High-temperature low-release mineral wool product

Abstract

The invention relates to a high-temperature low-release mineral fiber product suitable for use as a thermal insulation material.

Description

[0001] This application is a divisional application of Chinese patent application (PCT / EP2020 / 059660) filed on April 1, 2021, with application number 202180039336.7 and invention title "High Temperature Low Release Mineral Wool Product". Invention Field

[0002] This invention relates to mineral fiber products and the 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 glass fiber (MMVF)) such as glass fiber, ceramic fiber, basalt fiber, slag fiber, and stone fiber (rock fiber), which are 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, such as by a spinning cup process or a cascade rotor process. The fibers are blown into a forming chamber and, while still hot, are pneumatically sprayed with a binder solution and randomly deposited on a moving conveyor belt in the form of mats or webs. The fiber mats are then transferred to a curing furnace, where heated air is blown over the mats to cure the binder and firmly bond the mineral fibers together.

[0004] In the past, phenolic resins were the preferred binder resins, which could be economically produced and could be supplemented with urea before being used as binders. However, existing and proposed legislation aimed at reducing or eliminating formaldehyde release has led to the development of formaldehyde-free binders such as binder compositions based on polycarboxylated polymers and polyols or polyamines (e.g., 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 products of addition / elimination reactions of aliphatic and / or aromatic anhydrides with alkanolamines, 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 curing speed and cured density. WO 2008 / 023032 discloses urea-modified binders that provide mineral wool products with reduced hygroscopicity.

[0006] Because some of the starting materials used to produce these adhesives are rather expensive chemicals, there has been a need for formaldehyde-free adhesives that can be produced economically.

[0007] Another effect associated with previously known aqueous binder compositions for mineral fibers is that at least a majority of the starting materials used to produce these binders are derived from fossil fuels. A long-standing trend is the consumer preference for products made entirely or at least partially from renewable materials, thus creating a need for binders for mineral wool that are at least partially made from renewable materials.

[0008] In high-temperature applications, mineral fiber products may release organic components derived from the binder when used at such high temperatures, particularly when used for the first time at such temperatures and / or when used at such temperatures for short intervals. High-temperature applications include, for example, when mineral fiber products are used as insulation materials 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 materials for furnaces, where these products may be used at their maximum operating temperatures, such as 600°C, 650°C, or even 700°C.

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

[0010] The chemical formula for isocyanate is HNCO. A significant portion of ICA release from mineral fiber products is likely due to the use of urea or urea derivatives in adhesive compositions. ICA release can lead to health problems, and legislation aimed at reducing or eliminating ICA releases from mineral fiber products during installation and use, as well as during their manufacturing, already exists or has been proposed.

[0011] Other interesting chemical components from the heat release may include hydrogen cyanide (HCN), ammonia (NH3), and NOx, but may also include other nitrite-containing substances.

[0012] The present invention will now be described using two alternative solutions, namely, alternative solution A and alternative solution B.

[0013] Alternative Solution A (First to Fourth Aspects of the Invention) Invention Overview

[0014] Therefore, one object of the present invention is to provide a mineral fiber product that has improved high-temperature use, can be produced economically, and uses renewable materials as starting materials for the preparation of aqueous binder compositions.

[0015] Another object of the present invention is to provide uses for such mineral fiber products.

[0016] Another object of the present invention is to provide a method for transporting media through pipelines at high temperatures.

[0017] According to a first aspect of the invention, a mineral fiber product comprising mineral fibers bonded by a cured binder composition is provided, wherein the uncured binder composition comprises one or more oxylignins, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) / gram content / second.

[0018] According to a second aspect of the invention, the use of a mineral fiber product comprising mineral fibers bonded by a cured binder composition at a temperature of at least 300°C is provided, preferably as a heat insulation product, wherein the uncured binder composition comprises one or more oxylignins, wherein optionally, heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanic acid (ICA) / gram content / second.

[0019] According to a third aspect of the present invention, a method for conveying a medium is provided, the method comprising the following steps:

[0020] a) Covering pipes with mineral fiber products used as thermal insulation materials, and

[0021] b) The medium is transported through the pipeline.

[0022] The mineral fiber product used as thermal insulation material for heat pipes comprises mineral fibers bonded by a cured binder composition, wherein the uncured binder composition comprises one or more oxylignins, wherein optionally, heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) / gram content / second.

[0023] According to a fourth aspect of the invention, a pipe covered with a mineral fiber product as an insulation material is provided, wherein the mineral fiber product comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxylignins, wherein optionally, heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) / gram content / second.

[0024] The inventors have surprisingly discovered that when lignin-based binder compositions are used in mineral fiber products, mineral fiber products with low or even no ICA release can be used in high-temperature applications.

[0025] Description of preferred implementation scheme

[0026] The mineral fiber product of the present invention comprises mineral fibers bonded by a cured binder composition, wherein the uncured binder composition comprises one or more oxylignins, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) / gram content / second, preferably less than 1000 ppm isocyanate (ICA) / gram content / second, more preferably less than 750 ppm isocyanate (ICA) / gram content / second.

[0027] The heated mineral fiber product contains a cured binder composition. Regarding "Loss on Ignition (LOI)," the LOI refers to the amount of organic material (loss on ignition) in the mineral fiber product. This LOI typically refers to the cured binder composition and optional hydrophobic agents and / or impregnation oils contained in the mineral fiber product.

[0028] When a mineral fiber product containing a cured binder composition is heated at a certain temperature and the content of isocyanate (ICA) in the exhaust gas is quantitatively analyzed by Fourier transform infrared spectroscopy (FTIR), the result is a measurement of the amount of ICA released. This measurement is considered as the ICA release amount related to the amount of cured binder composition in the tested mineral fiber product.

[0029] For standardization, the release rates of 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. Note that the data obtained cannot be directly compared quantitatively to the release rates of these products determined under specific field conditions when these products are implemented by end customers in industrial insulation systems. For example, in actual end-customer installations, the products will not be crushed as in Procedure I described below, and the binder in mineral fiber products will not be completely burned off. In practice, the values ​​obtained using this Procedure I correspond to the worst-case scenario, both in terms of quantity and release time. Therefore, lower and slower release rates (reaching steady state in 2-48 hours) are expected for the products, whereas this Procedure I reached steady state in less than 2 hours after actual installation, compared to the values ​​obtained in this study. However, it can be readily assumed that mineral fiber products exhibiting lower release rates compared to other products according to Procedure I will also have lower release rates in actual end-customer installations.

[0030] Release measurements of different mineral wool products are typically performed by external research institutes such as RISE in Sweden using a combination of tests on different materials of varying thicknesses. The dependence of insulation thickness on the release curve is determined by quantification of the FID signal and infrared measurements of released gases such as CO, NH3, HCN, NOx, and ICA.

[0031] With regard to Option A of this application, the amount of released ICA was measured according to Procedure I described below. Internal measurements have been performed on different milled mineral wool products according to Procedure I to eliminate discussions regarding thickness and porosity. These experiments were conducted in a custom-designed release chamber (tube furnace) that heated the material to a specific temperature setpoint and maintained it for a specific time. During these experiments, air passed through the chamber at a specified rate and was sampled for quantification of different compounds. Four different temperatures (250°C, 350°C, 450°C, and 600°C) were tested, and the released gases were quantified using Fourier transform infrared spectroscopy. Details of Procedure I are given below in the experimental section.

[0032] Preferably, when the mineral fiber product containing the cured binder composition is heated, the mineral fiber product of the present invention also exhibits low release of other waste gases such as NH3, HCN and / or NOx.

[0033] In a preferred embodiment, heating the mineral fiber product of the present invention to 600°C releases less than 2500 ppm NH3 / gram content / second, for example less than 2000 ppm NH3 / gram content / second, for example less than 1500 ppm NH3 / gram content / second, and / or heating the mineral fiber product to 600°C releases less than 2000 ppm HCN / gram content / second, for example less than 1500 ppm HCN / gram content / second, for example less than 1000 ppm HCN / gram content / second.

[0034] For the purposes of this application, the amounts of NH3, HCN, and / or NOx released can be measured according to the same procedure I described below. Of course, gas analysis by FTIR will then be performed on the compound to be identified.

[0035] The mineral fiber products of this invention are suitable for high-temperature applications and also relate to thermal stability. In particular, the mineral fiber products of this 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 operating temperature plate test of EN14706:2012, the mineral fiber products of this invention generally meet the condition of a maximum operating temperature (MST) of at least 600°C, preferably at least 650°C. MST is not related to thermal degradation or exhaust gases, but rather to mechanical strength.

[0036] Typically, the uncured adhesive composition is an aqueous adhesive composition. In a preferred embodiment, the adhesive of the present invention is formaldehyde-free.

