, exceeding 1 billion tons globally.

[0327] Figure 1 A portion of a possible lignin structure is shown.

[0328] There are at least four groups of industrial lignins available on the market. These four groups are shown in Figure 3 A possible fifth group, biorefined lignin, is somewhat different in that it is not described by extraction method but by process source, such as biorefining, and therefore can be similar or different to any of the other groups mentioned. Each group is different from the others, and each is suitable for different applications. Lignin is a complex, heterogeneous material composed of up to three different phenylpropane monomers, depending on the source. Softwood lignin is primarily composed of coniferyl alcohol units (see Figure 2 ), and therefore they are more homogeneous than hardwood lignins, which have a higher syringol content (cf. Figure 2 ). The appearance and consistency of lignin varies greatly and depends largely on the process.

[0329] A summary of the properties of these industrial lignins is shown in Figure 4 middle.

[0330] Lignosulfonates derived from the sulfite pulping process remain the largest commercially available source of lignin, with a production capacity of 1.4 million tons. However, aside from these, the kraft process is currently the most widely used pulping process and is gradually replacing the sulfite process. An estimated 78 million tons of lignin are produced annually through the kraft pulping process globally, but much of this is burned to produce steam and energy. Current kraft recycling capacity is estimated at 160,000 tons, but sources indicate that only approximately 75,000 tons are currently recycled. Kraft lignin is developed from black liquor, the waste liquor from the kraft or kraft processes. Currently, three well-known processes are used to produce kraft lignin: LignoBoost, LignoForce, and SLRP. These three processes are similar in that they involve the addition of CO2 to lower the pH to 9-10, followed by acidification to further reduce the pH to approximately 2. The final step involves some combination of washing, leaching, and filtration to remove ash and other contaminants. These three processes are at varying stages of commercialization worldwide.

[0331] The sulfate process introduces thiol groups and stilbene, while retaining some carbohydrates. Since the lignin is precipitated from the liquor with sulfuric acid, sodium sulfate is also present as an impurity, but this could potentially be avoided by modifying the method used to isolate the lignin. The sulfate process results in a high concentration of phenolic hydroxyl groups, and when these groups are ionized (at a pH above about 10), the lignin becomes soluble in water.

[0332] Commercial kraft lignin is generally purer than lignin sulfonate and has a molecular weight of 1000-3000 g / mol.

[0333] Alkali lignin is derived from the sodium hydroxide pulping process used primarily for wheat straw, bagasse, and flax. g In terms of alkali lignin, the properties of alkali lignin are similar to those of kraft lignin. This process does not use sulfur, nor does it contain covalently bound sulfur. Ash levels are very low. Alkali lignin has low solubility in neutral and acidic media, but is fully soluble at pH 12 and above.

[0334] The ligninsulfonate process introduces a large number of sulfonate groups, making lignin soluble in water but also in acidic aqueous solutions. Lignosulfonates contain up to 8% sulfur in the form of sulfonates, while kraft lignin has 1-2% sulfur, primarily bound to the lignin. Lignosulfonates have a molecular weight of 15,000-50,000 g / mol. Compared to other types of lignin, this type of lignin contains more residual carbohydrates and has a higher average molecular weight. Lignin's characteristic hydrophobic core, combined with the large number of ionized sulfonate groups, makes this type of lignin attractive as a surfactant, and it is often used in applications such as dispersing cement.

[0335] Another group of lignins that is becoming available is lignin produced by biorefining processes, in which carbohydrates are separated from lignin by chemical or biochemical processes to produce a carbohydrate-rich fraction. This remaining lignin is called biorefining lignin. Biorefineries focus on producing energy and alternatives to products obtained from fossil fuels and petrochemicals, as well as lignin. Lignin from this process is generally considered a low-value product or even a waste that is primarily used for thermal combustion or as a low-grade feed or disposed of in other ways.

[0336] The availability of organosolv lignin is still being considered on a pilot scale. This process involves extracting lignin using water and various organic solvents (most commonly ethanol) and some organic acids. One advantage of this method is that the lignin obtained is relatively pure, but it is much more expensive than other industrial lignins and has solubility in organic solvents but not in water.

[0337] Previous attempts to use lignin as a base compound in binder compositions for mineral fibers failed because it proved difficult to find suitable crosslinkers capable of achieving the desired mechanical properties of the cured mineral wool product while avoiding harmful and / or corrosive components. Currently, lignin is used to replace petroleum-derived chemicals, such as phenol in binder applications or phenolic resins in asphalt. It is also used as a cement and concrete additive and, in some applications, as a dispersant.

[0338] The crosslinking of polymer will provide improved performance usually, as mechanical, chemical and thermal tolerance etc.Lignin has abundant phenolic hydroxyl group and aliphatic hydroxyl group especially, and they can react, and cause the crosslinked structure of lignin.Different lignins also will have other available functional groups, and they can be utilized potentially.The existence of these other groups depends on the mode (sulfonate radical in the mercaptan in the sulfate lignin, the lignin sulfonate etc.) of lignin and Mierocrystalline cellulose and hemicellulose separation to a great extent, depends on source.

[0339] It has been found that by using oxidized lignin, a binder composition for mineral fibers can be prepared which allows the mineral fiber products produced therefrom to have excellent properties, while not requiring other components to be included in the binder composition, enabling the mineral fiber products of the present invention to be used in high temperature applications with low levels of ICA emissions or even no ICA emissions.

[0340] In one embodiment, the component (i) is in the form of one or more oxidized kraft lignins.

[0341] In one embodiment, the component (i) is in the form of one or more oxidized alkali lignins.

[0342] In one embodiment, the component (i) is in the form of one or more ammonia-oxidized lignins. For the purposes of the present invention, the term "ammonia-oxidized lignin" is understood to mean lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.

[0343] In an alternative embodiment, the ammonia is partially or completely replaced by an alkali metal hydroxide, in particular sodium hydroxide and / or potassium hydroxide.

[0344] A typical oxidizing agent used to prepare the oxidized lignin is hydrogen peroxide.

[0345] In one embodiment, the ammonia-oxidized lignin comprises one or more compounds selected from ammonia, amines, hydroxides or any salts thereof.

[0346] In one embodiment, the component (i) has a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i).

[0347] In the binder composition, preferably an aqueous binder composition, used according to the present invention, component (i), i.e. the one or more oxidized lignins, may be present in an amount of 25-95% by weight, such as 30-90% by weight, such as 35-85% by weight, based on the dry weight of the binder composition.

[0348] In one embodiment, the component (i) has an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups per macromolecule of component (i), such as more than 2.5 groups per macromolecule of component (i).

[0349] It is believed that the carboxylic acid group content of the oxidized lignin plays an important role in the surprising advantages of the aqueous binder composition for mineral fibers of the present invention. In particular, it is believed that the carboxylic acid groups of the oxidized lignin improve the crosslinking properties and thus allow the cured mineral fiber product to have better mechanical properties.

[0350] In a preferred embodiment, the uncured binder composition, preferably an aqueous binder composition, used to prepare the mineral fiber product of the present invention comprises:

[0351] - component (i) in the form of one or more oxidized lignins;

[0352] - component (ii) in the form of one or more crosslinking agents;

[0353] - Optionally, component (iii) in the form of one or more plasticizers.

[0354] Component (ii)

[0355] Optional component (ii) is in the form of one or more cross-linking agents.

[0356] In one embodiment, component (ii) comprises one or more crosslinkers selected from β-hydroxyalkylamide crosslinkers and / or oxazoline crosslinkers.

[0357] β-Hydroxyalkylamide crosslinkers are curing agents for acid-functional macromolecules. They provide a hard, durable, corrosion-resistant, and solvent-resistant crosslinked polymer network. β-Hydroxyalkylamide crosslinkers are believed to cure via an esterification reaction to form multiple ester bonds. The hydroxyl functionality of the β-Hydroxyalkylamide crosslinker should average at least 2, preferably greater than 2, and more preferably between 2 and 4, for optimal curing response.

[0358] The oxazoline-containing crosslinking agent is a polymer containing one or more oxazoline groups in each molecule, and can generally be easily obtained by polymerizing oxazoline derivatives. Patent US6818699B2 discloses such a method.

[0359] In one embodiment, the component (ii) is an epoxidized oil based on fatty acid triglycerides.

[0360] It is noted that epoxidized oils based on fatty acid triglycerides are not considered hazardous and therefore the use of these compounds in the cement compositions of the present invention does not render these compositions unsafe to handle.

[0361] In one embodiment, the component (ii) is a molecule having three or more epoxy groups.

[0362] In one embodiment, the component (ii) is one or more flexible oligomers or polymers, such as low Tg acrylic polymers, such as low Tg vinyl polymers, such as low Tg polyethers, which contain reactive functional groups, such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

[0363] In one embodiment, component (ii) is selected from the group consisting of crosslinking agents that participate in the curing reaction, such as hydroxyalkylamides, alkanolamines, and reaction products of alkanolamines and polycarboxylic acids. Reaction products of alkanolamines and polycarboxylic acids can be found in US Pat. No. 6,706,853 B1.

[0364] Without wishing to be bound by any particular theory, it is believed that the very advantageous properties of the binder composition, preferably an aqueous binder composition, of the present invention are due to the interaction of the oxidized lignin used as component (i) and the crosslinking agent mentioned above. It is believed that the presence of carboxylic acid groups in the oxidized lignin enables the oxidized lignin to crosslink very effectively.

[0365] In one embodiment, the component (ii) is one or more crosslinking agents selected from the group consisting of polyfunctional organic amines, such as alkanolamines, diamines such as 1,6-hexanediamine, and triamines.

[0366] In one embodiment, the component (ii) is one or more crosslinking agents selected from the group consisting of polyethyleneimine, polyvinylamine, and fatty amine.

[0367] In one embodiment, the component (ii) is one or more fatty amides.

[0368] In one embodiment, the component (ii) is one or more cross-linking agents selected from the group consisting of dimethoxyacetaldehyde, glycolaldehyde, and glyoxylic acid.

[0369] In one embodiment, the component (ii) is one or more crosslinking agents selected from polyester polyols such as polycaprolactone.

[0370] In one embodiment, the component (ii) is one or more cross-linking agents selected from the group consisting of starch, modified starch, and CMC.

[0371] In one embodiment, the component (ii) is one or more crosslinking agents in the form of aliphatic polyfunctional carbodiimides.

[0372] In one embodiment, the component (ii) is one or more crosslinking agents selected from melamine-based crosslinking agents such as hexa(methylmethoxy)melamine (HMMM)-based crosslinking agents.

[0373] Examples of such compounds are Picassian XL 701, 702, 725 (Stahl Polymers), e.g. XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).

[0374] In one embodiment, component (ii) is PrimidXL552, which has the following structure:

[0375]

[0376] Component (ii) may also be any mixture of the above-mentioned compounds.

[0377] In one embodiment, the cement composition of the present invention comprises component (ii) in an amount of 1 to 40 wt%, such as 4 to 20 wt%, such as 6 to 12 wt%, based on the dry weight of component (i).

[0378] Component (iii)

[0379] Optional component (iii) is in the form of one or more plasticizers.

[0380] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids, such as adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides such as urea / urea, or any mixtures thereof.

[0381] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of carbonates, for example ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with a structure similar to lignin, such as vanillin, acetosyringone, solvents used as coalescents, such as alcohol ethers, polyvinyl alcohol.

[0382] In one embodiment, component (iii) is in the form of one or more non-reactive plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or other esters, solvents used as coalescing agents such as alcohol ethers, acrylic polymers, polyvinyl alcohol.

[0383] In one embodiment, component (iii) is one or more reactive plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tricarboxylic acids, such as adipic acid, or lactic acid, and / or vanillic acid and / or ferulic acid, polyurethane dispersions, acrylic acid-based polymers with free carboxyl groups, compounds with a structure similar to lignin, such as vanillin, acetosyringone.

[0384] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of fatty alcohols, monohydric alcohols such as amyl alcohol, stearyl alcohol.

[0385] In one embodiment, component (iii) comprises one or more plasticizers selected from the group consisting of polyethylene glycol, polyethylene glycol ethers.

[0386] Another particularly surprising aspect of the present invention is that the use of plasticizers with a boiling point above 100°C, in particular with a boiling point between 140 and 250°C, significantly improves the mechanical properties of the mineral fiber products of the present invention, even though, given their boiling point, these plasticizers are likely to at least partially evaporate during the curing of the binder, preferably an aqueous binder, in contact with the mineral fibers.

[0387] In one embodiment, component (iii) comprises one or more plasticizers having a boiling point above 100°C, for example from 110 to 280°C, more preferably from 120 to 260°C, more preferably from 140 to 250°C.

[0388] It is believed that the effectiveness of these plasticizers in the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention is related to the effect of increasing the mobility of the oxidized lignin during the curing process. It is believed that the increased mobility of the lignin or oxidized lignin during the curing process promotes effective crosslinking.

[0389] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, in particular 150 to 4,000 g / mol, more particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, more preferably 200 to 400 g / mol.

[0390] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4000 to 25000 g / mol, in particular 4000 to 15000 g / mol, more particularly 8000 to 12000 g / mol.

[0391] In one embodiment, component (iii) is capable of forming a covalent bond with component (i) and / or component (ii) during the curing process. Such a component will not evaporate and remain as part of the composition, but will be effectively modified so as not to introduce unwanted side effects such as water absorption of the cured product. Non-limiting examples of such components are caprolactone and acrylic acid-based polymers with free carboxyl groups.

[0392] In one embodiment, component (iii) is selected from the group consisting of fatty alcohols, monohydric alcohols, such as amyl alcohol, stearyl alcohol.

[0393] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxides, such as ethoxides, for example butanol ethoxides such as butoxytriglycol.

[0394] In one embodiment, component (iii) is selected from one or more propylene glycols.

[0395] In one embodiment, component (iii) is selected from one or more glycol esters.

[0396] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates.

[0397] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of phenol derivatives, such as alkyl or aryl substituted phenols.

[0398] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of silanols, siloxanes.

[0399] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkylarylsulfonates, for example alkylsulfonates, phosphates such as tripolyphosphates; for example tributyl phosphate.

[0400] In one embodiment, component (iii) is selected from one or more hydroxy acids.

[0401] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of monomeric amides, such as acetamide, benzamide, fatty acid amides, such as tall oil amide.

[0402] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of quaternary ammonium compounds, such as trimethylglycine, distearyldimethylammonium chloride.

[0403] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of vegetable oils, such as castor oil, palm oil, linseed oil, tall oil, soybean oil.

[0404] In one embodiment, component (iii) is in the form of tall oil.

[0405] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils.

[0406] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0407] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucosides, glucamides, aminoglucamides, sucrose esters, sorbitan esters.

[0408] It has surprisingly been found that the inclusion of a plasticizer in the binder composition, preferably an aqueous binder composition, used according to the invention greatly improves the mechanical properties of the mineral fiber product of the invention.

[0409] The term "plasticizer" refers to a substance added to a material to make the material softer, more flexible (by lowering the glass transition temperature, Tg), and easier to process.

[0410] Component (iii) may also be any mixture of the compounds mentioned above.

[0411] In one embodiment, component (iii) is present in an amount of 0.5 to 50 wt%, preferably 2.5 to 25 wt%, more preferably 3 to 15 wt%, based on the dry weight of component (i).

[0412] A binder composition for mineral fibers, preferably an aqueous binder composition, comprising components (i) and (iia)

[0413] In one embodiment, the present invention relates to a binder composition for mineral fibers, preferably an aqueous binder composition, comprising:

[0414] - component (i) in the form of one or more oxidized lignins;

[0415] - component (iia) in the form of one or more modifiers.

[0416] The inventors have found that the excellent binder properties can also be achieved by a two-component system comprising component (i) in the form of one or more oxidized lignins and component (iia) in the form of one or more modifiers, and optionally any other components mentioned above and below.

[0417] In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from the group consisting of epoxidized oils based on fatty acid triglycerides.

[0418] In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from the group consisting of molecules having three or more epoxy groups.

[0419] In one embodiment, component (iia) is a modifier in the form of one or more of the following: a flexible oligomer or polymer, such as a low Tg acrylic polymer, such as a low Tg vinyl polymer, such as a low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

[0420] In one embodiment, component (iia) is one or more modifiers selected from the group consisting of polyethyleneimine, polyvinylamine, and fatty amine.

[0421] In one embodiment, component (iia) is one or more modifying agents selected from the group consisting of aliphatic multifunctional carbodiimides.

[0422] Component (iia) may also be any mixture of the above-mentioned compounds.

[0423] Without wishing to be bound by any particular theory, the present inventors believe that the excellent binder properties achieved by the binder composition for mineral fibres comprising components (i) and (iia) and optionally further components are at least partly due to the effect of the modifier acting as component (iia) functioning at least partly as a plasticiser and a cross-linking agent.

[0424] In one embodiment, the cement composition, preferably an aqueous cement composition, comprises component (iia) in an amount of 1 to 40 wt%, such as 4 to 20 wt%, such as 6 to 12 wt%, based on the dry weight of component (i).

[0425] Additional components

[0426] In some embodiments, the cement composition, preferably an aqueous cement composition, used according to the present invention comprises additional components.

[0427] In one embodiment, the binder composition used according to the present invention, preferably an aqueous binder composition, contains a catalyst selected from the group consisting of: inorganic acids, such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid and / or phosphoric acid, and / or any salts thereof, such as sodium hypophosphite, and / or ammonium salts such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid and / or phosphoric acid, and / or sodium polyphosphate (STTP), and / or sodium metaphosphate (STMP), and / or phosphorus oxychloride. The presence of such a catalyst can improve the curing properties of the binder composition used according to the present invention, preferably an aqueous binder composition.

[0428] In one embodiment, the binder composition used according to the present invention, preferably an aqueous binder composition, comprises a catalyst selected from Lewis acids that can accept an electron pair from a donor compound forming a Lewis adduct, such as ZnCl2, Mg(ClO4)2, Sn[N(SO2-n-C8F 17 )2]4.

[0429] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the present invention comprises a catalyst selected from metal chlorides, such as KCl, MgCl2, ZnCl2, FeCl3 and SnCl2.

[0430] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises a catalyst selected from metal organic compounds, such as titanate-based catalysts and tin-based catalysts.

[0431] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention comprises a catalyst selected from chelating agents, such as transition metals, for example iron ions, chromium ions, manganese ions, copper ions.

[0432] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention further comprises a further component (iv) in the form of one or more silanes.

[0433] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention comprises a further component (iv) in the form of one or more coupling agents, such as organofunctional silanes.

[0434] In one embodiment, component (iv) is selected from the group consisting of organofunctional silanes, such as primary or secondary amino-functionalized silanes, epoxy-functionalized silanes, such as polymeric or oligomeric epoxy-functionalized silanes, methacrylate-functionalized silanes, alkyl- and aryl-functionalized silanes, urea-functionalized silanes, or vinyl-functionalized silanes.

[0435] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the present invention further comprises component (v) in the form of one or more components selected from ammonia, amines or any salts thereof.

[0436] It has been found that when oxidized lignin which has not been oxidized in the presence of ammonia is used in component (i), it may be particularly useful to include ammonia, an amine or any salt thereof as a further component.

[0437] In one embodiment, the binder composition used according to the invention, preferably an aqueous binder composition, further comprises a further component in the form of urea, in particular in an amount of 5 to 40% by weight, for example 10 to 30% by weight, 15 to 25% by weight, based on the dry weight of component (i).

[0438] In one embodiment, the binder composition used according to the present invention, preferably an aqueous binder composition, further comprises an additional component, which is in the form of one or more carbohydrates selected from the group consisting of sucrose, reducing sugars, in particular dextrose, polysaccharides, and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, more preferably glucose syrup with a dextrose equivalent value DE of 30 to less than 100, for example DE of 60 to less than 100, for example DE=60-99, for example DE=85-99, for example DE=95-99.

[0439] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the present invention further comprises an additional component in the form of one or more carbohydrates selected from sucrose and reducing sugars in an amount of 5 to 50% by weight, such as 5 to less than 50% by weight, such as 10-40% by weight, such as 15-30% by weight, based on the dry weight of component (i).

[0440] In the context of the present invention, a binder composition having a sugar content of 50% by weight or more based on the total dry weight of the binder components is considered to be a sugar-based binder. In the context of the present invention, a binder composition having a sugar content of less than 50% by weight based on the total dry weight of the binder components is considered to be a non-sugar-based binder.

[0441] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, further comprises an additional component in the form of one or more surfactants in the form of nonionic and / or ionic emulsifiers, such as polyoxyethylene (4) lauryl ether, soy lecithin, sodium lauryl sulfate.

[0442] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0443] - component (i) in the form of one or more ammonia-oxidized lignins having a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0444] - component (ii) in the form of one or more crosslinking agents selected from β-hydroxyalkylamide crosslinkers and / or oxazoline crosslinkers and / or one or more crosslinking agents selected from the group consisting of polyfunctional organic amines, for example alkanolamines, diamines such as 1,6-hexanediamine, triamines;

[0445] - component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, in particular 150 to 4,000 g / mol, more particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, more preferably 150 to 300 g / mol, or having an average molecular weight of 4,000 to 25,000 g / mol, in particular 4,000 to 15,000 g / mol, more particularly 8,000 to 12,000 g / mol; wherein preferably the binder composition, preferably an aqueous binder composition, comprises 1 to 40% by weight, for example 4 to 20% by weight, 6 to 12% by weight, based on the dry weight of component (i), of component (ii), and component (iii) is present in an amount of 0.5 to 50% by weight, preferably 2.5 to 25% by weight, more preferably 3 to 15% by weight, based on the dry weight of component (i).

[0446] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0447] - component (i) in the form of one or more ammonia-oxidized lignins having a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0448] - component (iia) in the form of one or more modifiers chosen from epoxidized oils based on fatty acid triglycerides.

[0449] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0450] - component (i) in the form of one or more ammonia-oxidized lignins having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups per macromolecule of component (i), for example more than 2.5 groups per macromolecule of component (i);

[0451] - component (ii) in the form of one or more crosslinking agents selected from β-hydroxyalkylamide crosslinkers and / or oxazoline crosslinkers and / or one or more crosslinking agents selected from the group consisting of polyfunctional organic amines, for example alkanolamines, diamines such as 1,6-hexanediamine, triamines;

[0452] - component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, in particular 150 to 4,000 g / mol, more particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, more preferably 150 to 300 g / mol, or having an average molecular weight of 4,000 to 25,000 g / mol, in particular 4,000 to 15,000 g / mol, more particularly 8,000 to 12,000 g / mol; wherein preferably the binder composition, preferably an aqueous binder composition, comprises 1 to 40% by weight, for example 4 to 20% by weight, 6 to 12% by weight, based on the dry weight of component (i), of component (ii), and component (iii) is present in an amount of 0.5 to 50% by weight, preferably 2.5 to 25% by weight, more preferably 3 to 15% by weight, based on the dry weight of component (i).

[0453] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0454] - component (i) in the form of one or more ammonia-oxidized lignins having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups per macromolecule of component (i), for example more than 2.5 groups per macromolecule of component (i);

[0455] - component (iia) in the form of one or more modifiers chosen from epoxidized oils based on fatty acid triglycerides.

[0456] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention consists essentially of the following components:

[0457] - component (i) in the form of one or more oxidized lignins;

[0458] - component (ii) in the form of one or more cross-linking agents;

[0459] - component (iii) in the form of one or more plasticizers;

[0460] - component (iv) in the form of one or more coupling agents such as organofunctional silanes;

[0461] - optional components in the form of one or more compounds selected from ammonia, amines or any salts thereof;

[0462] - optional components in the form of urea;

[0463] - optional components in the form of more reactive or non-reactive silicones;

[0464] - optionally a hydrocarbon oil;

[0465] - optionally one or more surfactants;

[0466] -water.

[0467] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention consists essentially of the following components:

[0468] - component (i) in the form of one or more oxidized lignins;

[0469] - component (iia) in the form of one or more modifiers chosen from epoxidized oils based on fatty acid triglycerides;

[0470] - component (iv) in the form of one or more coupling agents such as organofunctional silanes;

[0471] - optional components in the form of one or more compounds selected from ammonia, amines or any salts thereof;

[0472] - optional components in the form of urea;

[0473] - optional components in the form of more reactive or non-reactive silicones;

[0474] - optionally a hydrocarbon oil;

[0475] - optionally one or more surfactants;

[0476] -water.

[0477] Method for producing mineral fiber products

[0478] The mineral fiber product of the present invention can be prepared by conventional methods for producing mineral fiber products by binding mineral fibers with a binder composition. Therefore, the mineral fiber product of the present invention is preferably prepared by a method comprising the steps of contacting mineral fibers with an uncured, preferably aqueous, binder composition comprising one or more oxidized lignins.

[0479] In a preferred embodiment, the uncured, preferably aqueous, cement composition comprises:

[0480] - component (i) in the form of one or more oxidized lignins;

[0481] - component (ii) in the form of one or more crosslinking agents;

[0482] - optional component (iii) in the form of one or more plasticizers.

[0483] Curing

[0484] The uncured binder composition in a mineral fiber product precursor, such as a web in which the mineral fibers are in contact with the binder composition, is cured by chemical and / or physical reaction of the binder components.

[0485] In one embodiment, the curing is carried out in a curing apparatus.

[0486] In one embodiment, the curing is carried out at a temperature of 100-300°C, such as 170-270°C, such as 180-250°C, such as 190-230°C.

[0487] In one embodiment the curing is carried out in a conventional curing oven used for mineral wool production, operating at a temperature of 150 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.

[0488] In one embodiment, the curing is performed for a period of 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes.

[0489] In a typical embodiment, curing is performed at a temperature of 150 to 250° C. for a time period of 30 seconds to 20 minutes.

[0490] The curing process may begin immediately after the binder is applied to the fibers. Curing is defined as the process by which a binder composition undergoes a physical and / or chemical reaction (curing typically increases the molecular weight of compounds in the binder composition in the case of a chemical reaction) and thereby increases the viscosity of the binder composition, typically until the binder composition reaches a solid state.

[0491] In one embodiment, the curing process comprises drying by pressure.Pressure may be applied by blowing air or gas through / over the mixture of mineral fibres and binder.

[0492] Mineral fiber products of the present invention

[0493] The present invention relates to a mineral fibre product comprising mineral fibres in contact with a cured binder composition as described above, ie in contact with a cured binder resulting from the curing of a binder composition, preferably an aqueous binder composition, as described above.

[0494] The mineral fibers used can be any one of man-made vitreous fibers (MMVF), glass fibers, ceramic fibers, basalt fibers, slag fibers, rock fibers, stone fibers, etc. These fibers can be in the form of velvet products such as asbestos products.

[0495] Fiber / melt composition

[0496] Man-made vitreous fibers (MMVF) can have any suitable oxide composition. The fibers can be glass fibers, ceramic fibers, basalt fibers, slag fibers, or rock or stone fibers. The fibers are preferably of the type commonly referred to as rock fibers, stone fibers, or slag fibers, most preferably stone fibers.

[0497] Stone fiber usually contains the following oxides, expressed in weight percentage:

[0498] SiO2:30-51

[0499] CaO: 8-30

[0500] MgO: 2-25

[0501] FeO (including Fe2O3): 2-15

[0502] Na2O+K2O: no more than 10

[0503] CaO+MgO: 10-30

[0504] In some preferred embodiments, the MMVF has the following elemental levels, calculated as oxides and expressed in weight %:

[0505] SiO2: at least 30, 32, 35 or 37; not more than 51, 48, 45 or 43

[0506] Al2O3: at least 12, 16 or 17; not more than 30, 27 or 25

[0507] CaO: at least 8 or 10; no more than 30, 25 or 20

[0508] MgO: at least 2 or 5; no more than 25, 20 or 15

[0509] FeO (including Fe2O3): at least 4 or 5; not more than 15, 12 or 10

[0510] FeO+MgO: at least 10, 12 or 15; not more than 30, 25 or 20

[0511] Na2O+K2O: 0 or at least 1; not more than 10

[0512] CaO+MgO: at least 10 or 15; not more than 30 or 25

[0513] TiO2: 0 or at least 1; no more than 6, 4 or 2

[0514] TiO2+FeO: at least 4 or 6; not more than 18 or 12

[0515] B2O3: 0 or at least 1; no more than 5 or 3

[0516] P2O5: 0 or at least 1; not more than 8 or 5

[0517] Other: 0 or at least 1; no more than 8 or 5

[0518] The MMVF prepared by the method of the present invention preferably has the following composition (expressed in wt%): SiO2: 35-50

[0519] Al2O3: 12-30

[0520] TiO2: up to 2

[0521] Fe2O3: 3-12

[0522] CaO: 5-30

[0523] MgO: up to 15

[0524] Na2O: 0-15

[0525] K2O: 0-15

[0526] P2O5: up to 3

[0527] MnO: up to 3

[0528] B2O3: up to 3

[0529] Another preferred composition of MMVF is as follows (expressed in wt%):

[0530] SiO2: 39-55%, preferably 39-52%

[0531] Al2O3: 16-27%, preferably 16-26%

[0532] CaO: 6-20%, preferably 8-18%

[0533] MgO: 1-5%, preferably 1-4.9%

[0534] Na2O: 0-15%, preferably 2-12%

[0535] K2O: 0-15%, preferably 2-12%

[0536] R2O (Na2O + K2O): 10-14.7%, preferably 10-13.5%

[0537] P2O5: 0-3%, preferably 0-2%

[0538] Fe2O3 (total iron): 3-15%, preferably 3.2-8%

[0539] B2O3: 0-2%, preferably 0-1%

[0540] TiO2: 0-2%, preferably 0.4-1%

[0541] Others: 0-2.0%

[0542] Glass fibers typically contain the following oxides (expressed in wt%):

[0543] SiO2:50-70

[0544] Al2O3: 10-30

[0545] CaO: no more than 27

[0546] MgO: not more than 12

[0547] Glass fibers may also contain the following oxides (expressed in wt%):

[0548] Na2O+K2O: 8-18, especially Na2O+K2O is greater than CaO+MgO

[0549] B2O3:3-12

[0550] Certain glass fiber compositions may contain less than 2% Al2O3.

[0551] Suitable fiber formation methods and subsequent production steps for producing mineral fiber products are those conventional in the art. Typically, the binder is sprayed onto the airborne mineral fibers immediately after fibrillation of the mineral melt. The amount of uncured, preferably aqueous, binder composition applied is typically 0.1 to 18% by weight, preferably 0.2 to 8% by weight, of the mineral fiber product being bonded, calculated on a dry basis.

[0552] The sprayed mineral fiber web is usually cured in a curing oven using a stream of hot air, which can be introduced into the mineral fiber web from below or above or from alternating directions in different zones along the length of the curing oven.

[0553] Typically, the curing oven operates at a temperature of about 150° C. to about 300° C., such as 170 to 270° C., such as 180 to 250° C., such as 190 to 230° C. Typically, the curing oven residence time is 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes, depending on, for example, product density.

[0554] In a typical embodiment, the mineral fiber product of the invention is cured at a temperature of from 150°C to 250°C for a period of from 30 seconds to 20 minutes.

[0555] If desired, the mineral fiber web may be subjected to a shaping process before curing. The bonded mineral fiber product emerging from the curing oven may be cut into the desired form, for example in the form of a batt.

[0556] In a preferred embodiment, the mineral fiber product of the present invention is a thermal insulation product. The mineral fiber product is preferably in the form of preformed pipe sections, mats or slabs.

[0557] In a preferred embodiment, the mineral fiber product of the present invention has a thickness in the range of 20 mm to 500 mm, preferably 30 mm to 300 mm, such as 50 mm to 150 mm, wherein typically the mineral fiber product is in the form of a sheet.

[0558] The mineral fiber products of the present invention generally have a mass fraction of 6-250 kg / m 3 , preferably 20-200kg / m 3 The mineral fiber product typically has a loss on ignition (LOI) in the range of 0.25-18.0% or 0.3-18.0%, preferably 0.5-8.0%. In a preferred embodiment, the mineral fiber product has a loss on ignition (LOI) of 0.25-8.0% or 0.3-8.0%, more preferably 0.25-6.0%.

[0559] Use of the mineral fiber product of the invention

[0560] The inventive use of the mineral fiber product relates to high temperature applications. High temperature applications here mean using the mineral fiber product at temperatures of at least 300°C, preferably at least 400°C, for example at least 450°C and / or up to 700°C.