[0037] For the purposes of this application, the term "formaldehyde-free" is defined as indicating that the formaldehyde released from the mineral wool product is less than 5 μg / m³. 2 / h, preferably below 3μg / m2 / h of mineral wool product. Preferably, the test is performed according to ISO 16000 for testing aldehyde release.

[0038] The uncured binder composition used to prepare the mineral fiber products of the present invention contains one or more oxylignins as a component (i).

[0039] Component (i)

[0040] Component (i) is in the form of one or more oxylignins.

[0041] Lignin, cellulose, and hemicellulose are the three main organic compounds in plant cell walls. Lignin can be considered a glue, holding 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.

[0042] Figure 1 A portion of the possible lignin structure is shown.

[0043] At least four groups of industrial lignins are available on the market. These four groups of industrial lignins are shown... Figure 3 The fifth possible group, biorefined lignin, is somewhat different because it is not described by extraction methods but by process sources such as biorefining; therefore, it can be similar to or different from any of the other groups mentioned. Each group differs from one another, and each group 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 [link to relevant documentation]). Figure 2 ), and therefore they are more uniform in lignin than hardwood lignin, which has a higher eugenol content (see Figure 2 The appearance and consistency of lignin vary greatly and depend to a large extent on the processing method.

[0044] The performance of these industrial lignins is summarized as follows: Figure 4 middle.

[0045] Lignin sulfonates derived from sulfite pulping remain the largest commercially available source of lignin, with a capacity of 1.4 million tons. However, sulfite pulping is currently the most widely used pulping process and is gradually replacing sulfite pulping. It is estimated that 78 million tons of lignin are produced globally annually through sulfate pulping methods, but most of this is burned for steam and energy. Current kraft paper recycling capacity is estimated at 160,000 tons, but sources indicate that current recycling volume is only around 75,000 tons. Sulfate lignin is developed from black liquor, the waste liquid from sulfate or kraft paper processes. Currently, three well-known methods are used to produce sulfate lignin: LignoBoost, LignoForce, and SLRP. These three methods are similar in that they involve adding CO2 to lower the pH to 9-10, followed by acidification to further lower the pH to around 2. The final step includes some combination of washing, leaching, and filtration to remove ash and other contaminants. These three methods are at different stages of commercialization globally.

[0046] The sulfate process introduces thiol groups and 1,2-stilbene while retaining some carbohydrates. Sodium sulfate is also present as an impurity due to the precipitation of lignin from the liquid with sulfuric acid, but this can potentially be avoided by altering the method of lignin separation. The sulfate process results in a large number of phenolic hydroxyl groups, and this lignin is water-soluble when these groups are ionized (at pH values ​​above approximately 10).

[0047] Commercial lignin sulfates are typically of higher purity than lignin sulfonates. Their molecular weight ranges from 1000 to 3000 g / mol.

[0048] Alkali lignin is derived from sodium hydroxide pulping methods primarily used for wheat straw, sugarcane bagasse, and flax. Regarding solubility and T... g In this respect, alkali lignin exhibits properties similar to those of sulfate lignin. This method does not use sulfur, nor does it involve covalently bonded sulfur. Ash levels are very low. Alkali lignin has low solubility in neutral and acidic media, but is completely soluble at pH 12 and higher.

[0049] The lignin sulfonate 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 sulfonate form, while sulfate lignin contains 1-2% sulfur, which is primarily bonded to lignin. The molecular weight of lignin sulfonates is 15,000-50,000 g / mol. Compared to other types of lignin, this lignin contains more residual carbohydrates and has a higher average molecular weight. The typical hydrophobic core of lignin, along with a large number of ionized sulfonate groups, makes this lignin attractive as a surfactant, and it is frequently used in applications such as dispersing cement.

[0050] Another group of lignin becoming available is that produced through biorefining methods, where carbohydrates are separated from lignin through chemical or biochemical processes to produce a carbohydrate-rich fraction. This remaining lignin is called biorefined lignin. Biorefining plants focus on producing energy and alternatives to products derived from fossil fuels and petrochemicals, as well as lignin. Lignin from this method is often considered a low-value product, or even waste primarily intended for thermal combustion, use as low-grade animal feed, or otherwise disposed of.

[0051] The availability of organic solvent lignin is still under consideration at the pilot-scale level. This method involves extracting lignin using water, as well as various organic solvents (most commonly ethanol) and some organic acids. One advantage of this method is the high purity of the obtained lignin, but it is significantly more expensive than other industrial lignins and is soluble in organic solvents but not in water.

[0052] Previous attempts to use lignin as a base compound in binder compositions for mineral fibers failed because it proved difficult to find a suitable crosslinking agent capable of achieving the desired mechanical properties of cured mineral wool products while avoiding harmful and / or corrosive components. Currently, lignin is used as a substitute for 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 respects, as a dispersant.

[0053] Crosslinking of polymers typically provides improved properties such as mechanical, chemical, and thermal resistance. Lignin possesses a particularly rich array of phenolic and aliphatic hydroxyl groups, which can react to lead to crosslinked structures. Different lignins will also possess other available functional groups that can potentially be utilized. The presence of these other groups depends largely on how lignin is separated from cellulose and hemicellulose (thiols in sulfate lignin, sulfonates in lignin sulfonates, etc.), and depends on the source.

[0054] It has been discovered that a binder composition for mineral fibers can be prepared by using lignin oxide, which allows mineral fiber products produced therefrom to have excellent properties without requiring other components to be included in the binder composition. This enables the mineral fiber products of the present invention to be used in high-temperature applications with low or even no ICA release.

[0055] In one embodiment, the component (i) is in the form of one or more oxidized sulfate lignins.

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

[0057] In one embodiment, component (i) is in the form of one or more ammonia-oxidized lignins. For the purposes of this invention, the term "ammonia-oxidized lignin" should be understood as lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.

[0058] In an alternative embodiment, the ammonia is partially or completely replaced by an alkali metal hydroxide, particularly sodium hydroxide and / or potassium hydroxide.

[0059] A typical oxidizing agent used to prepare the oxylignin is hydrogen peroxide.

[0060] In one embodiment, the ammonia-oxidized lignin comprises one or more compounds selected from ammonia, amines, hydroxides, or any salts thereof.

[0061] In one embodiment, the component (i) has a carboxylic acid group content of 0.05 to 10 mmol / g, for example 0.1 to 5 mmol / g, for example 0.20 to 1.5 mmol / g, for example 0.40 to 1.2 mmol / g, for example 0.45 to 1.0 mmol / g, based on the dry weight of component (i).

[0062] In the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, component (i) namely the one or more oxylignins may be present in an amount of 25-95% by weight, for example 30-90% by weight, for example 35-85% by weight, based on the dry weight of the adhesive composition.

[0063] In one embodiment, the component (i) has an average carboxylic acid group content of more than 1.5 groups / component (i), such as more than 2 groups / component (i) or more than 2.5 groups / component (i).

[0064] It is believed that the carboxylic acid group content of the oxidized lignin plays a significant role in the surprising advantages of the water-based binder composition for mineral fibers of the present invention. In particular, it is believed that the carboxylic acid groups of the oxidized lignin improve crosslinking properties and thus allow the cured mineral fiber product to have better mechanical properties.

[0065] 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:

[0066] - Components in the form of one or more oxidized lignins (i);

[0067] - Components in the form of one or more crosslinking agents (ii);

[0068] -Optionally, components in the form of one or more plasticizers (iii).

[0069] Component (ii)

[0070] Optional component (ii) is in the form of one or more crosslinking agents.

[0071] In one embodiment, component (ii) comprises one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

[0072] β-hydroxyalkylamide crosslinking agents are curing agents for acid-functionalized macromolecules. They provide hard, durable, corrosion-resistant, and solvent-resistant crosslinked polymer networks. β-hydroxyalkylamide crosslinking agents are believed to cure via esterification to form multiple ester bonds. The hydroxyl functionality of the β-hydroxyalkylamide crosslinking agent should have an average of at least 2, preferably greater than 2, and more preferably 2-4, to obtain optimal curing response.

[0073] Oxazoline-containing crosslinking agents are polymers containing one or more oxazoline groups in each molecule, and are generally readily obtained by polymerizing oxazoline derivatives. Patent US6818699 B2 discloses such a method.

[0074] In one embodiment, component (ii) is an oil based on the epoxidation of fatty acid triglycerides.

[0075] It has been noted that epoxidized oils based on fatty acid triglycerides are not considered dangerous, and therefore the use of these compounds in the binder compositions of the present invention does not make these compositions unsafe to operate.

[0076] In one embodiment, component (ii) is a molecule having three or more epoxy groups.

[0077] In one embodiment, the component (ii) is one or more flexible oligomers or polymers, such as low-Tg acrylic polymers, low-Tg vinyl polymers, or low-Tg polyethers, containing reactive functional groups, such as carbodiimide groups, anhydride groups, oxazoline groups, amino groups, or epoxy groups.