[0561] The present invention therefore also relates to the use of a mineral fiber product comprising mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, at a temperature of at least 300° C., preferably at least 400° C., for example at least 450° C. Typically, the use according to the invention is at a temperature not exceeding 700° C., preferably not exceeding 650° C.

[0562] Generally, it is preferred that heating the mineral fiber product to a temperature of 600° C. releases less than 1000 μg isocyanic acid (ICA) per gram of sample, more preferably less than 750 μg isocyanic acid (ICA) per gram of sample, for example less than 500 μg isocyanic acid (ICA) per gram of sample, for example less than 250 μg isocyanic acid (ICA) per gram of sample, for example less than 100 μg isocyanic acid (ICA) per gram of sample. The method for determining the total ICA release is described below.

[0563] In a preferred embodiment of the use according to the invention, the mineral fiber product is used as a thermal insulation product, more preferably as a thermal pipe insulation material.

[0564] For use according to the invention, the pipe is preferably operated at a high use temperature of at least 300° C., preferably at least 400° C., for example at least 450° C. Typically, the temperature does not exceed 700° C., preferably does not exceed 650° C.

[0565] The pipeline is preferably a metal pipeline. In particular, the pipeline is used to transport a medium, such as gas, steam or fluid. The medium transported by the pipeline is usually a high-temperature medium with the above-mentioned minimum operating temperature.

[0566] The mineral fibre product for the use according to the invention may have all the features described above for the mineral fibre product according to the invention, to which description reference is therefore made.

[0567] Method for conveying medium of the present invention

[0568] The present invention also relates to a method for conveying a medium, comprising the following steps:

[0569] a) covering the pipes with mineral fiber products as thermal pipe insulation, and

[0570] b) transporting the medium through the pipeline,

[0571] The mineral fiber product comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins.

[0572] Generally, it is preferred that heating the mineral fiber product to a temperature of 600° C. releases less than 1000 μg isocyanic acid (ICA) / gram sample, such as less than 750 μg isocyanic acid (ICA) / gram sample, such as less than 500 μg isocyanic acid (ICA) / gram sample, such as less than 250 μg isocyanic acid (ICA) / gram sample, such as less than 100 μg isocyanic acid (ICA) / gram sample. The method for determining the total ICA release is described below.

[0573] In a preferred embodiment, the conveyed medium has a temperature of at least 300° C., preferably at least 400° C., for example at least 450° C. Preferably, the temperature does not exceed 700° C., preferably does not exceed 650° C.

[0574] The medium transported through the pipes may be, for example, gas, steam or fluid.

[0575] The mineral fibre product used in the process according to the invention may have all the features described above for the mineral fibre product according to the invention, to which description reference is therefore made.

[0576] Pipe with thermal insulation material of the present invention

[0577] The present invention also relates to a pipe covered or wrapped with a mineral fiber product as thermal insulation material, wherein the mineral fiber product comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins.

[0578] Generally, it is preferred that heating the mineral fiber product to a temperature of 600° C. releases less than 1000 μg isocyanic acid (ICA) / gram sample, such as less than 750 μg isocyanic acid (ICA) / gram sample, such as less than 500 μg isocyanic acid (ICA) / gram sample, such as less than 250 μg isocyanic acid (ICA) / gram sample, such as less than 100 μg isocyanic acid (ICA) / gram sample. The method for determining the total ICA release is described below.

[0579] The mineral fibre product for covering the pipe according to the invention may have all the features described above for the mineral fibre product according to the invention, to which reference is therefore made.

[0580] Oxidized lignin that can be used as a component of the binder composition for mineral fibers of the present invention, preferably an aqueous binder composition, according to the above-mentioned alternatives A and B, and a method for preparing such oxidized lignin

[0581] In the following, we describe oxidized lignins that can be used as components of binder compositions and their preparation.

[0582] Method for preparing oxidized lignin I

[0583] Oxidized lignin that can be used as a component of the binder used in the present invention can be prepared by a method comprising the following steps:

[0584] The following components were brought into contact:

[0585] - component (a) comprising one or more lignins;

[0586] - component (b) comprising ammonia, one or more amine components and / or any salts thereof;

[0587] - component (c) comprising one or more oxidizing agents.

[0588] Component (a)

[0589] Component (a) comprises one or more lignins.

[0590] In one embodiment of the process of the present invention, component (a) comprises one or more kraft lignins, one or more alkali lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from a biorefining process of a lignocellulosic raw material, or any mixture thereof.

[0591] In one embodiment, component (a) comprises one or more kraft lignins.

[0592] Component (b)

[0593] In one embodiment of the present invention, component (b) comprises ammonia, one or more amino components and / or any salts thereof. Without wishing to be bound by any particular theory, the present inventors believe that the replacement of the alkali metal hydroxides used in previously known lignin oxidation processes with ammonia, one or more amino components and / or any salts thereof plays an important role in improving the properties of the oxidized lignin prepared according to the process of the present invention.

[0594] The present inventors have surprisingly found that lignin oxidized by an oxidizing agent in the presence of ammonia or an amine contains a significant amount of nitrogen as part of the oxidized lignin structure. Without wishing to be bound by any particular theory, the present inventors believe that the improved fire resistance of the oxidized lignin when used in a product in which the oxidized lignin prepared by the process of the present invention is included in a binder composition is at least partially due to the nitrogen content of the oxidized lignin structure.

[0595] In one embodiment, component (b) comprises ammonia and / or any salts thereof.

[0596] Without wishing to be bound by any particular theory, the inventors believe that the improved stability properties of the derivatized lignin prepared according to the present invention are at least in part due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused. In contrast, it has proven difficult to remove residual amounts of alkali metal hydroxides used in previously known oxidation processes.

[0597] However, it may be advantageous in the process according to the invention for component (b) to comprise, in addition to ammonia, one or more amino components and / or any salts thereof, relatively small amounts of alkali metal and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0598] In embodiments where component (b) comprises an alkali metal and / or alkaline earth metal hydroxide such as sodium hydroxide and / or potassium hydroxide as a component other than ammonia, one or more amino components and / or any salts thereof, the amount of the alkali metal and / or alkaline earth metal hydroxide is generally small, for example, from 5 to 70 parts by weight, such as from 10 to 20 parts by weight, of the alkali metal and / or alkaline earth metal hydroxide, based on ammonia.

[0599] Component (c)

[0600] In the process of the present invention, component (c) comprises one or more oxidizing agents.

[0601] In one embodiment, component (c) comprises one or more oxidizing agents in the form of hydrogen peroxide, an organic or inorganic peroxide, molecular oxygen, ozone, air, a halogen-containing oxidizing agent, or any mixture thereof.

[0602] During the initial oxidation step, reactive free radicals from the oxidant typically abstract a proton from a phenolic group, as this bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize free radicals through intermediary action, multiple pathways are available to continue (but also terminate) the reaction and yield a variety of intermediates and final products. Due to this complexity (and the chosen conditions), the average molecular weight can increase as well as decrease, and in our experiments, we have typically observed modest increases of approximately 30% in average molecular weight.

[0603] In one embodiment, component (c) comprises hydrogen peroxide.

[0604] Hydrogen peroxide is probably the most commonly used oxidant due to its low price, high efficiency, and relatively low environmental impact. When hydrogen peroxide is used in the absence of a catalyst, alkaline conditions and temperature are important due to the following reactions that lead to the formation of free radicals:

[0605]

[0606]

[0607] The present inventors have found that the derivatized lignin prepared using the process of the present invention contains an increased amount of carboxylic acid groups as a result of the oxidation process. Without wishing to be bound by any particular theory, the present inventors believe that the carboxylic acid group content of the oxidized lignin prepared in the process of the present invention plays an important role in the desired reactivity properties of the derivatized lignin prepared by the process of the present invention.

[0608] Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. Higher hydrophilicity can increase solubility in water and promote adhesion to polar substrates such as mineral fibers.

[0609] Additional components

[0610] In one embodiment, the process of the invention comprises further components, in particular component (d) in the form of an oxidation catalyst, for example one or more transition metal catalysts, for example iron sulfate, for example catalysts containing manganese, palladium, selenium, tungsten.

[0611] Such oxidation catalysts can increase the reaction rate, thereby improving the properties of the oxidized lignin produced by the method of the present invention.

[0612] The mass ratio of the components

[0613] One skilled in the art will use the components (a), (b) and (c) in relative amounts to achieve the desired degree of lignin oxidation.

[0614] In one embodiment,

[0615] - component (a) comprises one or more lignins,

[0616] - component (b) comprises ammonia,

[0617] - component (c) comprises one or more oxidizing agents in the form of hydrogen peroxide,

[0618] wherein the mass ratio of lignin, ammonia and hydrogen peroxide is such that the amount of ammonia is 0.01 to 0.5 parts by weight, such as 0.1 to 0.3 parts by weight, for example 0.15 to 0.25 parts by weight of ammonia, based on the dry weight of lignin, and wherein the amount of hydrogen peroxide is 0.025 to 1.0 parts by weight, such as 0.05 to 0.2 parts by weight, for example 0.075 to 0.125 parts by weight of hydrogen peroxide, based on the dry weight of lignin.

[0619] method

[0620] There is more than one possibility for contacting the components (a), (b) and (c) to achieve the desired oxidation reaction.

[0621] In one embodiment, the method comprises the following steps:

[0622] - a step of providing component (a) in the form of an aqueous solution and / or dispersion of one or more lignins, the aqueous solution having a lignin content of 1 to 50% by weight, such as 5 to 25% by weight, such as 15 to 22% by weight, such as 18 to 20% by weight, based on the total weight of the aqueous solution;

[0623] - a pH adjustment step by adding component (b) comprising an aqueous solution of ammonia, one or more amine components and / or any of their salts;

[0624] - an oxidation step by adding component (c) comprising an oxidizing agent.

[0625] In one embodiment, the pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH value of ≥9, such as ≥10, for example ≥10.5.

[0626] In one embodiment, the pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH value in the range of 10.5 to 12.

[0627] In one embodiment the pH adjustment step is performed such that the temperature is allowed to rise to ≥ 25°C and then controlled in the range of 25 to 50°C, such as 30 to 45°C, for example 35 to 40°C.

[0628] In one embodiment, during the oxidation step the temperature is allowed to rise > 35°C and then controlled in the range of 35 to 150°C, such as 40 to 90°C, for example 45 to 80°C.

[0629] In one embodiment, the oxidation step is performed for a period of from 1 second to 48 hours, such as from 10 seconds to 36 hours, such as from 1 minute to 24 hours, such as from 2 to 5 hours.

[0630] Method II for preparing oxidized lignin

[0631] Oxidized lignin that can be used as a component of the binder used in the present invention can be prepared by a method comprising the following steps:

[0632] The following components were brought into contact:

[0633] - a component (a) comprising one or more lignins,

[0634] a component (b) comprising ammonia and / or one or more amine components and / or any of their salts and / or alkali and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide,

[0635] - component (c) comprising one or more oxidizing agents,

[0636] - component (d) in the form of one or more plasticizers.

[0637] Component (a)

[0638] Component (a) comprises one or more lignins.

[0639] In one embodiment of the process of the present invention, component (a) comprises one or more kraft lignins, one or more alkali lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from a biorefining process of a lignocellulosic raw material, or any mixture thereof.

[0640] In one embodiment, component (a) comprises one or more kraft lignins.

[0641] Component (b)

[0642] In one embodiment of the present invention, component (b) comprises ammonia, one or more amino components and / or any salts thereof, and / or alkali and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide.

[0643] "Ammonia oxidized lignin" is understood to be lignin which has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia oxidized lignin" is abbreviated as AOL.

[0644] In one embodiment, component (b) comprises ammonia and / or any salts thereof.

[0645] Without wishing to be bound by any particular theory, the inventors believe that the improved stability properties of the derivatized lignin prepared according to the present invention using ammonia and / or any salts thereof as component (b) are at least partly due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused.

[0646] However, it may be advantageous in this embodiment of the process of the invention for component (b) to comprise, in addition to ammonia, one or more amino components and / or any salts thereof, relatively small amounts of alkali metal and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide.

[0647] In embodiments where component (b) comprises an alkali metal and / or alkaline earth metal hydroxide such as sodium hydroxide and / or potassium hydroxide as a component other than ammonia, one or more amino components and / or any salts thereof, the amount of the alkali metal and / or alkaline earth metal hydroxide is generally small, for example, from 5 to 70 parts by weight, such as from 10 to 20 parts by weight, of the alkali metal and / or alkaline earth metal hydroxide, based on ammonia.

[0648] Component (c)

[0649] In the process of the present invention, component (c) comprises one or more oxidizing agents.

[0650] In one embodiment, component (c) comprises one or more oxidizing agents in the form of hydrogen peroxide, an organic or inorganic peroxide, molecular oxygen, ozone, air, a halogen-containing oxidizing agent, or any mixture thereof.

[0651] During the initial oxidation step, reactive free radicals from the oxidant typically abstract a proton from a phenolic group, as this bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize free radicals through intermediary action, multiple pathways are available to continue (but also terminate) the reaction and yield a variety of intermediates and final products. Due to this complexity (and the chosen conditions), the average molecular weight can increase as well as decrease, and in our experiments, we have typically observed modest increases of approximately 30% in average molecular weight.

[0652] In one embodiment, component (c) comprises hydrogen peroxide.

[0653] Hydrogen peroxide is probably the most commonly used oxidant due to its low price, high efficiency, and relatively low environmental impact. When hydrogen peroxide is used in the absence of a catalyst, alkaline conditions and temperature are important due to the following reactions that lead to the formation of free radicals:

[0654]

[0655]

[0656] The present inventors have found that the derivatized lignin prepared using the process of the present invention contains an increased amount of carboxylic acid groups as a result of the oxidation process. Without wishing to be bound by any particular theory, the present inventors believe that the carboxylic acid group content of the oxidized lignin prepared in the process of the present invention plays an important role in the desired reactivity properties of the derivatized lignin prepared by the process of the present invention.

[0657] Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. Higher hydrophilicity can increase solubility in water and promote adhesion to polar substrates such as mineral fibers.

[0658] Component (d)

[0659] Component (d) comprises one or more plasticizers.

[0660] In one embodiment of the present invention, component (d) comprises one or more plasticizers in the form of polyols, for example carbohydrates, hydrogenated sugars, for example sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids, for example adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides such as urea / urea, or any mixtures thereof.

[0661] The present inventors have found that the inclusion of component (d) in the form of one or more plasticizers provides a reduction in the viscosity of the reaction mixture, which makes the process for producing oxidized lignin very efficient.

[0662] In one embodiment of the present invention, component (d) comprises one or more plasticizers in the form of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyvinyl alcohol, acrylic acid-based polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides such as urea / carbamide, or any mixtures thereof.

[0663] In one embodiment of the present invention, component (d) comprises one or more plasticizers selected from the group consisting of polyethylene glycol, polyvinyl alcohol, urea or any mixture thereof.

[0664] Additional components

[0665] In one embodiment, the process of the invention comprises further components, in particular component (v) in the form of an oxidation catalyst, for example one or more transition metal catalysts, for example iron sulfate, for example catalysts containing manganese, palladium, selenium, tungsten.

[0666] Such oxidation catalysts can increase the reaction rate, thereby improving the properties of the oxidized lignin produced by the method.

[0667] The mass ratio of the components

[0668] One skilled in the art will use the components (a), (b), (c) and (d) in relative amounts to achieve the desired degree of lignin oxidation.

[0669] In one embodiment, the method of the present invention is performed such that the method comprises

[0670] - a component (a) comprising one or more lignins,

[0671] - a component (b) comprising ammonia,

[0672] - component (c) comprising one or more oxidizing agents in the form of hydrogen peroxide,

[0673] - component (d) comprising one or more plasticizers selected from polyethylene glycols,

[0674] wherein the mass ratio of lignin, ammonia, hydrogen peroxide and polyethylene glycol is such that the amount of ammonia is 0.01 to 0.5 part by weight, for example 0.1 to 0.3 part by weight, for example 0.15 to 0.25 part by weight of ammonia (25% by weight aqueous solution), based on the dry weight of the lignin, and wherein the amount of hydrogen peroxide (30% by weight aqueous solution) is 0.025 to 1.0 part by weight, for example 0.07 to 0.50 part by weight, for example 0.15 to 0.30 part by weight of hydrogen peroxide, based on the dry weight of the lignin, and wherein the amount of polyethylene glycol is 0.03 to 0.60 part by weight, for example 0.07 to 0.50 part by weight, for example 0.10 to 0.40 part by weight of polyethylene glycol, based on the dry weight of the lignin.