[0078] In one embodiment, component (ii) is selected from the group consisting of crosslinking agents involved in the curing reaction, such as hydroxyalkylamides, alkanolamines, and reaction products of alkanolamines and polycarboxylic acids. Reaction products of alkanolamines and polycarboxylic acids are available in US6706853B1.

[0079] Without wishing to be bound by any particular theory, it is believed that the highly advantageous properties of the adhesive compositions of the present invention, preferably aqueous adhesive compositions, are due to the interaction between lignin oxide used as component (i) and the aforementioned crosslinking agent. It is believed that the presence of carboxylic acid groups in the lignin oxide enables the lignin oxide to crosslink very effectively.

[0080] In one embodiment, 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.

[0081] In one embodiment, component (ii) is one or more crosslinking agents selected from the group consisting of polyethyleneimine, polyvinylamine, and aliphatic amines.

[0082] In one embodiment, component (ii) is one or more fatty amides.

[0083] In one embodiment, component (ii) is one or more crosslinking agents selected from the group consisting of dimethoxyacetaldehyde, glycolaldehyde, and glyoxylic acid.

[0084] In one embodiment, component (ii) is one or more crosslinking agents selected from polyester polyols such as polycaprolactone.

[0085] In one embodiment, component (ii) is one or more crosslinking agents selected from the group consisting of starch, modified starch, and CMC.

[0086] In one embodiment, component (ii) is one or more crosslinking agents in the form of aliphatic polyfunctional carbodiimides.

[0087] In one embodiment, component (ii) is one or more crosslinking agents selected from melamine-based crosslinking agents such as hexa(methylmethoxy)melamine (HMMM)-based crosslinking agents.

[0088] Examples of such compounds are Picassian XL 701, 702, 725 (Stahl Polymers), for example. XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).

[0089] In one embodiment, component (ii) is Primid XL552, which has the following structure:

[0090]

[0091] Component (ii) may also be any mixture of the compounds mentioned above.

[0092] In one embodiment, the adhesive composition of the present invention contains component (ii) in an amount of 1 to 40% by weight, for example 4 to 20% by weight, for example 6 to 12% by weight, based on the dry weight of component (i).

[0093] Component (iii)

[0094] Optional component (iii) is in the form of one or more plasticizers.

[0095] 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 having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides such as urea / urea, or any mixture thereof.

[0096] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of: carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds having a lignin-like structure such as vanillin, acetylsuccinone, and solvents used as coalescing agents such as alcohol ethers, polyvinyl alcohol.

[0097] In one embodiment, component (iii) is in the form of one or more non-reactive plasticizers selected from the group consisting of: polyethylene glycol, polyethylene glycol ether, polyether, hydrogenated sugar, phthalate and / or other esters, solvents used as coalescing agents such as alcohol ether, acrylic polymers, and polyvinyl alcohol.

[0098] 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 polymers having free carboxyl groups, and compounds having a lignin-like structure such as vanillin, acetylsuccinone.

[0099] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of: fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.

[0100] In one embodiment, component (iii) comprises one or more plasticizers selected from the group consisting of polyethylene glycol and polyethylene glycol ether.

[0101] Another particularly surprising aspect of the invention is that the use of plasticizers with boiling points exceeding 100°C, particularly 140 to 250°C, greatly improves the mechanical properties of the mineral fiber products of the invention, although, given their boiling points, these plasticizers are likely to evaporate at least partially during the curing process of the binder, preferably an aqueous binder, in contact with the mineral fibers.

[0102] In one embodiment, component (iii) comprises one or more plasticizers having a boiling point of more than 100°C, for example 110 to 280°C, more preferably 120 to 260°C, and even more preferably 140 to 250°C.

[0103] It is believed that the effectiveness of these plasticizers in the adhesive compositions, preferably aqueous adhesive compositions, used according to the invention is related to their effect of increasing the fluidity of lignin oxidized during the curing process. It is believed that the increased fluidity of lignin or lignin oxidized during curing promotes effective crosslinking.

[0104] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, particularly 150 to 4,000 g / mol, more specifically 150 to 1,000 g / mol, preferably 150 to 500 g / mol, and more preferably 200 to 400 g / mol.

[0105] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4,000 to 25,000 g / mol, particularly 4,000 to 15,000 g / mol, and more specifically 8,000 to 12,000 g / mol.

[0106] In one embodiment, component (iii) is capable of forming covalent bonds with components (i) and / or (ii) during the curing process. Such a component will not evaporate and will remain as part of the composition, but will be effectively altered so as not to introduce unwanted side effects such as the water absorption of the cured product. Non-limiting examples of such components are caprolactone and acrylic polymers having free carboxyl groups.

[0107] In one embodiment, component (iii) is selected from the group consisting of fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.

[0108] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxides, such as ethoxides, such as butanol ethoxides, such as butoxytriethylene glycol.

[0109] In one embodiment, component (iii) is selected from one or more propylene glycols.

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

[0111] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of adipate, acetate, benzoate, cyclobenzoate, citrate, stearate, sorbate, sebate, azelaate, butyrate, and valerate.

[0112] 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.

[0113] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of silanols and siloxanes.

[0114] 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 alkyl aryl sulfonates, alkyl sulfonates, phosphates such as tripolyphosphates, for example, tributyl phosphate.

[0115] In one embodiment, component (iii) is selected from one or more hydroxy acids.

[0116] 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 tallowamide.

[0117] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of quaternary ammonium compounds, such as trimethylglycine and distearate dimethylammonium chloride.

[0118] 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, and soybean oil.

[0119] In one embodiment, component (iii) is in the form of tall oil.

[0120] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of hydrogenated oils and acetylated oils.

[0121] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0122] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucoside, glucosamide, aminoglucosamide, sucrose ester, and sorbitol ester.

[0123] It has been surprisingly found that the inclusion of plasticizers in the binder compositions, preferably aqueous binder compositions, used according to the present invention greatly improves the mechanical properties of the mineral fiber products of the present invention.

[0124] The term "plasticizer" refers to a substance added to a material to make it softer, more flexible (by lowering its glass transition temperature Tg) and easier to process.

[0125] Component (iii) may also be any mixture of the compounds mentioned above.

[0126] In one embodiment, component (iii) is present in an amount of 0.5-50% by weight, preferably 2.5-25% by weight, more preferably 3-15% by weight, based on the dry weight of component (i).

[0127] A mineral fiber adhesive composition, preferably an aqueous adhesive composition, comprising components (i) and (iia).

[0128] In one embodiment, the present invention relates to a binder composition for mineral fibers, preferably an aqueous binder composition, comprising:

[0129] - Components in the form of one or more oxidized lignins (i);

[0130] - Components in the form of one or more modifiers (iia).

[0131] The inventors have discovered that the superior adhesive properties can also be achieved through a two-component system comprising a component (i) in the form of one or more lignin oxides and a component (iia) in the form of one or more modifiers, as well as any other components optionally mentioned above and below.

[0132] 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.

[0133] 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.

[0134] In one embodiment, component (iia) is a modifier in the form of one or more of the following substances: flexible oligomers or polymers, such as low-Tg acrylic polymers, low-Tg vinyl polymers, low-Tg polyethers, containing reactive functional groups such as carbodiimide groups, anhydride groups, oxazoline groups, amino groups, and epoxy groups.

[0135] In one embodiment, component (iia) is one or more modifiers selected from the group consisting of polyethyleneimine, polyvinylamine, and aliphatic amines.

[0136] In one embodiment, component (iia) is one or more modifiers selected from the group consisting of aliphatic multifunctional carbodiimides.

[0137] The component (iia) can also be any mixture of the compounds mentioned above.

[0138] Without wishing to be bound by any particular theory, the inventors believe that the superior adhesive properties achieved by the mineral fiber binder composition comprising components (i) and (iia) and optionally other components are at least in part attributable to the effect of the modifier used as component (iia) functioning at least in part as a plasticizer and crosslinking agent.

[0139] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, contains component (iia) in an amount of 1 to 40% by weight, for example 4 to 20% by weight, for example 6 to 12% by weight, based on the dry weight of component (i).

[0140] Other components

[0141] In some embodiments, the adhesive composition, preferably an aqueous adhesive composition, used according to the invention contains additional components.

[0142] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the invention comprises a catalyst selected from: inorganic acids, such as sulfuric acid, aminosulfonic acid, nitric acid, boric acid, hypophosphoric acid, and / or phosphoric acid, and / or any salt thereof, such as sodium hypophosphite, and / or ammonium salts such as ammonium salts of sulfuric acid, aminosulfonic acid, nitric acid, boric acid, hypophosphoric acid, and / or phosphoric acid, and / or sodium polyphosphate (STTP), and / or sodium metaphosphate (STMP), and / or phosphorus trichloride. The presence of such a catalyst can improve the curing properties of the adhesive composition, preferably an aqueous adhesive composition, used according to the invention.