[0675] For the purposes of the present invention, "dry weight of lignin" is preferably defined as the weight of lignin in the form in which it is provided.

[0676] method

[0677] There is more than one possibility for contacting the components (a), (b), (c) and (d) to achieve the desired oxidation reaction.

[0678] In one embodiment, the method comprises the following steps:

[0679] - a step of providing component (a) in the form of an aqueous solution and / or dispersion of one or more lignins, the aqueous solution having a lignin content of 5 to 90% by weight, such as 10 to 85% by weight, for example 15 to 70% by weight, based on the total weight of the aqueous solution;

[0680] - a pH adjustment step by adding component (b);

[0681] - a step of adding component (d);

[0682] - an oxidation step by adding component (c) comprising an oxidizing agent.

[0683] In one embodiment, the pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH value of ≥9, such as ≥10, for example ≥10.5.

[0684] In one embodiment, the pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH value in the range of 9.5 to 12.

[0685] In one embodiment the pH adjustment step is performed such that the temperature is allowed to rise to ≥ 25°C and then controlled in the range of 25 to 50°C, such as 30 to 45°C, for example 35 to 40°C.

[0686] In one embodiment, during the oxidation step, the temperature is allowed to rise to > 35°C and then controlled in the range of 35 to 150°C, such as 40 to 90°C, for example 45 to 80°C.

[0687] In one embodiment, the oxidation step is performed for a period of 1 second to 24 hours, such as 1 minute to 12 hours, such as 10 minutes to 8 hours, such as 5 minutes to 1 hour.

[0688] The inventors have found that the process of the invention allows the production of a reaction mixture with a high dry matter content and that high throughputs are therefore possible in the process of the invention, which allows the reaction product in the form of oxidized lignin to be used as a component for the industrial-scale production of products such as mineral fiber products.

[0689] In one embodiment, the process of the invention is carried out such that the dry matter content of the reaction mixture is from 20 to 80 wt%, such as from 40 to 70 wt%.

[0690] In one embodiment, the method of the present invention is carried out such that the viscosity of the oxidized lignin has a value of 100 cP to 100,000 cP, such as a value of 500 cP to 50,000 cP, such as a value of 1,000 cP to 25,000 cP.

[0691] For the purposes of the present invention, viscosity is dynamic viscosity and is defined as the resistance of a liquid / paste to change in shape or movement of adjacent parts relative to one another. Viscosity is measured in centipoise (cP), which is equivalent to 1 mPa·s (milliPascal second). Viscosity is measured using a viscometer at 20°C. For the purposes of the present invention, dynamic viscosity can be measured at 20°C using a cone-plate Wells Brookfield viscometer.

[0692] In one embodiment, the method of the present invention is carried out such that it comprises a rotor-stator apparatus.

[0693] In one embodiment, the method of the present invention is implemented such that the method is performed as a continuous or semi-continuous process.

[0694] Apparatus for carrying out the method

[0695] The invention also relates to an apparatus for carrying out the method described above.

[0696] In one embodiment, the apparatus for carrying out the method comprises:

[0697] -Rotor-stator equipment,

[0698] - a premixing device for components (a), (b), (d),

[0699] - one or more inlets for water, components (a), (b), (c) and (d),

[0700] - one or more outlets for oxidized lignin.

[0701] In one embodiment, the apparatus is constructed in such a way that an inlet for the premix of components (a), (b) and (d) is located in the rotor-stator device and the apparatus further comprises a chamber having an inlet for component (c) and an outlet for the oxidized lignin.

[0702] A rotor-stator device is a device for processing materials, comprising a stator constructed as an inner cone provided with a toothed ring. The stator cooperates with a rotor having arms protruding from a hub. Each of these arms carries teeth that mesh with the teeth of the stator's toothed ring. With each rotation of the rotor, the material to be processed is conveyed a little further outwards while being subjected to strong shearing, mixing and redistribution. The rotor arms of the upright device and the container chamber below allow the material to be permanently rearranged from the inside out and provide for multiple treatments of dry and / or highly viscous substances, so that the device is very useful for thorough mixing, kneading, fibrillation, disintegration and similar processes that are important in industrial production. The upright arrangement of the housing helps the material to fall back from the periphery to the center of the device.

[0703] In one embodiment, the rotor-stator apparatus used in the method of the present invention comprises a stator having a toothed ring and a rotor having teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator apparatus has the following features: a guide funnel protruding between the arms of the rotor focuses the incoming material flow from above into the central area of ​​the container. The outer surface of the guide funnel defines an annular gap that restricts the material flow. A feed screw is provided at the rotor to feed the working area of ​​the apparatus. The guide funnel retains the product in the active area of ​​the apparatus, and the feed screw generates increased material pressure in the center.

[0704] For more details on the rotor-stator apparatus used in one embodiment of the method of the present invention, reference is made to US 2003 / 0042344 A1 , which is incorporated herein by reference.

[0705] In one embodiment, the method is carried out so that the method uses a rotor-stator apparatus. In this embodiment, the mixing of the components and the reaction of the components are carried out in the same rotor-stator apparatus.

[0706] In one embodiment, the method is carried out such that it uses two or more rotor-stator devices, wherein at least one rotor-stator device is used for mixing the components and at least one rotor-stator device is used for reacting the components.

[0707] This method can be divided into two steps:

[0708] 1. Preparation of lignin substances (a) + (b) + (d), and

[0709] 2. Oxidation of lignin.

[0710] Typically, two different types of rotor / stator motors are used:

[0711] 1. Open rotor / stator motor suitable for mixing lignin powder into water at very high concentrations (30 to 50 wt%). The mixing intensity is low, but specialized auxiliary equipment (inlet funnel, screw, etc.) is required to handle highly viscous materials. The machine operates at a low peripheral speed (up to 15 m / s). It can be used as a batch or continuous system.

[0712] 2. In-line rotor / stator motors, which have much higher shear forces (circumferential speeds up to 55 m / s) and create favorable conditions for very fast chemical reactions. The machine should be used continuously.

[0713] In the open rotor / stator system, a high lignin / water concentrate (45 to 50 wt%) is prepared. The lignin powder is slowly added to warm water (30 to 60°C) to which an appropriate amount of ammonia and / or alkali metal base has been added. This can be done in batch mode, or the materials can be added intermittently / continuously to create a continuous stream for the next step.

[0714] The resulting mass should be kept at a temperature of about 60 degrees to keep the viscosity as low as possible and thus keep the material pumpable. The hot mass of lignin / water at a pH of 9 to 12 is then transferred to the oxidation step using a suitable pump such as a screw pump or other positive displacement pump.

[0715] In one embodiment, the oxidation is carried out as a continuous, in-line reaction in a closed rotor / stator system. An aqueous solution of ammonia and / or alkali metal base is metered into the rotor / stator chamber at the point of highest turbulence / shear using a metering pump. This ensures a rapid oxidation reaction. The oxidized material (AOL) exits the in-line reactor and is collected in a suitable tank.

[0716] Reaction products

[0717] The present inventors have surprisingly found that the oxidized lignins produced have very desirable reactivity properties while showing improved fire resistance when used in products in which they are included in binder compositions and showing improved long-term stability compared to previously known oxidized lignins.

[0718] The oxidized lignin also exhibits improved hydrophilicity.

[0719] An important parameter for the reactivity of the prepared oxidized lignin is the carboxylic acid group content of the oxidized lignin.

[0720] In one embodiment, the oxidized lignin prepared has a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 2.0 mmol / g, such as 0.40 to 1.5 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (a).

[0721] Another way to describe the carboxylic acid group content is to use the average carboxylic acid group content per lignin macromolecule calculated according to the following formula:

[0722]

[0723] In one embodiment, the oxidized lignin produced has an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (a), such as more than 2 groups per macromolecule of component (a), such as more than 2.5 groups per macromolecule of component (a).

[0724] Method III for preparing oxidized lignin

[0725] Oxidized lignin that can be used as a component of the binder used in the present invention can be prepared by a method comprising the following steps:

[0726] The following components were brought into contact:

[0727] - a component (a) comprising one or more lignins,

[0728] a component (b) comprising ammonia and / or one or more amine components and / or any of their salts and / or alkali and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide,

[0729] - component (c) comprising one or more oxidizing agents,

[0730] - optional component (d) in the form of one or more plasticizers,

[0731] and allowing a mixing / oxidation step to proceed, wherein an oxidized mixture is produced, followed by an oxidation step, wherein the oxidized mixture is allowed to continue reacting for a residence time of 1 second to 10 hours, such as 10 seconds to 6 hours, such as 30 seconds to 2 hours.

[0732] Components (a), (b), (c) and (d) are as defined above in process II for preparing oxidized lignin.

[0733] In one embodiment of the invention, the process comprises a premixing step, wherein the components are brought into contact with one another.

[0734] During the premixing step, the following components may be brought into contact with each other:

[0735] - component (a) and component (b), or

[0736] - component (a), component (b) and component (c), or

[0737] - component (a), component (b) and component (d), or

[0738] - component (a), component (b), component (c) and component (d).

[0739] In one embodiment of the present invention, the premixing step can be carried out as a separate step and the mixing / oxidation step can be carried out after the premixing step. In this embodiment of the present invention, it is particularly advantageous to bring components (a) and (b) and optionally (d) into contact with each other in the premixing step. Component (c) is then added to the premix produced in the premixing step in a subsequent mixing / oxidation step.

[0740] In another embodiment of the present invention, the premixing step may correspond to the mixing / oxidation step. In this embodiment of the present invention, the components (a), (b), and (c) are mixed and the oxidation process is initiated simultaneously. The subsequent residence time can be carried out in the same equipment used to carry out the mixing / oxidation step. This embodiment of the present invention is particularly advantageous if component (c) is air.

[0741] The present inventors have found that by carrying out an oxidation step after the mixing / oxidation step, preferably without further mixing of the reaction mixture, the oxidation rate can be controlled in a very efficient manner. At the same time, since the oxidation step after the mixing / oxidation step requires less complex equipment, the cost of carrying out the process is reduced.

[0742] Another advantage is that the oxidized lignin produced is particularly stable. Another surprising advantage is that the viscosity of the oxidized lignin produced can be well adjusted. Another surprising advantage is that the concentration of the oxidized lignin can be very high.

[0743] In one embodiment, the residence time is selected to allow the oxidation reaction to reach a desired degree of completion, preferably complete completion.

[0744] System I for carrying out said method III

[0745] In one embodiment, a system for performing the method comprises:

[0746] - at least one rotor-stator device,

[0747] - one or more inlets for water and components (a) and (b),

[0748] - one or more outlets of the rotor-stator device,

[0749] At least one reaction device, in particular at least one reaction tube, is arranged downstream of at least one or more outlets in the process flow direction.

[0750] In one embodiment, the system comprises one or more inlets for component (c) and / or component (d).

[0751] In one embodiment, the system comprises a premixing device.

[0752] The premixing device may comprise one or more inlets for water and / or component (a) and / or component (b) and / or component (c) and / or component (d).

[0753] In one embodiment of the present invention, the premixing device comprises inlets for water and components (a) and (b).

[0754] Component (c) may also be mixed with the three ingredients (water, component (a), and component (b)) during the premixing step. The premixing device may then also have an inlet for component (c). If component (c) is air, the premixing device may be formed by an open mixing container, so that in this case component (c) already comes into contact with the other components (water, component (a), and component (b)) through the opening of the container. Furthermore, in this embodiment of the invention, the premixing device may optionally include an inlet for component (d).

[0755] In one embodiment, the system is constructed in such a way that the inlet for components (a), (b) and (d) is the inlet of a premixing device, in particular the inlet of an open rotor-stator device, whereby the system also comprises an additional rotor-stator device having an inlet for component (c) and the additional rotor-stator device having an outlet for the oxidized lignin.

[0756] The premixing step and the mixing / oxidation step may be performed simultaneously. In this case, the premixing device and the mixing / oxidation device are a single device, ie a rotor-stator device.

[0757] In one embodiment, a rotor-stator apparatus used in the method of the present invention comprises a stator having a toothed ring and a rotor having teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator apparatus has the following features: a guide funnel protruding between the arms of the rotor focuses the incoming material flow from above into the central area of ​​the container. The outer surface of the guide funnel defines an annular gap that restricts the material flow. A feed screw is provided at the rotor to feed the working area of ​​the apparatus. The guide funnel retains the product in the active area of ​​the apparatus, and the feed screw generates increased material pressure in the center.

[0758] System II for carrying out said method III

[0759] In one embodiment, a system for performing the method comprises:

[0760] - one or more inlets for water, components (a) and (b),

[0761] - at least one mixing and oxidation device having one or more outlets, and

[0762] - At least one mixer / heat exchanger arranged downstream of at least one or more outlets in the direction of process flow, wherein said mixer / heat exchanger comprises a temperature control device.

[0763] In one embodiment, the system comprises an additional inlet or inlets for component (c) and / or component (d).

[0764] In one embodiment, the system comprises a premixing device.

[0765] The premixing device may comprise one or more inlets for water and / or component (a) and / or component (b) and / or component (c) and / or component (d).

[0766] In one embodiment, the premixing apparatus comprises inlets for water and components (a) and (b).

[0767] Component (c) may also be mixed with the three ingredients (water, component (a), and component (b)) during the premixing step. The premixing device may then also have an inlet for component (c). If component (c) is air, the premixing device may be formed by an open mixing container, so that in this case component (c) already comes into contact with the other components (water, component (a), and component (b)) through the opening of the container. Furthermore, in this embodiment of the invention, the premixing device may optionally include an inlet for component (d).

[0768] In one embodiment, the system is constructed in such a way that the inlets for components (a), (b) and (d) are inlets of an open rotor-stator apparatus, whereby the system also comprises a mixer / heat exchanger with an inlet for component (c) and an outlet for oxidized lignin.

[0769] The premixing step and the mixing / oxidation step may be performed simultaneously. In this case, the premixing device and the mixing / oxidation device are a single device.

[0770] In one embodiment, a rotor-stator apparatus used in the method of the present invention comprises a stator having a toothed ring and a rotor having teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator apparatus has the following features: a guide funnel protruding between the arms of the rotor focuses the incoming material flow from above into the central area of ​​the container. The outer surface of the guide funnel defines an annular gap that restricts the material flow. A feed screw is provided at the rotor to feed the working area of ​​the apparatus. The guide funnel retains the product in the active area of ​​the apparatus, and the feed screw generates increased material pressure in the center.

[0771] Of course, other equipment can also be used as premixing equipment. Moreover, the premixing step can be carried out in a mixing and oxidation device.

[0772] In one embodiment, the mixing and oxidation device is a static mixer. A static mixer is a device with no moving parts for continuous mixing of fluid materials. One design of a static mixer is a plate mixer, and another common device type consists of a mixer element contained in a cylindrical (tube) or square housing.

[0773] In one embodiment, the mixer / heat exchanger is designed as a multi-tube heat exchanger with mixing elements. The mixing elements are preferably fixed devices through which the mixture must flow, thereby mixing by flowing through them. The mixer / heat exchanger can be designed as a plug flow reactor.

[0774] Example 1

[0775] Example IA - Lignin Oxidation by Hydrogen Peroxide in Aqueous Ammonia Solution:

[0776] The amounts of the ingredients used according to Example IA are provided in Tables IA 1.1 and IA 1.2.

[0777] Although kraft lignin is soluble in water at higher pH values, it is known that the viscosity of the solution increases significantly at certain weight percentages. This increase in viscosity is believed to be due to a combination of strong hydrogen bonding and π-electron interactions of the numerous aromatic rings present in lignin. For kraft lignin, a sudden increase in viscosity is observed at approximately 21-22 wt% in water, and 19 wt% kraft lignin was used in the examples presented.

[0778] Aqueous ammonia solution was used as the base in the pH adjustment step. The amount was fixed at 4 wt % based on the total reaction weight. The pH at the start of oxidation after the pH adjustment step was 10.7.

[0779] Table IA2 shows the results of CHNS elemental analysis of kraft lignin before and after oxidation. Prior to analysis, the sample was heat treated at 160° C. to remove adsorbed ammonia. The analysis showed that a certain amount of nitrogen became part of the structure of the oxidized lignin during the oxidation process.