[0143] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, comprises a catalyst selected from Lewis acids that can accept electron pairs from donor compounds forming Lewis adducts, such as ZnCl2, Mg(ClO4)2, Sn[N(SO2-n-C8F] 17 )2]4.

[0144] In one embodiment, the binder composition used according to the invention, preferably an aqueous binder composition, comprises a catalyst selected from metal chlorides, such as KCl, MgCl2, ZnCl2, FeCl3, and SnCl2.

[0145] In one embodiment, the binder composition used according to the invention, preferably an aqueous binder composition, comprises a catalyst selected from organometallic compounds, such as titanate-based catalysts and tin-based catalysts.

[0146] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, and copper ions.

[0147] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, further comprises an additional component (iv) in the form of one or more silanes.

[0148] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, comprises an additional component (iv) in the form of one or more coupling agents such as organically functional silanes.

[0149] In one embodiment, component (iv) is selected from the group consisting of: organically functionalized silanes, such as silanes functionalized with primary or secondary amino groups, epoxy-functionalized silanes such as polymer or oligomeric epoxy-functionalized silanes, methacrylate-functionalized silanes, alkyl and aryl-functionalized silanes, urea-functionalized silanes, or vinyl-functionalized silanes.

[0150] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, further comprises a component (v) in the form of one or more components selected from ammonia, amines, or any salts thereof.

[0151] It has been found that when oxylignin, which is not oxidized in the presence of ammonia, is used in component (i), it may be particularly useful to include ammonia, amines, or any of their salts as an additional component.

[0152] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, further comprises an additional component in the form of urea, particularly in an amount of 5 to 40% by weight, for example 10 to 30% by weight, or 15 to 25% by weight, based on the dry weight of component (i).

[0153] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, further comprises an additional component in the form of one or more carbohydrates selected from the group consisting of sucrose, reducing sugars, particularly dextrose, polysaccharides, and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, and 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, glucose syrup with DE = 95-99.

[0154] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, 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, for example 5 to less than 50% by weight, for example 10 to 40% by weight, for example 15 to 30% by weight, based on the dry weight of component (i).

[0155] In the context of this 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 a sugar-based binder. In the context of this 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 a non-sugar-based binder.

[0156] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, further comprises an additional component in the form of one or more surfactants, said surfactants being in the form of nonionic and / or ionic emulsifiers, such as polyoxyethylene (4) lauryl ether, soybean lecithin, sodium dodecyl sulfate.

[0157] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, comprises:

[0158] - Component (i) in the form of one or more amino-oxidized lignins, having a carboxylic acid group content of 0.05 to 10 mmol / g, for example 0.1 to 5 mmol / g, for example 0.20 to 1.5 mmol / g, for example 0.40 to 1.2 mmol / g, for example 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0159] - Component (ii) in the form of one or more crosslinking agents, selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents, and / or one or more crosslinking agents selected from the group consisting of: multifunctional organic amines, such as alkanolamines, diamines such as 1,6-hexanediamine, and triamines;

[0160] - Component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, particularly 150 to 4,000 g / mol, more specifically 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, particularly 4,000 to 15,000 g / mol, more specifically 8,000 to 12,000 g / mol; wherein preferably the adhesive composition, preferably the aqueous adhesive composition, comprises 1 to 40% by weight, for example 4 to 20% by weight, 6 to 12% by weight of component (ii) based on the dry weight of component (i), and the amount of component (iii) present is 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).

[0161] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, comprises:

[0162] - Component (i) in the form of one or more amino-oxidized lignins, having a carboxylic acid group content of 0.05 to 10 mmol / g, for example 0.1 to 5 mmol / g, for example 0.20 to 1.5 mmol / g, for example 0.40 to 1.2 mmol / g, for example 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0163] - Components (iia) in the form of one or more modifiers, selected from epoxidized oils based on fatty acid triglycerides.

[0164] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, comprises:

[0165] - Component (i) in the form of one or more amino-oxidized lignins, having a macromolecule with more than 1.5 groups / component (i), such as a macromolecule with more than 2 groups / component (i), such as a macromolecule with more than 2.5 groups / component (i) with an average carboxylic acid group content.

[0166] - Component (ii) in the form of one or more crosslinking agents, selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents, and / or one or more crosslinking agents selected from the group consisting of: multifunctional organic amines, such as alkanolamines, diamines such as 1,6-hexanediamine, and triamines;

[0167] - Component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, particularly 150 to 4,000 g / mol, more specifically 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, particularly 4,000 to 15,000 g / mol, more specifically 8,000 to 12,000 g / mol; wherein preferably the adhesive composition, preferably the aqueous adhesive composition, comprises 1 to 40% by weight, for example 4 to 20% by weight, 6 to 12% by weight of component (ii) based on the dry weight of component (i), and the amount of component (iii) present is 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).

[0168] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, comprises:

[0169] - Component (i) in the form of one or more amino-oxidized lignins, having a macromolecule with more than 1.5 groups / component (i), such as a macromolecule with more than 2 groups / component (i), such as a macromolecule with more than 2.5 groups / component (i) with an average carboxylic acid group content.

[0170] - Components (iia) in the form of one or more modifiers, selected from epoxidized oils based on fatty acid triglycerides.

[0171] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, consists essentially of the following components:

[0172] - Components in the form of one or more oxylignins (i);

[0173] - Components in the form of one or more crosslinking agents (ii);

[0174] - Components in the form of one or more plasticizers (iii);

[0175] - Components in the form of one or more coupling agents such as organofunctional silanes (iv);

[0176] - Optional components in the form of one or more compounds selected from ammonia, amines, or any salts thereof;

[0177] - Optional components in the form of urea;

[0178] - Optional components in the form of more reactive or non-reactive organosilicon;

[0179] -Optional hydrocarbon oil;

[0180] -One or more surfactants may be selected;

[0181] -water.

[0182] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, consists essentially of the following components:

[0183] - Components in the form of one or more oxylignins (i);

[0184] - Components (iia) in the form of one or more modifiers, selected from epoxidized oils based on fatty acid triglycerides;

[0185] - Components in the form of one or more coupling agents such as organically functional silanes (iv);

[0186] - Optional components in the form of one or more compounds selected from ammonia, amines, or any salts thereof;

[0187] - Optional components in the form of urea;

[0188] - Optional components in the form of more reactive or non-reactive organosilicon;

[0189] -Optional hydrocarbon oil;

[0190] -One or more surfactants may be selected;

[0191] -water.

[0192] Methods for producing mineral fiber products

[0193] The mineral fiber products of the present invention can be prepared by common methods of producing mineral fiber products by bonding mineral fibers with a binder composition. Therefore, the mineral fiber products of the present invention are preferably prepared by a method comprising the following steps: contacting the mineral fibers with an uncured and preferably aqueous binder composition containing one or more lignin oxides.

[0194] In a preferred embodiment, the uncured and preferably water-based adhesive composition comprises:

[0195] - Components in the form of one or more oxidized lignins (i);

[0196] - Components in the form of one or more crosslinking agents (ii);

[0197] - Optional components in the form of one or more plasticizers (iii).

[0198] Curing

[0199] The mineral fiber product precursor is cured by chemical and / or physical reactions of the binder components, such as the uncured binder composition in a web in which the mineral fibers come into contact with the binder composition.

[0200] In one embodiment, the curing is performed in a curing apparatus.

[0201] In one embodiment, the curing is carried out at a temperature of 100-300°C, for example 170-270°C, for example 180-250°C, for example 190-230°C.

[0202] In one embodiment, the curing is carried out in a conventional curing oven used for mineral wool production, the curing oven operating at temperatures of 150 to 300°C, for example 170 to 270°C, for example 180 to 250°C, for example 190 to 230°C.

[0203] In one embodiment, the curing process takes 30 seconds to 20 minutes, for example, 1 to 15 minutes, or for example, 2 to 10 minutes.

[0204] In a typical implementation, curing is carried out at a temperature of 150 to 250°C for 30 seconds to 20 minutes.

[0205] The curing process can begin immediately after the adhesive is applied to the fibers. Curing is defined as the process by which the adhesive composition undergoes a physical and / or chemical reaction (in the case of a chemical reaction, curing typically increases the molecular weight of the compounds in the adhesive composition) and thereby increases the viscosity of the adhesive composition, typically until the adhesive composition reaches a solid state.

[0206] In one embodiment, the curing process includes pressure drying. Pressure can be applied by blowing air or gas through / over the mixture of mineral fibers and binder.

[0207] The mineral fiber product of the present invention

[0208] This invention relates to mineral fiber products comprising mineral fibers in contact with the cured adhesive composition described above (i.e., in contact with a cured adhesive resulting from the curing of the adhesive composition described above, preferably an aqueous adhesive composition).

[0209] The mineral fibers used can be any of the following: man-made glass fiber (MMVF), glass fiber, ceramic fiber, basalt fiber, slag fiber, rock fiber, stone fiber, etc. These fibers can exist in the form of wool products such as asbestos products.

[0210] Fiber / melt composition

[0211] Man-made glass fiber (MMVF) can have any suitable oxide composition. The fiber can be glass fiber, ceramic fiber, basalt fiber, slag fiber, or rock or stone fiber. The fiber is preferably of the type commonly referred to as rock fiber, stone fiber, or slag fiber, and most preferably stone fiber.

[0212] Stone fibers typically contain the following oxides, expressed as a percentage by weight:

[0213] SiO2: 30-51

[0214] CaO: 8-30

[0215] MgO: 2-25

[0216] FeO (including Fe2O3): 2-15

[0217] Na₂O + K₂O: not exceeding 10

[0218] CaO + MgO: 10-30

[0219] In some preferred embodiments, the MMVF has the following elemental levels, calculated as oxides and expressed as a percentage by weight:

[0220] SiO2: at least 30, 32, 35, or 37; not exceeding 51, 48, 45, or 43.

[0221] Al2O3: at least 12, 16, or 17; not exceeding 30, 27, or 25

[0222] CaO: at least 8 or 10; not exceeding 30, 25 or 20

[0223] MgO: at least 2 or 5; not more than 25, 20 or 15

[0224] FeO (including Fe2O3): at least 4 or 5; not exceeding 15, 12 or 10

[0225] FeO+MgO: at least 10, 12, or 15; not exceeding 30, 25, or 20

[0226] Na₂O + K₂O: 0 or at least 1; not exceeding 10

[0227] CaO + MgO: at least 10 or 15; not exceeding 30 or 25

[0228] TiO2: 0 or at least 1; not exceeding 6, 4 or 2

[0229] TiO2+FeO: at least 4 or 6; not exceeding 18 or 12

[0230] B2O3: 0 or at least 1; not exceeding 5 or 3

[0231] P2O5: 0 or at least 1; not exceeding 8 or 5

[0232] Other: 0 or at least 1; not exceeding 8 or 5

[0233] The MMVF prepared by the method of the present invention preferably has the following composition (expressed in wt%):

[0234] SiO2: 35-50

[0235] Al2O3: 12-30

[0236] TiO2: Maximum 2

[0237] Fe2O3: 3-12

[0238] CaO: 5-30

[0239] MgO: up to 15

[0240] Na2O: 0-15

[0241] K2O: 0-15

[0242] P2O5: up to 3

[0243] MnO: Maximum 3

[0244] B2O3: Maximum 3

[0245] Another preferred composition of MMVF is as follows (expressed in wt%):

[0246] SiO2: 39-55%, preferably 39-52%

[0247] Al2O3: 16-27%, preferably 16-26%

[0248] CaO: 6-20%, preferably 8-18%

[0249] MgO: 1-5%, preferably 1-4.9%

[0250] Na2O: 0-15%, preferably 2-12%

[0251] K2O: 0-15%, preferably 2-12%

[0252] R2O (Na2O+K2O): 10-14.7%, preferably 10-13.5%

[0253] P2O5: 0-3%, preferably 0-2%

[0254] Fe2O3 (total iron): 3-15%, preferably 3.2-8%

[0255] B2O3: 0-2%, preferably 0-1%

[0256] TiO2: 0-2%, preferably 0.4-1%

[0257] Other: 0-2.0%

[0258] Glass fibers typically contain the following oxides (expressed in wt%):

[0259] SiO2: 50-70

[0260] Al2O3: 10-30

[0261] CaO: not exceeding 27

[0262] MgO: not exceeding 12

[0263] Glass fibers may also contain the following oxides (in wt%):

[0264] Na₂O + K₂O: 8-18, especially Na₂O + K₂O is greater than CaO + MgO.

[0265] B2O3: 3-12

[0266] Some glass fiber compositions may contain less than 2% Al2O3.

[0267] Suitable fiber-forming methods and subsequent production steps for manufacturing mineral fiber products are those conventional in the art. Typically, a binder is sprayed onto airborne mineral fibers immediately after the mineral melt fibrillation. The amount of the uncured and preferably aqueous binder composition applied is typically 0.1 to 18% by weight, preferably 0.2 to 8% by weight, of the bonded mineral fiber product, on a dry weight basis.

[0268] The sprayed mineral fiber mesh is typically cured in a curing oven using a flow of hot air. This hot air flow can be introduced into the mineral fiber mesh from below, above, or from alternating directions in different regions along the length of the curing oven.

[0269] Typically, curing ovens operate at temperatures ranging from about 150°C to about 300°C, for example, 170 to 270°C, 180 to 250°C, or 190 to 230°C. The typical curing oven dwell time is from 30 seconds to 20 minutes, for example, 1 to 15 minutes, or 2 to 10 minutes, depending on factors such as product density.

[0270] In a typical embodiment, the mineral fiber product of the present invention is cured at a temperature of 150°C to 250°C for 30 seconds to 20 minutes.

[0271] If necessary, the mineral fiber web can be shaped before curing. The bonded mineral fiber product exiting the curing oven can be cut into the desired form, such as in a fuzzy form.

[0272] In a preferred embodiment, the mineral fiber product of the present invention is an insulation product. The mineral fiber product is preferably in the form of pre-formed tube sections, wire-reinforced gaskets, or sheets.

[0273] In a preferred embodiment, the mineral fiber product of the present invention has a thickness of 20 mm to 500 mm, preferably 30 mm to 300 mm, for example, in the range of 50 mm to 150 mm, wherein the mineral fiber product is typically in sheet form.

[0274] The mineral fiber products of this invention typically have a strength of 6-250 kg / m³. 3 Preferred weight: 20-200 kg / m 3 The density is within the range specified. 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%.

[0275] Uses of the mineral fiber products of this invention

[0276] The present invention relates to the use of mineral fiber products in high-temperature applications. Here, high-temperature applications refer to the use of mineral fiber products at temperatures of at least 300°C, preferably at least 400°C, for example at least 450°C, and / or up to 700°C.

[0277] Therefore, the present invention also relates to the use of mineral fiber products at temperatures of at least 300°C, preferably at least 400°C, for example at least 450°C, said mineral fiber products comprising mineral fibers bonded by a cured binder composition, wherein the uncured binder composition comprises one or more oxylignins. Typically, the use of the present invention is at temperatures not exceeding 700°C, preferably not exceeding 650°C.

[0278] Typically, it is preferred that heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) / gram content / second, more preferably less than 1000 ppm isocyanate (ICA) / gram content / second, and still more preferably less than 750 ppm isocyanate (ICA) / gram content / second. The method for determining the ICA release rate is described below.

[0279] In a preferred embodiment of the invention, the mineral fiber product is used as an insulation product, more preferably as a thermal insulation material for heat pipes.

[0280] Regarding the application of the invention, the pipeline is preferably operated at a high operating 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 not exceeding 650°C.

[0281] The pipeline is preferably a metal pipeline. Specifically, the pipeline is used to transport media, such as gases, steam, or fluids. The media transported through the pipeline are typically high-temperature media having the aforementioned minimum operating temperature.

[0282] Mineral fiber products used for purposes of this invention may have all the features described above for mineral fiber products of this invention, and therefore refer to the description.

[0283] The method for conveying the medium of the present invention

[0284] The present invention also relates to a method for conveying a medium, the method comprising the following steps:

[0285] a) Covering pipes with mineral fiber products used as thermal insulation materials, and

[0286] b) The medium is transported through the pipeline.

[0287] The mineral fiber product comprises mineral fibers bonded by a cured binder composition, wherein the uncured binder composition comprises one or more oxylignins.

[0288] Typically, it is preferred that heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) / gram content / second, for example less than 1000 ppm isocyanate (ICA) / gram content / second, and more preferably less than 750 ppm isocyanate (ICA) / gram content / second. The method for determining the ICA release rate is described below.

[0289] In a preferred embodiment, the medium being transported 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, and more preferably does not exceed 650°C.

[0290] The medium transported through the pipeline can be, for example, gas, steam, or fluid.

[0291] The mineral fiber products used in the method of the present invention may have all the features described above for the mineral fiber products of the present invention, and therefore refer to the description thereon.

[0292] The pipe with heat insulation material of the present invention

[0293] The present invention also relates to pipes covered or wrapped with mineral fiber products as insulation materials, wherein the mineral fiber products comprise mineral fibers bonded by a cured adhesive composition, and the uncured adhesive composition comprises one or more oxylignins.