[0780] During batch experimental testing, it was determined that adding the entire amount of hydrogen peroxide in small time intervals was beneficial for oxidation, as opposed to adding the peroxide in multiple small portions over a long period of time. In this example, 2.0 wt % H2O2 based on the total reaction weight was used.

[0781] The oxidation is an exothermic reaction and a temperature increase will be noticed after the addition of the peroxide. In this example, the temperature was maintained at 60°C during the three hour reaction.

[0782] After oxidation, by 31 The amount of lignin functional groups per gram of sample was determined by P NMR and water titration. 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphosphacyclopentane (TMDP) was used as the phosphitylation reagent and cholesterol was used as the internal standard. 31 Preparation of Samples for P NMR NMR spectra were obtained for kraft lignin before and after oxidation and the results are summarized in Table IA3.

[0783] The change in COOH groups was determined by water titration using the following formula:

[0784]

[0785] Where V 2s and V 1s is the endpoint volume of the sample, and V 2b and V 1b is the void volume. C 酸 In this case it is 0.1M HCl, and m sis the weight of the sample. The values ​​obtained from the water titration before and after oxidation are shown in Table IA4.

[0786] The average COOH functionality can also be quantified by the saponification value, which represents the number of milligrams of KOH required to saponify 1 g of lignin. Such a method can be found in AOCS Official Method Cd 3-25.

[0787] The average molecular weight was also determined before and after oxidation using a PSS PolarSil column (9:1 (v / v) dimethyl sulfoxide / water eluent containing 0.05 M LiBr) and a UV detector at 280 nm. The combination of COOH concentration and average molecular weight also allowed the calculation of the average carboxylic acid group content per lignin macromolecule. These results are shown in Table IA5.

[0788] Example 1B - Scaling up lignin oxidation by hydrogen peroxide in ammonia to pilot scale

[0789] Lignin oxidation with hydrogen peroxide is an exothermic process, and even at the laboratory scale, a significant temperature increase can be observed after the addition of peroxide. This presents a natural problem when scaling up chemical processes, as the heat generated scales with the cube of the size (volume), while cooling typically only increases with the square of the size (area). Furthermore, due to the high viscosity of the adhesive intermediate, process equipment must be carefully selected or designed. Therefore, scale-up is carefully planned and carried out in several steps.

[0790] The first scale-up step used a professional stainless steel mixer with very efficient mechanical mixing from 1 L (laboratory scale) to 9 L. The scale-up resulted in only slightly higher final temperatures than those obtained at the lab scale, which was attributed to the efficient air cooling of the reactor and the slow addition of hydrogen peroxide.

[0791] The next scale-up step was conducted in a closed 200-L reactor equipped with a high-efficiency water jacket and a high-efficiency propeller stirrer. This time, the scale was 180 liters, and the hydrogen peroxide was added in two steps, approximately 30 minutes apart. This scale-up went relatively smoothly, although considerable foaming was a problem, partly due to the high reactor fill. To control foaming, a small amount of food-grade defoamer was sprayed onto the foam. Crucially, external water cooling was used to achieve a manageable temperature and a final temperature below 70°C.

[0792] The pilot-scale reaction was conducted in an 800-L reactor equipped with a water-cooled jacket and a two-blade propeller. 158 kg of lignin (UPM LignoBoost™ BioPiva 100) with a dry matter content of 67 wt% was delumped and suspended in 224 kg of water, which was stirred to form a homogeneous suspension. While stirring continued, 103 kg of 25% aqueous ammonia was pumped into the reactor and stirred for an additional 2 hours to form a dark, viscous lignin solution.

[0793] To the stirred lignin solution was added 140 kg of 7.5 wt% hydrogen peroxide at 20-25° C. over 15 minutes. The temperature and foam level were carefully monitored during and after the addition of the hydrogen peroxide, and cooling water was added to the cooling jacket to maintain an acceptable foam level and a temperature rise below 4° C. / minute and a final temperature below 70° C. After the temperature rise ceased, cooling was stopped and the product mixture was stirred for an additional 2 hours before being transferred to a transfer vessel.

[0794] Based on the scaled-up run, it can be concluded that even though the reaction is exothermic, most of the heat of reaction is actually balanced by the heat capacity of water from room temperature to approximately 60°C; only the final portion must be removed by cooling. It should be noted that due to this and the short reaction time, this process is ideal for scale-up and process intensification using continuous reactors such as in-line mixers, tubular reactors, or CSTR-type reactors. This will ensure good temperature control and a more defined reaction course.

[0795] Testing of the scaled-up batches showed that the oxidized lignin produced had properties consistent with laboratory-produced batches.

[0796] Table IA 1.1 - Quantities of Materials Used in Supplied Form:

[0797]

[0798] Table IA 1.2 - Amounts of active materials used:

[0799]

[0800] Table IA 2 - Elemental analysis of kraft lignin before and after oxidation:

[0801]

[0802] Table IA 3-Pass 31 Functional group distribution of kraft lignin before and after oxidation obtained by P NMR:

[0803]

[0804] Table IA 4 - COOH group content determined by water titration (in mmol / g):

[0805] Table IA 5 - Number-average molar mass (Mn) and weight-average molar mass (Mw) (expressed in g / mol) and average carboxylic acid group content per lignin macromolecule before and after oxidation determined by size exclusion chromatography

[0806]

[0807] Example II

[0808] In the following examples, several oxidized lignins were prepared.

[0809] The following properties were determined for the oxidized lignin:

[0810] Solid content of components:

[0811] The amount of each component in a given oxidized lignin solution is based on the water-free mass of the component or as described below.

[0812] Kraft lignin is produced by UPM as BioPival TM Supplied as dry powder. 25% NH4OH was supplied by Sigma-Aldrich and used as supplied. 30% H2O2 (Cas No. 7722-84-1) was supplied by Sigma-Aldrich and used as supplied or diluted with water. PEG 200 was supplied by Sigma-Aldrich and, for simplicity, was assumed to be anhydrous and used as is. PVA (Mw 89,000-98,000, Mw 85,000-124,000, Mw 130,000, Mw 146,000-186,000) (Cas No. 9002-89-5) was supplied by Sigma-Aldrich and, for simplicity, was assumed to be anhydrous and used as is. Urea (Cas No. 57-13-6) was supplied by Sigma-Aldrich and used as supplied or diluted with water. Glycerol (Cas No. 56-81-5) was supplied by Sigma-Aldrich and was assumed to be anhydrous for simplicity and used as received.

[0813] Oxidized lignin solid content

[0814] The content of oxidized lignin after heating to 200°C for 1 h is referred to as the "dry solids content" and is expressed as a percentage of the weight remaining after heating.

[0815] A disc-shaped asbestos sample (5 cm in diameter and 1 cm in height) was cut from the asbestos and heat-treated at 580°C for at least 30 minutes to remove all organic matter. The solid content of the binder mixture was measured by distributing a sample of the binder mixture (approximately 2 g) onto the heat-treated asbestos disc in a tinfoil container. The tinfoil container containing the asbestos disc was weighed immediately before and after adding the binder mixture. Two asbestos discs loaded with this binder mixture in tinfoil containers were produced and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the sample was weighed and the dry solid content was calculated as the average of the two results.

[0816] COOH group content

[0817] The change in the COOH group content was also determined by water titration using the following formula:

[0818]

[0819] Where V 2s and V 1s is the endpoint volume of the sample, and V 2b and V 1b is the blank sample volume. C 酸 In this case it is 0.1M HCl, and m s,g is the weight of the sample.

[0820] Method for producing oxidized lignin:

[0821] 1) Water and lignin were mixed in a three-necked glass bottom flask in a water bath at room temperature (20-25° C.), and the flask was connected to a condenser and a temperature recording device during stirring. Stirring was continued for 1 hour.

[0822] 2) Add ammonia all at once during stirring.

[0823] 3) If the slightly exothermic reaction with ammonia does not increase the temperature, raise the temperature to 35°C by heating.

[0824] 4) Measure pH.

[0825] 5) Add plasticizer PEG200 and stir for 10 minutes.

[0826] 6) After about 1 hour when the lignin is completely dissolved, slowly add 30% H2O2 in one go.

[0827] 7) The exothermic reaction of adding H2O2 increases the temperature in the glass bottom flask - if the reaction temperature is below 60°C, increase the temperature to 60°C and place the sample at 60°C for 1 hour.

[0828] 8) The round-bottom flask was then removed from the water bath and cooled to room temperature.

[0829] 9) Take samples for determination of dry solids content, COOH, viscosity, density and pH.

[0830] Oxidized lignin composition

[0831] In the following, the entry numbers for the oxidized lignin examples correspond to the entry numbers used in Table II.

[0832] Example IIA

[0833] 71.0 g of UPM Biopiva 100 lignin was dissolved in 149.0 g of water at 20°C. 13.3 g of 25% NH₄OH was added and stirred with a magnetic stirrer for 1 hour. Then, 16.8 g of 30% HO was slowly added while stirring. The temperature was raised to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled, thereby stopping the reaction. The resulting material was analyzed for COOH content, dry solids content, pH, viscosity, and density.

[0834] Example IIE

[0835] 71.0 g of UPM Biopiva 100 lignin was dissolved in 88.8 g of water at 20°C. 13.3 g of 25% NH₄OH was added and stirred with a magnetic stirrer for 1 hour. 22.8 g of PEG 200 was added and stirred for 10 minutes, after which 16.7 g of 30% HO was slowly added with stirring. The temperature was raised to 60°C in a water bath. After 1 hour of oxidation, the bath was cooled, thereby terminating the reaction. The resulting material was analyzed for COOH content, dry solids content, pH, viscosity, and density.

[0836] Example IIC

[0837] 71.0 g of UPM Biopiva 100 lignin was dissolved in 57.1 g of water at 20°C. 13.3 g of 25% NH₄OH was added and stirred with a magnetic stirrer for 1 hour. Then, 16.6 g of 30% HO was slowly added while stirring. The temperature was raised to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled, thereby stopping the reaction. The resulting material was analyzed for COOH content, dry solids content, pH, viscosity, and density.

[0838] Example IIF

[0839] 71.0 g of UPM Biopiva 100 lignin was dissolved in 57.1 g of water at 20°C. 13.3 g of 25% NH₄OH was added and stirred with a magnetic stirrer for 1 hour. 19.0 g of PEG 200 was added and stirred for 10 minutes, after which 16.6 g of 30% HO was slowly added with stirring. The temperature was raised to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled, thereby terminating the reaction. The resulting material was analyzed for COOH content, dry solids content, pH, viscosity, and density.

[0840]

[0841] Example III:

[0842] 8.5 liters of hot water (50° C.) and 1.9 liters of NH 4 OH (24.7%) were mixed, and then 9.0 kg of lignin (UPM biopiva 100) were slowly added thereto over a period of 10 minutes under high-speed stirring (660 rpm, 44 Hz).

[0843] The temperature increased due to the high shear forces. After 30 minutes, 4 liters of hot water were added and the material was stirred for a further 15 minutes before the remainder of the hot water (5 liters) was added. Samples were taken for analysis of undissolved lignin and pH measurement using a Hegman Scale.

[0844] The premix was then transferred to a rotor-stator apparatus and a reaction apparatus, where oxidation was carried out using H2O2 (17.5 vol%). The reaction apparatus used in this example consisted at least partially of a reaction tube and a reaction vessel. The premix was dosed at 150 l / h, and the H2O2 at 18 l / h.

[0845] In this example, a Cavitron CD1000 rotor-stator apparatus was used for the mixing / oxidation step. The rotor-stator apparatus was operated at 250 Hz (55 m / s peripheral speed) and a back pressure of 2 bar. The residence time in the reaction tube was 3.2 minutes, and the residence time in the reaction vessel was 2 hours.

[0846] The temperature of the premix was 62°C and the oxidation step raised the temperature to 70°C.

[0847] The final products were analyzed for COOH group content, dry solids content, pH, viscosity and residual H2O2.

[0848] Table III:

[0849]

[0850] Example IV:

[0851] 484 liters of hot water (70°C) and 47.0 liters of NH4OH (24.7%) were mixed, and then 224.0 kg of lignin (UPM biopiva 100) was slowly added thereto over 15 minutes with high-speed stirring. Samples were taken for analysis of undissolved lignin using a Hegman Scale and pH measurement.

[0852] The premix was then transferred to a static mixer and a mixer / heat exchanger, where oxidation was carried out using H2O2 (35 vol%). The premix was dosed at 600 l / h and the H2O2 at 17.2 l / h. The residence time in the mixer / heat exchanger was 20 minutes.

[0853] The temperature of the mixture was raised to 95°C during the oxidation step.

[0854] The final products were analyzed for COOH group content, dry solids content, pH, viscosity and residual H2O2.

[0855] An adhesive was prepared based on this AOL: 49.3 g AOL (19.0% solids), 0.8 g primid XL552 (100% solids) and 2.4 g PEG200 (100% solids) were mixed with 0.8 g water to give a solids content of 19%; this adhesive was then used to test mechanical properties in a strip test.

[0856] Strip test

[0857] The mechanical strength of the adhesives was tested in a strip test. For each adhesive, 16 strips were produced from a mixture of the adhesive and asbestos balls from an asbestos spinning production.

[0858] A sample of binder solution (16.0 g) with a 15% dry solids content was thoroughly mixed with asbestos balls (80.0 g). The resulting mixture was then filled into four grooves of a heat-resistant silicone mold to make small strips (4 x 5 grooves per mold; groove top dimensions: length = 5.6 cm, width = 2.5 cm; groove bottom dimensions: length = 5.3 cm, width = 2.2 cm; groove height = 1.1 cm). The mixture then placed in the groove was pressed with a flat metal strip of appropriate size to produce a flat strip surface. 16 strips were prepared in this way by each binder. The resulting strips were then cured at 200 ° C. The curing time was 1 hour. After cooling to room temperature, the strips were carefully taken out from the container. Five of the strips were aged for 3 hours in a water bath at 80 ° C.

[0859] After drying for 1-2 days, the aged bars and 5 unaged bars were broken in a 3-point bending test on a Bent Tram machine (test speed: 10.0 mm / min; break level: 50%; nominal strength: 30 N / mm 2 Support distance: 40 mm; Maximum deflection: 20 mm; Nominal e-modulus: 10,000 N / mm 2 ) to investigate their mechanical strength. The strips were placed in the machine with the "top side" (ie the side with the dimensions length = 5.6 cm, width = 2.5 cm) facing upwards.

[0860]

[0861] Experimental part for Alternative A Example

[0862] In the following examples, several mineral wool products containing binders falling within the definition of the present invention were prepared and compared to mineral wool products containing prior art binders.

[0863] Unless otherwise indicated, indicated values ​​in percentage (%) refer to percentages by weight.

[0864] The following properties of the mineral wool product containing the binder of the present invention and the mineral wool product containing the binder of the prior art were tested respectively:

[0865] Determination of isocyanic acid (ICA) release:

[0866] The amount of ICA released from a mineral fiber product containing a cured binder composition can be measured according to the following Procedure I. The same Procedure I can also be used to analyze the amount of NH3 and / or HCN released.

[0867] Program I

[0868] Samples of mineral wool products were analyzed using thermal testing. The thermal testing system consisted of a temperature-controlled tube furnace equipped with a quartz glass tube, connected to a GASMET DX4000 FTIR (Fourier Transform Infrared Spectroscopy) analyzer via heat-traced transport tubes. The tube in the tube furnace was a quartz tube (23 mm diameter, 800 mm length, 2.0 mm thickness) with tapered internally threaded glass joints (NS 24 / 29) at both ends. The tube furnace used was a Nabertherm model R30 / 500 / 12-B170.

[0869] The GASMET analyzer is equipped with an internal pump that can provide the required amount of gas to perform a proper analysis of the gas. The quartz glass tube is open to the surrounding environment to ensure that the appropriate amount of carrier gas enters the analyzer along with the gas released from the test sample.

[0870] The mineral wool product was homogenized by crushing. Approximately 2 g of sample was weighed and evenly distributed in a porcelain crucible. This was then placed into the quartz tube at the pre-set temperature. The current test temperature of the sample was monitored by a thermocouple. Throughout the test, air was passed through the tube at a rate of 1 L / min at 25°C.

[0871] Before any test is run, the system is tested for leaks and the cleanliness of the quartz tubes by analyzing the compressed air passing through the system. Cleanliness is only accepted if the tested gas is 0 ppm. Values ​​above 0 ppm will trigger cleaning of the quartz tubes.