[0294] Typically, it is preferred that heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) / gram content / second, more preferably less than 1000 ppm isocyanate (ICA) / gram content / second, and even more preferably less than 750 ppm isocyanate (ICA) / gram content / second. The method for determining the ICA release rate is described below.

[0295] The mineral fiber product used to cover the pipes of the present invention may have all the features described above for the mineral fiber product of the present invention, and therefore refer to the description thereon.

[0296] Alternative solution B (Fifth to Eighth Aspects of the Invention) Invention Overview

[0298] As noted above, one object of the present invention is to provide a mineral fiber product that has improved high-temperature use, can be produced economically, and uses renewable materials as starting materials for the preparation of aqueous binder compositions.

[0299] Another object of the present invention is to provide uses for such mineral fiber products.

[0300] Another object of the present invention is to provide a method for transporting media through pipelines at high temperatures.

[0301] According to a fifth aspect of the invention, a mineral fiber product comprising mineral fibers bonded by a cured binder composition is provided, wherein the uncured binder composition comprises one or more oxylignins, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1000 μg isocyanate (ICA) / g sample, for example less than 750 μg isocyanate (ICA) / g sample, for example less than 500 μg isocyanate (ICA) / g sample, for example less than 250 μg isocyanate (ICA) / g sample, for example less than 100 μg isocyanate (ICA) / g sample.

[0302] According to a sixth aspect of the invention, the use of a mineral fiber product comprising mineral fibers bonded by a cured binder composition at a temperature of at least 300°C is provided, preferably as a heat insulation product, wherein the uncured binder composition comprises one or more oxylignins, wherein optionally, heating the mineral fiber product to a temperature of 600°C releases less than 1000 μg isocyanate (ICA) / g sample, for example less than 750 μg isocyanate (ICA) / g sample, for example less than 500 μg isocyanate (ICA) / g sample, for example less than 250 μg isocyanate (ICA) / g sample, for example less than 100 μg isocyanate (ICA) / g sample.

[0303] According to a seventh aspect of the present invention, a method for conveying a medium is provided, the method comprising the following steps:

[0304] a) Covering pipes with mineral fiber products used as thermal insulation materials, and

[0305] b) The medium is transported through the pipeline.

[0306] The mineral fiber product used as thermal insulation material for heat pipes comprises mineral fibers bonded by a cured binder composition, wherein the uncured binder composition comprises one or more oxylignins, wherein optionally, heating the mineral fiber product to a temperature of 600°C releases less than 1000 μg isocyanate (ICA) / g sample, for example less than 750 μg isocyanate (ICA) / g sample, for example less than 500 μg isocyanate (ICA) / g sample, for example less than 250 μg isocyanate (ICA) / g sample, for example less than 100 μg isocyanate (ICA) / g sample.

[0307] According to an eighth aspect of the invention, a pipe covered with a mineral fiber product as an insulation material is provided, wherein the mineral fiber product comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxylignins, wherein optionally, heating the mineral fiber product to a temperature of 600°C releases less than 1000 μg isocyanate (ICA) / g sample, for example less than 750 μg isocyanate (ICA) / g sample, for example less than 500 μg isocyanate (ICA) / g sample, for example less than 250 μg isocyanate (ICA) / g sample, for example less than 100 μg isocyanate (ICA) / g sample.

[0308] The inventors have surprisingly discovered that when lignin-based binder compositions are used in mineral fiber products, mineral fiber products with low or even no ICA release can be used in high-temperature applications.

[0309] Description of preferred implementation scheme

[0310] The mineral fiber product of the present invention comprises mineral fibers bonded by a cured binder composition, wherein the uncured binder composition comprises one or more oxylignins, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1000 μg isocyanate (ICA) / g sample, preferably less than 750 μg isocyanate (ICA) / g sample, for example less than 500 μg isocyanate (ICA) / g sample, for example less than 250 μg isocyanate (ICA) / g sample, for example less than 100 μg isocyanate (ICA) / g sample.

[0311] The heated mineral fiber product contains a cured binder composition. Regarding "gram sample," the gram sample refers to the sample weight as defined according to Procedure II below.

[0312] When a mineral fiber product containing a cured binder composition is heated at a certain temperature and the content of isocyanate (ICA) in the exhaust gas is quantitatively analyzed by Fourier transform infrared spectroscopy (FTIR), the result is a measurement of the amount of ICA released. This measurement is considered as the ICA release amount related to the amount of cured binder composition in the tested mineral fiber product.

[0313] For standardization, the total emissions of the ICA and other given exhaust gases were determined according to Procedure II as described below to obtain comparable data for different products tested at different temperatures. Note that the data obtained cannot be directly compared quantitatively to the emissions of these products determined under specific field conditions when these products are implemented by end customers in industrial insulation systems. For example, in an actual end-customer installation, the products will not be crushed as in Procedure II described below, and the binder in the mineral fiber products will not be completely burned off. In fact, the values ​​obtained using this Procedure II correspond to the worst-case scenario, both in terms of quantity and release time. Therefore, lower and slower emissions (reaching steady state in 2-48 hours) are expected for the products, whereas this Procedure II achieves steady state in less than 2 hours after actual installation, compared to the values ​​obtained in this study. However, it can be readily assumed that the mineral fiber products, which exhibit lower total emissions compared to other products according to Procedure II, will also have lower total emissions in an actual end-customer installation.

[0314] Release measurements of different mineral wool products are typically performed by external research institutes such as RISE in Sweden using a combination of tests on different materials of varying thicknesses. The dependence of insulation thickness on the release curve is determined by quantification of the FID signal and infrared measurements of released gases such as CO, NH3, HCN, NOx, and ICA.

[0315] With regard to Alternative B of this application, the total amount of ICA released was measured according to Procedure II described below. Internal measurements have been performed on different milled mineral wool products according to Procedure II to eliminate discussions regarding thickness and porosity. These experiments were conducted in a custom-designed release chamber (tube furnace) that heats the material to a specific temperature setpoint and sustains it for a specific time. During these experiments, air passed through the chamber at a specified rate and was sampled for quantification of different compounds. Four different temperatures (250°C, 350°C, 450°C, and 600°C) were tested, and the released gases were quantified using Fourier transform infrared spectroscopy. Details of Procedure II are given below in the experimental section.

[0316] Preferably, when the mineral fiber product containing the cured binder composition is heated, the mineral fiber product of the present invention also exhibits low release of other waste gases such as NH3, HCN and / or NOx.

[0317] In a preferred embodiment, heating the mineral fiber product to a temperature of 600°C releases less than 500 μg HCN / g sample, for example less than 250 μg HCN / g sample, for example less than 100 μg HCN / g sample, for example less than 50 μg HCN / g sample.

[0318] For the purposes of this application, the total amount of HCN released can be measured according to the same procedure II described below. Of course, gas analysis by FTIR will then be performed on the compound to be identified.

[0319] The mineral fiber products of this invention are suitable for high-temperature applications and also relate to thermal stability. In particular, the mineral fiber products of this 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 operating temperature plate test of EN14706:2012, the mineral fiber products of this invention generally meet the condition of a maximum operating temperature (MST) of at least 600°C, preferably at least 650°C. MST is not related to thermal degradation or exhaust gases, but rather to mechanical strength.

[0320] Typically, the uncured adhesive composition is an aqueous adhesive composition. In a preferred embodiment, the adhesive of the present invention is formaldehyde-free.

[0321] For the purposes of this application, the term "formaldehyde-free" is defined as indicating that the formaldehyde released from the mineral wool product is less than 5 μg / m³. 2 / h, preferably below 3μg / m 2 / h of mineral wool product. Preferably, the test is performed according to ISO 16000 for testing aldehyde release.

[0322] The uncured binder composition used to prepare the mineral fiber products of the present invention contains one or more oxylignins as a component (i).

[0323] Component (i)

[0324] Component (i) is in the form of one or more oxylignins.

[0325] Lignin, cellulose, and hemicellulose are the three main organic compounds in plant cell walls. Lignin can be considered a glue, holding 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.

[0326] Figure 1 A portion of the possible lignin structure is shown.

[0327] At least four groups of industrial lignins are available on the market. These four groups of industrial lignins are shown... Figure 3 The fifth possible group, biorefined lignin, is somewhat different because it is not described by extraction methods but by process sources such as biorefining; therefore, it can be similar to or different from any of the other groups mentioned. Each group differs from one another, and each group 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 [link to relevant documentation]). Figure 2 ), and therefore they are more uniform in lignin than hardwood lignin, which has a higher eugenol content (see Figure 2 The appearance and consistency of lignin vary greatly and depend to a large extent on the processing method.

[0328] The performance of these industrial lignins is summarized as follows: Figure 4 middle.

[0329] Lignin sulfonates derived from sulfite pulping remain the largest commercially available source of lignin, with a capacity of 1.4 million tons. However, sulfite pulping is currently the most widely used pulping process and is gradually replacing sulfite pulping. It is estimated that 78 million tons of lignin are produced globally annually through sulfate pulping methods, but most of this is burned for steam and energy. Current kraft paper recycling capacity is estimated at 160,000 tons, but sources indicate that current recycling volume is only around 75,000 tons. Sulfate lignin is developed from black liquor, the waste liquid from sulfate or kraft paper processes. Currently, three well-known methods are used to produce sulfate lignin: LignoBoost, LignoForce, and SLRP. These three methods are similar in that they involve adding CO2 to lower the pH to 9-10, followed by acidification to further lower the pH to around 2. The final step includes some combination of washing, leaching, and filtration to remove ash and other contaminants. These three methods are at different stages of commercialization globally.

[0330] The sulfate process introduces thiol groups and 1,2-stilbene while retaining some carbohydrates. Sodium sulfate is also present as an impurity due to the precipitation of lignin from the liquid with sulfuric acid, but this can potentially be avoided by altering the method of lignin separation. The sulfate process results in a large number of phenolic hydroxyl groups, and this lignin is water-soluble when these groups are ionized (at pH values ​​above approximately 10).

[0331] Commercial lignin sulfates are typically of higher purity than lignin sulfonates. Their molecular weight ranges from 1000 to 3000 g / mol.

[0332] Alkali lignin is derived from sodium hydroxide pulping methods primarily used for wheat straw, sugarcane bagasse, and flax. Regarding solubility and T... g In this respect, alkali lignin exhibits properties similar to those of sulfate lignin. This method does not use sulfur, nor does it involve covalently bonded sulfur. Ash levels are very low. Alkali lignin has low solubility in neutral and acidic media, but is completely soluble at pH 12 and higher.

[0333] The lignin sulfonate 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 sulfonate form, while sulfate lignin contains 1-2% sulfur, which is primarily bonded to lignin. The molecular weight of lignin sulfonates is 15,000-50,000 g / mol. Compared to other types of lignin, this lignin contains more residual carbohydrates and has a higher average molecular weight. The typical hydrophobic core of lignin, along with a large number of ionized sulfonate groups, makes this lignin attractive as a surfactant, and it is frequently used in applications such as dispersing cement.

[0334] Another group of lignin becoming available is that produced through biorefining methods, where carbohydrates are separated from lignin through chemical or biochemical processes to produce a carbohydrate-rich fraction. This remaining lignin is called biorefined lignin. Biorefining plants focus on producing energy and alternatives to products derived from fossil fuels and petrochemicals, as well as lignin. Lignin from this method is often considered a low-value product, or even waste primarily intended for thermal combustion, use as low-grade animal feed, or otherwise disposed of.

[0335] The availability of organic solvent lignin is still under consideration at the pilot-scale level. This method involves extracting lignin using water, as well as various organic solvents (most commonly ethanol) and some organic acids. One advantage of this method is the high purity of the obtained lignin, but it is significantly more expensive than other industrial lignins and is soluble in organic solvents but not in water.

[0336] Previous attempts to use lignin as a base compound in binder compositions for mineral fibers failed because it proved difficult to find a suitable crosslinking agent capable of achieving the desired mechanical properties of cured mineral wool products while avoiding harmful and / or corrosive components. Currently, lignin is used as a substitute for 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 respects, as a dispersant.

[0337] Crosslinking of polymers typically provides improved properties such as mechanical, chemical, and thermal resistance. Lignin possesses a particularly rich array of phenolic and aliphatic hydroxyl groups, which can react to lead to crosslinked structures. Different lignins will also possess other available functional groups that can potentially be utilized. The presence of these other groups depends largely on how lignin is separated from cellulose and hemicellulose (thiols in sulfate lignin, sulfonates in lignin sulfonates, etc.), and depends on the source.

[0338] It has been discovered that a binder composition for mineral fibers can be prepared by using lignin oxide, which allows mineral fiber products produced therefrom to have excellent properties without requiring other components to be included in the binder composition. This enables the mineral fiber products of the present invention to be used in high-temperature applications with low or even no ICA release.

[0339] In one embodiment, the component (i) is in the form of one or more oxidized sulfate lignins.

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

[0341] In one embodiment, component (i) is in the form of one or more ammonia-oxidized lignins. For the purposes of this invention, the term "ammonia-oxidized lignin" should be understood as lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.

[0342] In an alternative embodiment, the ammonia is partially or completely replaced by an alkali metal hydroxide, particularly sodium hydroxide and / or potassium hydroxide.

[0343] A typical oxidizing agent used to prepare the oxylignin is hydrogen peroxide.

[0344] In one embodiment, the ammonia-oxidized lignin comprises one or more compounds selected from ammonia, amines, hydroxides, or any salts thereof.

[0345] In one embodiment, the component (i) has a carboxylic acid group content of 0.05 to 10 mmol / g, for example 0.1 to 5 mmol / g, for example 0.20 to 1.5 mmol / g, for example 0.40 to 1.2 mmol / g, for example 0.45 to 1.0 mmol / g, based on the dry weight of component (i).

[0346] In the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, component (i) namely the one or more oxylignins may be present in an amount of 25-95% by weight, for example 30-90% by weight, for example 35-85% by weight, based on the dry weight of the adhesive composition.

[0347] In one embodiment, the component (i) has an average carboxylic acid group content of more than 1.5 groups / component (i), such as more than 2 groups / component (i) or more than 2.5 groups / component (i).

[0348] It is believed that the carboxylic acid group content of the oxidized lignin plays a significant role in the surprising advantages of the water-based binder composition for mineral fibers of the present invention. In particular, it is believed that the carboxylic acid groups of the oxidized lignin improve crosslinking properties and thus allow the cured mineral fiber product to have better mechanical properties.

[0349] 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:

[0350] - Components in the form of one or more oxidized lignins (i);

[0351] - Components in the form of one or more crosslinking agents (ii);

[0352] -Optionally, components in the form of one or more plasticizers (iii).

[0353] Component (ii)

[0354] Optional component (ii) is in the form of one or more crosslinking agents.

[0355] In one embodiment, component (ii) comprises one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

[0356] β-hydroxyalkylamide crosslinking agents are curing agents for acid-functionalized macromolecules. They provide hard, durable, corrosion-resistant, and solvent-resistant crosslinked polymer networks. β-hydroxyalkylamide crosslinking agents are believed to cure via esterification to form multiple ester bonds. The hydroxyl functionality of the β-hydroxyalkylamide crosslinking agent should have an average of at least 2, preferably greater than 2, and more preferably 2-4, to obtain optimal curing response.

[0357] Oxazoline-containing crosslinking agents are polymers containing one or more oxazoline groups in each molecule, and are generally readily obtained by polymerizing oxazoline derivatives. Patent US6818699 B2 discloses such a method.

[0358] In one embodiment, component (ii) is an oil based on the epoxidation of fatty acid triglycerides.

[0359] It has been noted that epoxidized oils based on fatty acid triglycerides are not considered dangerous, and therefore the use of these compounds in the binder compositions of the present invention does not make these compositions unsafe to operate.

[0360] In one embodiment, component (ii) is a molecule having three or more epoxy groups.

[0361] In one embodiment, the component (ii) is one or more flexible oligomers or polymers, such as low-Tg acrylic polymers, low-Tg vinyl polymers, or low-Tg polyethers, containing reactive functional groups, such as carbodiimide groups, anhydride groups, oxazoline groups, amino groups, or epoxy groups.

[0362] In one embodiment, component (ii) is selected from the group consisting of crosslinking agents involved in the curing reaction, such as hydroxyalkylamides, alkanolamines, and reaction products of alkanolamines and polycarboxylic acids. Reaction products of alkanolamines and polycarboxylic acids are available in US6706853B1.

[0363] Without wishing to be bound by any particular theory, it is believed that the highly advantageous properties of the adhesive compositions of the present invention, preferably aqueous adhesive compositions, are due to the interaction between lignin oxide used as component (i) and the aforementioned crosslinking agent. It is believed that the presence of carboxylic acid groups in the lignin oxide enables the lignin oxide to crosslink very effectively.

[0364] In one embodiment, 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.

[0365] In one embodiment, component (ii) is one or more crosslinking agents selected from the group consisting of polyethyleneimine, polyvinylamine, and aliphatic amines.

[0366] In one embodiment, component (ii) is one or more fatty amides.

[0367] In one embodiment, component (ii) is one or more crosslinking agents selected from the group consisting of dimethoxyacetaldehyde, glycolaldehyde, and glyoxylic acid.

[0368] In one embodiment, component (ii) is one or more crosslinking agents selected from polyester polyols such as polycaprolactone.

[0369] In one embodiment, component (ii) is one or more crosslinking agents selected from the group consisting of starch, modified starch, and CMC.