[0872] All sample points were repeated three times to ensure high reliability of the measured values.

[0873] After the sample is loaded, GASMET data sampling is started. The sampling frequency is adjusted to 5 seconds, and then approximately 2 seconds of processing is performed, resulting in an average duration of 6.77 seconds per sample point.

[0874] GASMET has an accuracy of 8cm -1 .

[0875] During data collection, the samples were monitored to observe the burnout time of each species released. Data collection was stopped when all species had significantly decreased. Samples collected at 250°C and 350°C were stopped after the times (average durations) shown in Table A, although not all emissions decreased to zero (but very close), while samples collected at 450°C and 600°C burned to near-zero values ​​more quickly (sometimes in just a few minutes).

[0876] Spectra were analyzed using Calcmet software, and the system was pre-calibrated for each species.

[0877] The emissions for each sample are compiled and the data are cut off after all emissions for each species (ICA or any other species to be measured) are close to zero. The integration under the curve is performed by summing up the contributions of the individual measurements (approximate numerical integration).

[0878] The release rate is calculated by taking into account the weight, solids content and duration. The result is given in the unit "ppm isocyanate / gram solids content / second". With respect to "gram solids content", the solids content (LOI) refers to the amount of organic material in the mineral fiber product (loss on ignition).

[0879] Example of ICA release measurement:

[0880] ICA release of the sample product at 450°C: The integral under the curve totals 6134 ppm ICA, the cutoff time is 503 seconds, the sample weight is 2.215 g, and the solids content (by weight) is 2.3%. This yields: 6134 ppm ICA / (2.3%·503 seconds·2.215 g) = 239 ppm ICA / (grams solids·seconds)

[0881] Determination of solid content (loss on ignition (LOI))

[0882] The amount of organic material (loss on ignition) is determined as the weight loss of the sample obtained by burning off the organic material at 590°C. Typically, the organic material is the binder and the impregnation oil. This is done in accordance with the specifications in EN 13820. The binder content is taken as LOI. The binder includes the oil and other binder additives, if present.

[0883] Determination of maximum operating temperature

[0884] The maximum operating temperature of mineral fiber products is determined according to the maximum operating temperature panel test of standard EN 14706:2012.

[0885] Determination of solid content of binder

[0886] The content of the binder after curing is called "binder solid content".

[0887] A disc-shaped asbestos sample (5 cm in diameter and 1 cm in height) was cut from the asbestos and heat-treated at 580°C for at least 30 minutes to remove all organic matter. The solid content of the binder mixture was measured by distributing a sample of the binder mixture (approximately 2 g) onto the heat-treated asbestos disc in a tinfoil container. The tinfoil container containing the asbestos disc was weighed immediately before and after adding the binder mixture. Two asbestos discs loaded with this binder mixture in tinfoil containers were produced and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the sample was weighed and the binder solid content was calculated as the average of the two results.

[0888] Unless otherwise specified, the following reagents were used as received:

[0889] Lignin UPM BioPiva 100: Kraft lignin supplied by UPM, BioPiva 100 TM dry powder.

[0890] PEG 200: Supplied by Sigma-Aldrich, assumed to be anhydrous for simplicity and used as received.

[0891] Primid XL552: Hydroxyalkylamide crosslinker supplied by EMS-CHEMIE AG.

[0892] Momentive VS142: VS-142 is a water-based oligomeric aminosilane supplied by Momentive.

[0893] Preparation of Ammonia Oxidized Lignin (AOL) Resin

[0894] To a 6,000-liter reactor, add 3,267 kg of water, followed by 287 kg of 24.7% aqueous ammonia. Then, slowly add 1,531 kg of UPM BioPiva 100 lignin over 30 to 45 minutes. Heat the mixture to 40°C and maintain it at that temperature for 1 hour. After 1 hour, check for undissolved lignin. This can be done by inspecting the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in the brown binder. During the dissolution step, the color of the lignin solution changes from brown to shiny black.

[0895] After the lignin was completely dissolved, 1 liter of defoamer (obtained from of 11-10). The batch temperature was maintained at 40°C.

[0896] Then, the addition of 307.5 kg of 35% hydrogen peroxide was started. The hydrogen peroxide was added at a rate of 200-300 liters / hour. The first half of the hydrogen peroxide was added at a rate of 200 liters / hour, after which the addition rate was increased to 300 liters / hour.

[0897] During the addition of hydrogen peroxide, the temperature of the reaction mixture was controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[0898] After reacting at 65° C. for 15 minutes, the reaction mixture was cooled to a temperature below 50° C. A resin having a COOH value of 1.2 mmol / g solid was thus obtained.

[0899] Preparation of the final binder (uncured binder composition suitable for preparing the mineral fiber product of the present invention)

[0900] A binder was formulated from the above AOL resin by adding 270 kg of polyethylene glycol 200 (PEG 200) and 433 kg of a 31% solution of Primid XL-552 in water.

[0901] Analysis of the final adhesive showed the following data:

[0902] Solid content: 18.9%

[0903] pH: 9.7

[0904] Viscosity: 25.5 mPas·s

[0905] Density: 1.066 kg / l

[0906] Comparative Example 1

[0907] The adhesive is a phenolic resin PUF-resol modified with urea.

[0908] A phenolic resin was prepared by reacting 37% aqueous formaldehyde (606 kg) and phenol (189 kg) in the presence of 46% aqueous potassium hydroxide (25.5 kg) at a temperature of 84° C. with a heating rate of approximately 1° C. / minute to the reaction temperature. The reaction was continued at 84° C. until the acid resistance of the resin was 4 and most of the phenol was converted. Urea (241 kg) was then added and the mixture was cooled.

[0909] The acid resistance (AT) indicates how many times a given volume of cement can be diluted with acid without the mixture becoming cloudy (precipitation of the cement). Sulfuric acid is used to determine the stopping criterion in cement production, and an acid resistance below 4 indicates that the cement reaction is complete.

[0910] To measure AT, prepare a titrant by diluting 2.5 ml of concentrated sulfuric acid (>99%) with 1 L of ion-exchanged water. This titrant is then titrated against 5 ml of the adhesive to be investigated at room temperature while manually shaking the adhesive to keep it in motion; a magnetic stirrer and bar magnet can be used if desired. The titration is continued until a slight turbidity appears in the adhesive that does not disappear upon shaking.

[0911] The acid tolerance (AT) was calculated by dividing the amount of acid used for titration (mL) by the amount of sample (mL):

[0912] AT = (titration volume used (mL)) / (sample volume (mL))

[0913] Using the obtained urea-modified phenolic resin, a binder was prepared by adding 25% ammonia water (90 L) and ammonium sulfate (13.2 kg), and then adding water (1300 kg).

[0914] To the above mixture was added 18% dextrose (127.5 kg) based on the dry matter of the above binder and dextrose. The binder solids content was then measured as described above and the mixture was diluted with the required amount of water and silane for mechanical testing.

[0915] A mineral fiber product was prepared comprising 100 mm thick mineral wool bonded with the prior art binder composition. The density of the mineral fiber product was 145 kg / m 3 The loss on ignition was 2.4%. Due to the 0.1% mineral oil, the proportion of the cured binder composition in the mineral fiber product was 2.3%.

[0916] The mineral fiber products produced were tested as described in Procedure I. The results are given in Table A below.

[0917] Comparative Example 2

[0918] A mixture of 75.1% aqueous glucose syrup (19.98 kg, effectively equivalent to 15.0 kg of glucose syrup), 50% aqueous hypophosphorous acid (0.60 kg, effectively equivalent to 0.30 kg / 4.55 mol hypophosphorous acid), and sulfamic acid (0.45 kg, 4.63 mol) in water (30.0 kg) was stirred at room temperature until a clear solution was obtained. 28% aqueous ammonia (0.80 kg, effectively equivalent to 0.22 kg / 13.15 mol ammonia) was then added dropwise until the pH reached 7.9. The binder solids content was then measured (21.2%). To obtain the appropriate binder composition (15% binder solids solution, 0.5% silane per binder solids), the binder mixture was diluted with water (0.403 kg / kg binder mixture) and 10% aqueous silane (0.011 kg / kg binder mixture, Momentive VS-142). The final pH of the binder mixture was 7.9.

[0919] Preparation thickness is 100mm and density is 145kg / m 3 and a mineral fiber product having an LOI of 2.5%.The conventional method for producing mineral fiber products as described in the above description was used.

[0920] The mineral fiber products produced were tested as described in Procedure I. The results are given in Table A below.

[0921] Example 1

[0922] In a 6,000-liter reactor, 3,267 kg of water was added, followed by 861 kg of 24.7% aqueous ammonia. Next, 1,531 kg of UPM BioPiva 100 lignin was slowly added over 30 to 45 minutes. The mixture was heated to 40°C and held at that temperature for 1 hour. After 1 hour, the mixture was checked for undissolved lignin. This can be done by inspecting the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in the brown binder. During the dissolution step, the color of the lignin solution will change from brown to shiny black.

[0923] After the lignin was completely dissolved, 1 liter of defoamer (obtained from of 11-10). The batch temperature was maintained at 40°C.

[0924] Then, the addition of 307.5 kg of 35% hydrogen peroxide was started. The hydrogen peroxide was added at a rate of 200-300 liters / hour. The first half of the hydrogen peroxide was added at a rate of 200 liters / hour, after which the addition rate was increased to 300 liters / hour.

[0925] During the addition of hydrogen peroxide, the temperature of the reaction mixture was controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[0926] After reacting at 65° C. for 15 minutes, the reaction mixture was cooled to a temperature below 50° C. A resin having a COOH value of 1.1 mmol / g solid was thus obtained.

[0927] Preparation of the final adhesive

[0928] A binder was formulated from the above AOL resin by adding 270 kg of polyethylene glycol 200 and 396 kg of a 31% solution of Primid XL-552 in water.

[0929] Analysis of the final adhesive showed the following data:

[0930] Solid content: 18.9%

[0931] pH: 10.2

[0932] Viscosity: 25.5 mPas·s

[0933] Density: 1.066kg / l.

[0934] A mineral fiber product according to the invention was prepared having 100 mm of bonded mineral wool and the resulting binder composition to obtain a cured binder composition based on oxidized lignin. The conventional method for producing mineral fiber products described above in the description was used. The density of the mineral fiber product was 145 kg / m 3 The loss on ignition was 2.3%. The proportion of the cured binder composition in the mineral fiber product was 2.2%. The binder composition used was as described above, including 0.1% mineral oil.

[0935] The mineral fiber products produced were tested as described in Procedure I. The results are given in Table A below.

[0936] Example 2

[0937] To a 6,000-liter reactor, add 3,267 kg of water, followed by 287 kg of 24.7% aqueous ammonia. Then, slowly add 1,531 kg of UPM BioPiva 100 lignin over 30 to 45 minutes. Heat the mixture to 40°C and maintain it at that temperature for 1 hour. After 1 hour, check for undissolved lignin. This can be done by inspecting the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in the brown binder. During the dissolution step, the color of the lignin solution changes from brown to shiny black.

[0938] After the lignin was completely dissolved, 1 liter of defoamer (obtained from of 11-10). The batch temperature was maintained at 40°C.

[0939] Then, the addition of 307.5 kg of 35% hydrogen peroxide was started. The hydrogen peroxide was added at a rate of 200-300 liters / hour. The first half of the hydrogen peroxide was added at a rate of 200 liters / hour, after which the addition rate was increased to 300 liters / hour.

[0940] During the addition of hydrogen peroxide, the temperature of the reaction mixture was controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[0941] After reacting at 65° C. for 15 minutes, the reaction mixture was cooled to a temperature below 50° C. A resin having a COOH value of 1.2 mmol / g solid was thus obtained.

[0942] Preparation of the final adhesive

[0943] A binder was formulated from the above AOL resin by adding 270 kg of polyethylene glycol 200 and 433 kg of a 31% solution of Primid XL-552 in water.

[0944] Analysis of the final adhesive showed the following data:

[0945] Solid content: 18.9%

[0946] pH: 9.7

[0947] Viscosity: 25.5 mPas·s

[0948] Density: 1.066kg / l.

[0949] This binder composition is used with 100mm mineral wool to produce a density of 145kg / m 3A mineral wool product with a thickness of 100 mm and a loss on ignition of 2.4% was prepared. The conventional method for producing mineral fiber products described above in the description was used. The material was used as described in Procedure I. The results are given in Table A below.

[0950] Heat release of Examples 1 and 2 and Comparative Examples 1 and 2

[0951] The release characteristics of isocyanate (ICA), NH3, and HCN of the mineral fiber products of Examples 1 and 2 and Comparative Examples 1 and 2 at temperatures of 250°C, 350°C, 450°C, and 600°C were tested according to Procedure I described above.

[0952] The results are shown below in Table A. The output values ​​given are the average release of each species in units of ppm per gram solids per second (ppm / g solids·s).

[0953] Table A

[0954]

[0955] The release rates for the four mineral wool products tested were obtained to enable us to rank the release rates from the systems relative to each other.

[0956] Overall, the release rate of Comparative Example 1 is significantly higher than that of Comparative Example 2 and Examples 1 and 2. Examples 1 and 2 have approximately the same release rates for all species at all temperatures, regardless of the chemical composition of the binder used in these mineral wool products.

[0957] As can be seen from the results, Comparative Example 1 showed the highest level of released substances (ICA, NH3 and HCN). Comparative Example 1 released the highest amount of ICA. The ICA release rate of Comparative Example 2 was higher than that of Examples 1 and 2. Examples 1 and 2 had approximately the same release rate at all temperatures.

[0958] With respect to ammonia, Comparative Example 1 showed the highest level of NH3 release. The NH3 release rates of Comparative Example 2 and Examples 1 and 2 were comparable.

[0959] The HCN release rates were increasingly higher (by increasing the temperature) in Comparative Examples 1 and 2 compared to Examples 2 and 3. Again, Comparative Example 1 showed the highest level of emitted gases.

[0960] Maximum operating temperature test of Example 1 and Comparative Example 1

[0961] The performance of the products of Example 1 and Comparative Example 1 was tested according to the following test methods: Maximum Operating Temperature Panel Test; EN 14706:2012, to demonstrate the thermal stability of mineral wool products at high temperatures. Both products were tested multiple times.

[0962] The measurement and test results of the product of Example 1 are as follows:

[0963]

[0964] Therefore, the maximum operating temperature value of Example 1 is measured to be ST(+)=650° C.±10° C. This value is consistent with the selected test temperature ST(+)=650° C., but is at the upper limit of the exothermic reaction.

[0965] The measurement and test results of the product of Comparative Example 1 are as follows:

[0966]

[0967] Therefore, the maximum operating temperature value measured is ST(+) = 650° C. ± 10° C. This value does not meet the selected test temperature ST(+) = 650° C. because the upper limit of the exothermic reaction has been reached.

[0968] The product of Example 1 met the requirements of the Maximum Operating Temperature Panel Test EN 14706:2012 for an exothermic reaction during the test. The product of Comparative Example 1 did not meet the criteria for an exothermic reaction during the test because the half-height temperature of the test specimen rose above the temperature set point during the test. Both products met all other test criteria for passing the Maximum Operating Temperature Panel Test EN 14706:2012.

[0969] Experimental part for alternative B

[0970] Example

[0971] In the following examples, several mineral wool products containing binders falling within the definition of the present invention were prepared and compared to mineral wool products containing prior art binders.

[0972] Unless otherwise indicated, indicated values ​​in percentage (%) refer to percentages by weight.

[0973] The following properties of the mineral wool product containing the binder of the present invention and the mineral wool product containing the binder of the prior art were tested respectively:

[0974] Determination of isocyanic acid (ICA) release:

[0975] The total amount of ICA released from a mineral fiber product containing a cured binder composition can be measured according to the following Procedure II. The same Procedure II can also be used to analyze the total amount of HCN released.

[0976] Program II

[0977] Samples of mineral wool products were analyzed in thermal tests. The thermal test system consisted of a temperature-controlled tube furnace equipped with a quartz glass tube, connected to a GASMET DX4000 FTIR (Fourier Transform Infrared Spectroscopy) analyzer via a heat transfer tube. The tube in the tube furnace was a quartz tube (23 mm diameter, 800 mm length, 2.0 mm thickness) with tapered internally threaded glass joints (NS 24 / 29) at both ends. The tube furnace used was a Nabertherm model R30 / 500 / 12-B170.

[0978] The GASMET analyzer is equipped with an internal pump that can provide the required amount of gas to perform a proper analysis of the gas. The quartz glass tube is open to the surrounding environment to ensure that the appropriate amount of carrier gas enters the analyzer along with the gas released from the test sample.

[0979] The mineral wool product was homogenized by crushing. Approximately 2 g of sample was weighed and evenly distributed in a porcelain crucible. This was then placed into the quartz tube at the pre-set temperature. The current test temperature of the sample was monitored by a thermocouple. Throughout the test, air was passed through the tube at a rate of 3 L / min at 25°C.

[0980] Before any test is run, the system is tested for leaks and the cleanliness of the quartz tubes by analyzing the air passing through the system. Cleanliness is only accepted if the tested gas is 0 ppm. Values ​​above 0 ppm will trigger cleaning of the quartz tubes.

[0981] All sample points were repeated three times to ensure high reliability of the measured values.

[0982] After the sample is loaded, GASMET data sampling is started. The sampling frequency is adjusted to 30 seconds, followed by approximately 2 seconds of processing, resulting in an average duration of 32 seconds per sample point.

[0983] GASMET has an accuracy of 8cm -1 .

[0984] During data collection, samples were monitored to observe the burnout time of all released species. Data collection was stopped when the responses of all species had decreased to zero or stabilized near-zero levels. Samples collected at 250°C and 350°C were stopped after approximately one hour, while samples collected at 450°C and 600°C burned to near-zero values ​​much more quickly, sometimes within just a few minutes.

[0985] Spectra were analyzed using Calcmet software, and the system was pre-calibrated for each species.

[0986] The release of each sample was processed individually by measuring the exact time elapsed from the start of species release to the time it dropped to zero or near zero. The integration under the curve was performed by summing the contributions of the individual measurements (approximate numerical integration).

[0987] The total release is calculated by taking into account the sample weight, the molar volume at 0°C and 1 atmosphere, the applied gas flow rate and the molecular weight of the released species. The results are given in "micrograms per gram of sample".

[0988] Examples:

[0989] ICA release of the sample product at 250°C: The average ICA release from 1.501 g of sample was 2.35 ppm over a period of 34 minutes at a flow rate of 3 liters / minute. This yields: 2.35 ppm ICA 43.03 g / mol / 22.4 liters 34 minutes 3 liters / minute / 1.501 g = 306 μg / g sample.

[0990] Determination of solid content (loss on ignition (LOI))

[0991] The amount of organic material (loss on ignition) is determined as the weight loss of the sample obtained by burning off the organic material at 590°C. Typically, the organic material is the binder and the impregnation oil. This is done in accordance with the specifications in EN 13820. The binder content is taken as LOI. The binder includes the oil and other binder additives, if present.

[0992] Determination of maximum operating temperature

[0993] The maximum operating temperature of mineral fiber products is determined according to the maximum operating temperature panel test of standard EN 14706:2012.

[0994] Determination of solid content of binder

[0995] The content of the binder after curing is called "binder solid content".

[0996] A disc-shaped asbestos sample (5 cm in diameter and 1 cm in height) was cut from the asbestos and heat-treated at 580°C for at least 30 minutes to remove all organic matter. The solid content of the binder mixture was measured by distributing a sample of the binder mixture (approximately 2 g) onto the heat-treated asbestos disc in a tinfoil container. The tinfoil container containing the asbestos disc was weighed immediately before and after adding the binder mixture. Two asbestos discs loaded with this binder mixture in tinfoil containers were produced and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the sample was weighed and the binder solid content was calculated as the average of the two results.

[0997] Unless otherwise specified, the following reagents were used as received:

[0998] Lignin UPM BioPiva 100: Kraft lignin supplied by UPM, BioPiva 100 TM dry powder.

[0999] PEG 200: Supplied by Sigma-Aldrich, assumed to be anhydrous for simplicity and used as received.

[1000] Primid XL552: Hydroxyalkylamide crosslinker supplied by EMS-CHEMIE AG.

[1001] Momentive VS142: VS-142 is a water-based oligomeric aminosilane supplied by Momentive.

[1002] Preparation of Ammonia Oxidized Lignin (AOL) Resin

[1003] To a 6,000-liter reactor, add 3,267 kg of water, followed by 287 kg of 24.7% aqueous ammonia. Then, slowly add 1,531 kg of UPM BioPiva 100 lignin over 30 to 45 minutes. Heat the mixture to 40°C and maintain it at that temperature for 1 hour. After 1 hour, check for undissolved lignin. This can be done by inspecting the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in the brown binder. During the dissolution step, the color of the lignin solution changes from brown to shiny black.

[1004] After the lignin was completely dissolved, 1 liter of defoamer (obtained from of 11-10). The batch temperature was maintained at 40°C.

[1005] Then, the addition of 307.5 kg of 35% hydrogen peroxide was started. The hydrogen peroxide was added at a rate of 200-300 liters / hour. The first half of the hydrogen peroxide was added at a rate of 200 liters / hour, after which the addition rate was increased to 300 liters / hour.

[1006] During the addition of hydrogen peroxide, the temperature of the reaction mixture was controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[1007] After reacting at 65° C. for 15 minutes, the reaction mixture was cooled to a temperature below 50° C. A resin having a COOH value of 1.2 mmol / g solid was thus obtained.

[1008] Preparation of the final binder (uncured binder composition suitable for preparing the mineral fiber product of the present invention)

[1009] A binder was formulated from the above AOL resin by adding 270 kg of polyethylene glycol 200 (PEG 200) and 433 kg of a 31% solution of Primid XL-552 in water.

[1010] Analysis of the final adhesive showed the following data:

[1011] Solid content: 18.9%

[1012] pH: 9.7

[1013] Viscosity: 25.5 mPas·s

[1014] Density: 1.066 kg / l

[1015] Comparative Example 3

[1016] The adhesive is a phenolic resin PUF-resol modified with urea.

[1017] A phenolic resin was prepared by reacting 37% aqueous formaldehyde (606 kg) and phenol (189 kg) in the presence of 46% aqueous potassium hydroxide (25.5 kg) at a temperature of 84° C. with a heating rate of approximately 1° C. / minute to the reaction temperature. The reaction was continued at 84° C. until the acid resistance of the resin was 4 and most of the phenol was converted. Urea (241 kg) was then added and the mixture was cooled.

[1018] The acid resistance (AT) indicates how many times a given volume of cement can be diluted with acid without the mixture becoming cloudy (precipitation of the cement). Sulfuric acid is used to determine the stopping criterion in cement production, and an acid resistance below 4 indicates that the cement reaction is complete.

[1019] To measure AT, prepare a titrant by diluting 2.5 ml of concentrated sulfuric acid (>99%) with 1 L of ion-exchanged water. This titrant is then titrated against 5 ml of the adhesive to be investigated at room temperature while manually shaking the adhesive to keep it in motion; a magnetic stirrer and bar magnet can be used if desired. The titration is continued until a slight turbidity appears in the adhesive that does not disappear upon shaking.

[1020] The acid tolerance (AT) was calculated by dividing the amount of acid used for titration (mL) by the amount of sample (mL):

[1021] AT = (titration volume used (mL)) / (sample volume (mL))

[1022] Using the obtained urea-modified phenolic resin, a binder was prepared by adding 25% ammonia water (90 L) and ammonium sulfate (13.2 kg), and then adding water (1300 kg).

[1023] To the above mixture was added 18% dextrose (127.5 kg) based on the dry matter of the above binder and dextrose.

[1024] The binder solids content was then measured as described above, and the mixture was diluted with the required amounts of water and silane for mechanical testing.

[1025] A mineral fiber product in the form of a pipe element was prepared having a thickness of 40 mm (with an inner diameter of 219 mm), a pressure of 100 kg / m 3 The conventional method for producing mineral fiber products as described above was used.

[1026] The mineral fiber products produced were tested as described in Procedure II. The results are given in Table B below.

[1027] Comparative Example 4

[1028] The adhesive is a phenolic resin PUF-resol modified with urea.

[1029] A phenolic resin was prepared by reacting 37% aqueous formaldehyde (606 kg) and phenol (189 kg) in the presence of 46% aqueous potassium hydroxide (25.5 kg) at a temperature of 84° C. with a heating rate of approximately 1° C. / minute to the reaction temperature. The reaction was continued at 84° C. until the acid resistance of the resin was 4 and most of the phenol was converted. Urea (241 kg) was then added and the mixture was cooled.

[1030] The acid resistance (AT) indicates how many times a given volume of cement can be diluted with acid without the mixture becoming cloudy (precipitation of the cement). Sulfuric acid is used to determine the stopping criterion in cement production, and an acid resistance below 4 indicates that the cement reaction is complete.

[1031] To measure AT, prepare a titrant by diluting 2.5 ml of concentrated sulfuric acid (>99%) with 1 L of ion-exchanged water. This titrant is then titrated against 5 ml of the adhesive to be investigated at room temperature while manually shaking the adhesive to keep it in motion; a magnetic stirrer and bar magnet can be used if desired. The titration is continued until a slight turbidity appears in the adhesive that does not disappear upon shaking.

[1032] The acid tolerance (AT) was calculated by dividing the amount of acid used for titration (mL) by the amount of sample (mL):

[1033] AT = (titration volume used (mL)) / (sample volume (mL))

[1034] Using the obtained urea-modified phenolic resin, a binder was prepared by adding 25% ammonia water (90 L) and ammonium sulfate (13.2 kg), and then adding water (1300 kg).

[1035] To the above mixture was added 18% dextrose (127.5 kg) based on the dry matter of the above binder and dextrose.

[1036] The binder solids content was then measured as described above, and the mixture was diluted with the required amounts of water and silane for mechanical testing.

[1037] A mineral fiber product in the form of a wire mat was prepared having a thickness of 100 mm, a load of 100 kg / m 3 The conventional method for producing mineral fiber products as described above was used.

[1038] The mineral fiber products produced were tested as described in Procedure II. The results are given in Table B below.

[1039] Example 3

[1040] To a 6,000-liter reactor, add 3,267 kg of water, followed by 861 kg of 24.7% aqueous ammonia. Then, slowly add 1,531 kg of UPM BioPiva 100 lignin over 30 to 45 minutes. Heat the mixture to 40°C and maintain it at that temperature for 1 hour. After 1 hour, check for undissolved lignin. This can be done by inspecting the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in the brown binder. During the dissolution step, the color of the lignin solution changes from brown to shiny black.

[1041] After the lignin was completely dissolved, 1 liter of defoamer (obtained from of 11-10). The batch temperature was maintained at 40°C.

[1042] Then, the addition of 307.5 kg of 35% hydrogen peroxide was started. The hydrogen peroxide was added at a rate of 200-300 liters / hour. The first half of the hydrogen peroxide was added at a rate of 200 liters / hour, after which the addition rate was increased to 300 liters / hour.

[1043] During the addition of hydrogen peroxide, the temperature of the reaction mixture was controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[1044] After reacting at 65° C. for 15 minutes, the reaction mixture was cooled to a temperature below 50° C. A resin having a COOH value of 1.1 mmol / g solid was thus obtained.

[1045] Preparation of the final adhesive

[1046] A binder was formulated from the above AOL resin by adding 270 kg of polyethylene glycol 200 and 396 kg of a 31% solution of Primid XL-552 in water.

[1047] Analysis of the final adhesive showed the following data:

[1048] Solid content: 18.9%

[1049] pH: 10.2

[1050] Viscosity: 25.5 mPas·s

[1051] Density: 1.066kg / l.

[1052] A mineral fiber product in the form of a wire mat was prepared having a thickness of 80 mm, a load of 100 kg / m 3 The conventional method for producing mineral fiber products as described above was used.

[1053] The mineral fiber products produced were tested as described in Procedure II. The results are given in Table B below.

[1054] Heat release of Example 3 and Comparative Examples 3-4

[1055] The mineral fiber products of Example 3 and Comparative Examples 3 to 4 were tested for their isocyanic acid (ICA) and HCN release properties at temperatures of 250°C, 350°C, 450°C and 600°C, respectively, according to Procedure II above.

[1056] The results are shown below in Table B. The output values ​​given are the average of the release of each species in micrograms per gram of sample (μg / g sample).

[1057] Table B

[1058]

[1059]

[1060] The release levels of the three mineral wool products tested were obtained to enable us to rank the overall release levels of the systems relative to one another.

[1061] In general, the total release amount of Comparative Example 3 is significantly higher than that of Comparative Example 4, and in particular, higher than that of Example 3.

[1062] From the results it can be seen that Comparative Example 3 showed by far the highest levels of released substances (ICA and HCN), as can be seen from the relatively high LOI content of the products tested.

[1063] The total ICA and HCN release in Comparative Example 4 was still higher than that in Example 3, even though the LOI contents of the two were similar.

[1064] Maximum operating temperature test of Example 3

[1065] The performance of the product of Example 3 was tested according to the following test methods: Maximum Operating Temperature Panel Test; EN14706:2012, to demonstrate the thermal stability of the mineral wool product at high temperatures. The product was tested multiple times.

[1066] The maximum operating temperature of Example 3 was measured to be ST(+)=660°C±10°C, which is consistent with the selected test temperature ST(+)=660°C.

Claims

1. A mineral fiber product comprising mineral fibers bonded by a cured binder composition, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) per gram of solids content per second, The uncured adhesive composition comprises: - component (i) in the form of one or more oxidized lignins; and - component (ii) in the form of one or more cross-linking agents, and According to the maximum operating temperature board test of EN 14706:2012, the mineral fiber product meets the maximum operating temperature condition of at least 600°C.

2. The mineral fiber product of claim 1 , wherein heating the mineral fiber product to a temperature of 600°C releases less than 1000 ppm isocyanic acid (ICA) per gram of solids per second.

3. The mineral fiber product of claim 1 , wherein heating the mineral fiber product to a temperature of 600° C. releases less than 750 ppm isocyanic acid (ICA) per gram solids per second.

4. The mineral fiber product according to any one of claims 1 to 3, which is a thermal insulation product.

5. The mineral fiber product of any one of claims 1 to 3, wherein the mineral fiber product is in the form of a preformed pipe section, a mat or a slab.

6. The mineral fiber product of any one of claims 1 to 3, wherein the mineral fiber product has a thickness in the range of 20 mm to 500 mm.

7. The mineral fiber product of claim 6, wherein the mineral fiber product has a thickness in the range of 30 mm to 300 mm.

8. The mineral fiber product of claim 6, wherein the mineral fiber product has a thickness in the range of 50 mm to 150 mm.

9. The mineral fiber product of any one of claims 1 to 3, wherein heating the mineral fiber product to a temperature of 600°C releases less than 2500 ppm NH3 / gram solids content / second, and / or wherein heating the mineral fiber product to a temperature of 600°C releases less than 2000 ppm HCN / gram solids content / second.

10. The mineral fiber product of claim 9, wherein heating the mineral fiber product to a temperature of 600°C releases less than 2000 ppm NH3 / gram solids content / second, and / or wherein heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm HCN / gram solids content / second.

11. The mineral fiber product of claim 9, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm NH3 / gram solids content / second, and / or wherein heating the mineral fiber product to a temperature of 600°C releases less than 1000 ppm HCN / gram solids content / second.

12. The mineral fiber product of any one of claims 1 to 3, wherein the uncured binder composition further comprises: - component (iii) in the form of one or more plasticizers.

13. The mineral fiber product of any one of claims 1 to 3, wherein the one or more oxidized lignins are oxidation products of lignin selected from the group consisting of kraft lignin, alkali lignin, lignosulfonate lignin, organosolv lignin, lignin from a biorefining process of a lignocellulosic raw material, or any mixture thereof.

14. The mineral fiber product of any one of claims 1 to 3, wherein the one or more oxidized lignins are in the form of one or more ammonia-oxidized lignins.

15. The mineral fiber product of any one of claims 1 to 3, wherein the one or more oxidized lignins have a carboxylic acid group content of 0.05 to 10 mmol / g, based on the dry weight of the one or more oxidized lignins.

16. The mineral fiber product of claim 15, wherein the one or more oxidized lignins have a carboxylic acid group content of 0.1 to 5 mmol / g, based on the dry weight of the one or more oxidized lignins.

17. The mineral fiber product of claim 15, wherein the one or more oxidized lignins have a carboxylic acid group content of 0.20 to 1.5 mmol / g, based on the dry weight of the one or more oxidized lignins.

18. The mineral fiber product of claim 15, wherein the one or more oxidized lignins have a carboxylic acid group content of 0.40 to 1.2 mmol / g, based on the dry weight of the one or more oxidized lignins.

19. The mineral fiber product according to any one of claims 1 to 3, wherein the component (ii) is in the form of one or more cross-linking agents selected from: a) a β-hydroxyalkylamide crosslinking agent and / or an oxazoline crosslinking agent, and / or b) polyfunctional organic amines, and / or c) epoxidized oils based on fatty acid triglycerides or one or more flexible oligomers or polymers containing reactive functional groups selected from carbodiimide groups, anhydride groups, oxazoline groups, amino groups and epoxy groups, and / or d) molecules having three or more epoxy groups, and / or e) one or more cross-linking agents selected from the group consisting of polyethyleneimine, polyvinylamine, fatty amine; and / or f) one or more cross-linking agents in the form of fatty amides; and / or g) one or more cross-linking agents selected from the group consisting of dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid; and / or h) one or more cross-linking agents selected from polyester polyols; and / or i) one or more cross-linking agents selected from the group consisting of starch, CMC; and / or j) one or more cross-linking agents in the form of aliphatic polyfunctional carbodiimides; and / or k) one or more cross-linking agents selected from melamine-based cross-linking agents.

20. The mineral fiber product of any one of claims 1 to 3, wherein the component (ii) is in the form of one or more cross-linking agents selected from: - Alkanolamines, diamines, triamines, and / or - Low T g Acrylic acid based polymer, low T g Vinyl polymer, low T g Polyethers containing reactive functional groups selected from carbodiimide groups, anhydride groups, oxazoline groups, amino groups and epoxy groups, and / or - polycaprolactone; and / or - modified starch; and / or - Hexa(methylmethoxy)melamine-based crosslinker.

21. The mineral fiber product of claim 12, wherein component (iii) is contained in the uncured binder composition in the form of one or more plasticizers selected from the group consisting of polyethylene glycol, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates, adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides.

22. The mineral fiber product of claim 12, wherein component (iii) is contained in the uncured binder composition in the form of: - one or more plasticizers selected from the group consisting of acrylic acid-based polymers having free carboxyl groups, and / or polyurethane dispersions having free carboxyl groups, and / or One or more plasticizers selected from the group consisting of fatty alcohols; and / or One or more plasticizers selected from the group consisting of alkoxides; and / or one or more plasticizers in the form of propylene glycol; and / or one or more plasticizers in the form of glycol esters; and / or One or more plasticizers selected from the group consisting of adipates, acetates, benzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates; and / or One or more plasticizers selected from the group consisting of alkyl or aryl substituted phenols; and / or One or more plasticizers selected from the group consisting of silanols, siloxanes; and / or One or more plasticizers selected from the group consisting of sulfates, sulfonates; and / or - phosphate esters; and / or one or more plasticizers in the form of hydroxy acids; and / or One or more plasticizers selected from the group consisting of monomeric amides; and / or One or more plasticizers selected from the group consisting of quaternary ammonium compounds; and / or One or more plasticizers selected from the group consisting of vegetable oils; and / or Tall oil, and / or One or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils; and / or One or more plasticizers selected from acid methyl esters; and / or One or more plasticizers selected from the group consisting of alkyl polyglucosides, glucamides, sucrose esters, sorbitan esters; and / or One or more plasticizers selected from the group consisting of polyethylene glycol and polyethylene glycol ethers.

23. The mineral fiber product of claim 12, wherein component (iii) is contained in the uncured binder composition in the form of: One or more plasticizers selected from the group consisting of monohydric alcohols; and / or One or more plasticizers selected from the group consisting of ethoxylates; and / or One or more plasticizers selected from the group consisting of alkyl sulfates, alkyl or aryl sulfonates; and / or - tripolyphosphate; and / or One or more plasticizers selected from the group consisting of acetamide, benzamide, fatty acid amide; and / or One or more plasticizers selected from the group consisting of trimethylglycine, distearyldimethylammonium chloride; and / or One or more plasticizers selected from the group consisting of castor oil, palm oil, linseed oil, soybean oil; and / or One or more plasticizers selected from the group consisting of aminoglucosamide.

24. The mineral fiber product of any one of claims 1 to 3, wherein the mineral fiber product meets the maximum service temperature condition of at least 650°C according to the maximum service temperature panel test of EN 14706:2012.

25. The mineral fiber product of any one of claims 1 to 3, wherein the mineral fiber product has a loss on ignition of 0.25 to 6.0%.

26. Use of a mineral fiber product comprising mineral fibers bonded by a cured binder composition at a temperature of at least 300°C, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanic acid (ICA) / g solids content / second, wherein the uncured binder composition comprises: - component (i) in the form of one or more oxidized lignins; and - component (ii) in the form of one or more cross-linking agents, and According to the maximum operating temperature board test of EN 14706:2012, the mineral fiber product meets the maximum operating temperature condition of at least 600°C.

27. The use according to claim 26, wherein the mineral fiber product is used as a thermal insulation product.

28. The use according to claim 26, wherein the mineral fiber product is used as thermal pipe insulation material.

29. The use of claim 26 or claim 27, wherein the use is at a temperature of at least 400°C and at most 700°C.

30. The use of claim 28, wherein the pipe operates at a high service temperature of at least 400°C and up to 700°C.

31. The use of claim 28 or claim 30, wherein the pipe is a metal pipe.

32. The use according to claim 28, wherein a medium is transported in the pipeline.

33. The use of claim 26, wherein the mineral fiber product is as defined in any one of claims 2 to 25.

34. A method for conveying a medium, the method comprising the steps of: a) covering the pipes with mineral fiber products as thermal pipe insulation, and b) transporting the medium through the pipeline, wherein the mineral fiber product comprises mineral fibers bonded by a cured binder composition, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) per gram solids content per second, The uncured adhesive composition comprises: - component (i) in the form of one or more oxidized lignins; and - component (ii) in the form of one or more cross-linking agents, and According to the maximum operating temperature board test of EN 14706:2012, the mineral fiber product meets the maximum operating temperature condition of at least 600°C.

35. The method of claim 34, wherein the conveyed medium has a temperature of at least 300°C and at most 700°C.

36. The method of claim 34, wherein the conveyed medium has a temperature of at least 400°C and at most 700°C.

37. The method of claim 34, wherein the conveyed medium has a temperature of at least 450°C and at most 700°C.

38. A method as claimed in any one of claims 34 to 37, wherein the mineral fibre product is as defined in any one of claims 2 to 25.

39. A pipe covered with a mineral fiber product as thermal insulation material, wherein the mineral fiber product comprises mineral fibers bonded by a cured binder composition, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) per gram of solids content per second, The uncured adhesive composition comprises: - component (i) in the form of one or more oxidized lignins; and - component (ii) in the form of one or more cross-linking agents, and According to the maximum operating temperature board test of EN 14706:2012, the mineral fiber product meets the maximum operating temperature condition of at least 600°C.

40. The pipe of claim 39, wherein the mineral fibre product is as defined in any one of claims 2 to 25.

41. A mineral fiber product comprising mineral fibers bonded by a cured binder composition, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1000 μg isocyanic acid (ICA) per gram of sample, The uncured adhesive composition comprises: - component (i) in the form of one or more oxidized lignins; and - component (ii) in the form of one or more cross-linking agents, and According to the maximum operating temperature board test of EN 14706:2012, the mineral fiber product meets the maximum operating temperature condition of at least 600°C.

42. The mineral fiber product of claim 41 , wherein heating the mineral fiber product to a temperature of 600°C releases less than 750 μg isocyanic acid (ICA) per gram of sample.

43. The mineral fiber product of claim 41 , wherein heating the mineral fiber product to a temperature of 600°C releases less than 500 μg isocyanic acid (ICA) per gram of sample.

44. The mineral fiber product of claim 41 , wherein heating the mineral fiber product to a temperature of 600°C releases less than 250 μg isocyanic acid (ICA) per gram of sample.

45. The mineral fiber product of claim 41 , wherein heating the mineral fiber product to a temperature of 600°C releases less than 100 μg isocyanic acid (ICA) per gram of sample.

46. ​​The mineral fibre product of any one of claims 41 to 45 which is a thermal insulation product.

47. The mineral fiber product as claimed in any one of claims 41 to 45, wherein the mineral fiber product is in the form of preformed pipe sections, mats or planks.

48. The mineral fiber product as claimed in any one of claims 41 to 45, wherein the mineral fiber product has a thickness in the range 20 mm to 500 mm.

49. The mineral fiber product as claimed in any one of claims 41 to 45, wherein the mineral fiber product has a thickness in the range 30 mm to 300 mm.

50. The mineral fiber product as claimed in any one of claims 41 to 45, wherein the mineral fiber product has a thickness in the range of 50 mm to 150 mm.

51. The mineral fiber product as claimed in any one of claims 41 to 45, wherein heating the mineral fiber product to a temperature of 600°C releases less than 500 μg HCN per gram of sample.

52. The mineral fiber product as claimed in any one of claims 41 to 45, wherein heating the mineral fiber product to a temperature of 600°C releases less than 250 μg HCN per gram of sample.

53. The mineral fiber product as claimed in any one of claims 41 to 45, wherein heating the mineral fiber product to a temperature of 600°C releases less than 100 μg HCN per gram of sample.

54. The mineral fiber product as claimed in any one of claims 41 to 45, wherein heating the mineral fiber product to a temperature of 600°C releases less than 50 μg HCN per gram of sample.

55. The mineral fiber product as claimed in any one of claims 41 to 45, wherein the uncured binder composition further comprises: - component (iii) in the form of one or more plasticizers.

56. The mineral fiber product of any one of claims 41-45, wherein the one or more oxidized lignins are oxidation products of lignin selected from the group consisting of kraft lignin, alkali lignin, lignosulfonate lignin, organosolv lignin, lignin from a biorefining process of a lignocellulosic feedstock, or any mixture thereof.

57. The mineral fiber product of any one of claims 41 to 45, wherein the one or more oxidized lignins are in the form of one or more ammonia-oxidized lignins.

58. The mineral fiber product of any one of claims 41 to 45, wherein the one or more oxidized lignins have a carboxylic acid group content of from 0.05 to 10 mmol / g, based on the dry weight of the one or more oxidized lignins.

59. The mineral fiber product of any one of claims 41 to 45, wherein the one or more oxidized lignins have a carboxylic acid group content of 0.1 to 5 mmol / g, based on the dry weight of the one or more oxidized lignins.

60. The mineral fiber product of any one of claims 41 to 45, wherein the one or more oxidized lignins have a carboxylic acid group content of from 0.20 to 1.5 mmol / g, based on the dry weight of the one or more oxidized lignins.

61. The mineral fiber product of any one of claims 41 to 45, wherein the one or more oxidized lignins have a carboxylic acid group content of from 0.40 to 1.2 mmol / g, based on the dry weight of the one or more oxidized lignins.

62. The mineral fiber product of any one of claims 41 to 45, wherein the one or more oxidized lignins have a carboxylic acid group content of from 0.45 to 1.0 mmol / g, based on the dry weight of the one or more oxidized lignins.

63. The mineral fiber product of any one of claims 41 to 45, wherein component (ii) is in the form of one or more cross-linking agents selected from: a) a β-hydroxyalkylamide crosslinking agent and / or an oxazoline crosslinking agent, and / or b) polyfunctional organic amines, and / or c) epoxidized oils based on fatty acid triglycerides or one or more flexible oligomers or polymers containing reactive functional groups selected from carbodiimide groups, anhydride groups, oxazoline groups, amino groups and epoxy groups, and / or d) molecules having three or more epoxy groups, and / or e) one or more cross-linking agents selected from the group consisting of polyethyleneimine, polyvinylamine, fatty amine; and / or f) one or more cross-linking agents in the form of fatty amides; and / or g) one or more cross-linking agents selected from the group consisting of dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid; and / or h) one or more cross-linking agents selected from polyester polyols; and / or i) one or more cross-linking agents selected from the group consisting of starch, CMC; and / or j) one or more cross-linking agents in the form of aliphatic polyfunctional carbodiimides; and / or k) one or more cross-linking agents selected from melamine-based cross-linking agents.

64. The mineral fiber product of any one of claims 41 to 45, wherein component (ii) is in the form of one or more cross-linking agents selected from: - Alkanolamines, diamines, triamines, and / or - Low T g Acrylic acid based polymer, low T g Vinyl polymer, low T g Polyethers containing reactive functional groups selected from carbodiimide groups, anhydride groups, oxazoline groups, amino groups and epoxy groups, and / or - crosslinking agents for polycaprolactone, and / or - modified starch, and / or - Hexa(methylmethoxy)melamine-based crosslinker.

65. The mineral fiber product of claim 55, wherein component (iii) is contained in the uncured binder composition in the form of one or more plasticizers selected from the group consisting of polyethylene glycol, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates, adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, and lactides.

66. The mineral fiber product of claim 55, wherein component (iii) is contained in the uncured binder composition in the form of: - one or more plasticizers selected from the group consisting of acrylic acid-based polymers having free carboxyl groups, and / or polyurethane dispersions having free carboxyl groups, and / or One or more plasticizers selected from the group consisting of fatty alcohols; and / or One or more plasticizers selected from the group consisting of alkoxides; and / or one or more plasticizers in the form of propylene glycol; and / or one or more plasticizers in the form of glycol esters; and / or One or more plasticizers selected from the group consisting of adipates, acetates, benzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates; and / or One or more plasticizers selected from the group consisting of alkyl or aryl substituted phenols; and / or One or more plasticizers selected from the group consisting of silanols, siloxanes; and / or One or more plasticizers selected from the group consisting of sulfates, sulfonates; and / or - phosphate esters; and / or one or more plasticizers in the form of hydroxy acids; and / or One or more plasticizers selected from the group consisting of monomeric amides; and / or One or more plasticizers selected from the group consisting of quaternary ammonium compounds; and / or One or more plasticizers selected from the group consisting of vegetable oils; and / or Tall oil, and / or One or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils; and / or One or more plasticizers selected from acid methyl esters; and / or One or more plasticizers selected from the group consisting of alkyl polyglucosides, glucamides, sucrose esters, sorbitan esters; and / or One or more plasticizers selected from the group consisting of polyethylene glycol and polyethylene glycol ethers.

67. The mineral fiber product of claim 55, wherein component (iii) is contained in the uncured binder composition in the form of: One or more plasticizers selected from the group consisting of monohydric alcohols; and / or One or more plasticizers selected from the group consisting of ethoxylates; and / or One or more plasticizers selected from the group consisting of alkyl sulfates, alkyl or aryl sulfonates; and / or - tripolyphosphate; and / or One or more plasticizers selected from the group consisting of acetamide, benzamide, fatty acid amide; and / or One or more plasticizers selected from the group consisting of trimethylglycine, distearyldimethylammonium chloride; and / or One or more plasticizers selected from the group consisting of castor oil, palm oil, linseed oil, soybean oil; and / or One or more plasticizers selected from the group consisting of aminoglucosamide.

68. The mineral fiber product of any one of claims 41 to 45, wherein the mineral fiber product meets the maximum service temperature condition of at least 650°C according to the maximum service temperature panel test of EN 14706:2012.

69. The mineral fiber product of any one of claims 41 to 45, wherein the mineral fiber product has a loss on ignition of 0.25 to 6.0%.

70. Use of the mineral fiber product of any one of claims 41 to 69 at a temperature of at least 300°C.

71. The use according to claim 70, wherein the mineral fiber product is used as a thermal insulation product.

72. The use according to claim 70, wherein the mineral fiber product is used as thermal pipe insulation.

73. The use of claim 70 or claim 71 , wherein the use is at a temperature of at least 400°C and at most 700°C.

74. The use of claim 72, wherein the pipe operates at a high service temperature of at least 400°C and up to 700°C.

75. The use of claim 72 or claim 74, wherein the pipe is a metal pipe.

76. The use according to claim 72, wherein a medium is transported in the conduit.

77. A method for conveying a medium, the method comprising the steps of: a) coating a pipe with the mineral fiber product of any one of claims 41 to 69 as thermal pipe insulation, and b) conveying the medium through the pipeline.

78. The method of claim 77, wherein the conveyed medium has a temperature of at least 300°C and at most 700°C.

79. A pipe covered with the mineral fibre product of any one of claims 41 to 69 as thermal insulation material.

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