[0370] In one embodiment, component (ii) is one or more crosslinking agents in the form of aliphatic polyfunctional carbodiimides.

[0371] In one embodiment, component (ii) is one or more crosslinking agents selected from melamine-based crosslinking agents such as hexa(methylmethoxy)melamine (HMMM)-based crosslinking agents.

[0372] Examples of such compounds are Picassian XL 701, 702, 725 (Stahl Polymers), for example. XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).

[0373] In one embodiment, component (ii) is Primid XL552, which has the following structure:

[0374]

[0375] Component (ii) may also be any mixture of the compounds mentioned above.

[0376] In one embodiment, the adhesive composition of the present invention contains component (ii) in an amount of 1 to 40% by weight, for example 4 to 20% by weight, for example 6 to 12% by weight, based on the dry weight of component (i).

[0377] Component (iii)

[0378] Optional component (iii) is in the form of one or more plasticizers.

[0379] 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 having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides such as urea / urea, or any mixture thereof.

[0380] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of: carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds having a lignin-like structure such as vanillin, acetylsuccinone, and solvents used as coalescing agents such as alcohol ethers, polyvinyl alcohol.

[0381] In one embodiment, component (iii) is in the form of one or more non-reactive plasticizers selected from the group consisting of: polyethylene glycol, polyethylene glycol ether, polyether, hydrogenated sugar, phthalate and / or other esters, solvents used as coalescing agents such as alcohol ether, acrylic polymers, and polyvinyl alcohol.

[0382] 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 polymers having free carboxyl groups, and compounds having a lignin-like structure such as vanillin, acetylsuccinone.

[0383] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of: fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.

[0384] In one embodiment, component (iii) comprises one or more plasticizers selected from the group consisting of polyethylene glycol and polyethylene glycol ether.

[0385] Another particularly surprising aspect of the invention is that the use of plasticizers with boiling points exceeding 100°C, particularly 140 to 250°C, greatly improves the mechanical properties of the mineral fiber products of the invention, although, given their boiling points, these plasticizers are likely to evaporate at least partially during the curing process of the binder, preferably an aqueous binder, in contact with the mineral fibers.

[0386] In one embodiment, component (iii) comprises one or more plasticizers having a boiling point of more than 100°C, for example 110 to 280°C, more preferably 120 to 260°C, and even more preferably 140 to 250°C.

[0387] It is believed that the effectiveness of these plasticizers in the adhesive compositions, preferably aqueous adhesive compositions, used according to the invention is related to their effect of increasing the fluidity of lignin oxidized during the curing process. It is believed that the increased fluidity of lignin or lignin oxidized during curing promotes effective crosslinking.

[0388] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, particularly 150 to 4,000 g / mol, more specifically 150 to 1,000 g / mol, preferably 150 to 500 g / mol, and more preferably 200 to 400 g / mol.

[0389] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4,000 to 25,000 g / mol, particularly 4,000 to 15,000 g / mol, and more specifically 8,000 to 12,000 g / mol.

[0390] In one embodiment, component (iii) is capable of forming covalent bonds with components (i) and / or (ii) during the curing process. Such a component will not evaporate and will remain as part of the composition, but will be effectively altered so as not to introduce unwanted side effects such as the water absorption of the cured product. Non-limiting examples of such components are caprolactone and acrylic polymers having free carboxyl groups.

[0391] In one embodiment, component (iii) is selected from the group consisting of fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.

[0392] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxides, such as ethoxides, such as butanol ethoxides, such as butoxytriethylene glycol.

[0393] In one embodiment, component (iii) is selected from one or more propylene glycols.

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

[0395] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of adipate, acetate, benzoate, cyclobenzoate, citrate, stearate, sorbate, sebate, azelaate, butyrate, and valerate.

[0396] 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.

[0397] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of silanols and siloxanes.

[0398] 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 alkyl aryl sulfonates, alkyl sulfonates, phosphates such as tripolyphosphates, for example, tributyl phosphate.

[0399] In one embodiment, component (iii) is selected from one or more hydroxy acids.

[0400] 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 tallowamide.

[0401] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of quaternary ammonium compounds, such as trimethylglycine and distearate dimethylammonium chloride.

[0402] 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, and soybean oil.

[0403] In one embodiment, component (iii) is in the form of tall oil.

[0404] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of hydrogenated oils and acetylated oils.

[0405] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0406] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucoside, glucosamide, aminoglucosamide, sucrose ester, and sorbitol ester.

[0407] It has been surprisingly found that the inclusion of plasticizers in the binder compositions, preferably aqueous binder compositions, used according to the present invention greatly improves the mechanical properties of the mineral fiber products of the present invention.

[0408] The term "plasticizer" refers to a substance added to a material to make it softer, more flexible (by lowering its glass transition temperature Tg) and easier to process.

[0409] Component (iii) may also be any mixture of the compounds mentioned above.

[0410] In one embodiment, component (iii) is present in an amount of 0.5-50% by weight, preferably 2.5-25% by weight, more preferably 3-15% by weight, based on the dry weight of component (i).

[0411] A mineral fiber adhesive composition, preferably an aqueous adhesive composition, comprising components (i) and (iia).

[0412] In one embodiment, the present invention relates to a binder composition for mineral fibers, preferably an aqueous binder composition, comprising:

[0413] - Components in the form of one or more oxidized lignins (i);

[0414] - Components in the form of one or more modifiers (iia).

[0415] The inventors have discovered that the superior adhesive properties can also be achieved through a two-component system comprising a component (i) in the form of one or more lignin oxides and a component (iia) in the form of one or more modifiers, as well as any other components optionally mentioned above and below.

[0416] 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.

[0417] 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.

[0418] In one embodiment, component (iia) is a modifier in the form of one or more of the following substances: flexible oligomers or polymers, such as low-Tg acrylic polymers, low-Tg vinyl polymers, low-Tg polyethers, containing reactive functional groups such as carbodiimide groups, anhydride groups, oxazoline groups, amino groups, and epoxy groups.

[0419] In one embodiment, component (iia) is one or more modifiers selected from the group consisting of polyethyleneimine, polyvinylamine, and aliphatic amines.

[0420] In one embodiment, component (iia) is one or more modifiers selected from the group consisting of aliphatic multifunctional carbodiimides.

[0421] The component (iia) can also be any mixture of the compounds mentioned above.

[0422] Without wishing to be bound by any particular theory, the inventors believe that the superior adhesive properties achieved by the mineral fiber binder composition comprising components (i) and (iia) and optionally other components are at least in part attributable to the effect of the modifier used as component (iia) functioning at least in part as a plasticizer and crosslinking agent.

[0423] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, contains component (iia) in an amount of 1 to 40% by weight, for example 4 to 20% by weight, for example 6 to 12% by weight, based on the dry weight of component (i).

[0424] Other components

[0425] In some embodiments, the adhesive composition, preferably an aqueous adhesive composition, used according to the invention contains additional components.

[0426] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the invention comprises a catalyst selected from: inorganic acids, such as sulfuric acid, aminosulfonic acid, nitric acid, boric acid, hypophosphoric acid, and / or phosphoric acid, and / or any salt thereof, such as sodium hypophosphite, and / or ammonium salts such as ammonium salts of sulfuric acid, aminosulfonic acid, nitric acid, boric acid, hypophosphoric acid, and / or phosphoric acid, and / or sodium polyphosphate (STTP), and / or sodium metaphosphate (STMP), and / or phosphorus trichloride. The presence of such a catalyst can improve the curing properties of the adhesive composition, preferably an aqueous adhesive composition, used according to the invention.

[0427] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, comprises a catalyst selected from Lewis acids that can accept electron pairs from donor compounds forming Lewis adducts, such as ZnCl2, Mg(ClO4)2, Sn[N(SO2-n-C8F] 17 )2]4.

[0428] In one embodiment, the binder composition used according to the invention, preferably an aqueous binder composition, comprises a catalyst selected from metal chlorides, such as KCl, MgCl2, ZnCl2, FeCl3, and SnCl2.

[0429] In one embodiment, the binder composition used according to the invention, preferably an aqueous binder composition, comprises a catalyst selected from organometallic compounds, such as titanate-based catalysts and tin-based catalysts.

[0430] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, and copper ions.

[0431] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, further comprises an additional component (iv) in the form of one or more silanes.

[0432] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, comprises an additional component (iv) in the form of one or more coupling agents such as organically functional silanes.

[0433] In one embodiment, component (iv) is selected from the group consisting of: organically functionalized silanes, such as silanes functionalized with primary or secondary amino groups, epoxy-functionalized silanes such as polymer or oligomeric epoxy-functionalized silanes, methacrylate-functionalized silanes, alkyl and aryl-functionalized silanes, urea-functionalized silanes, or vinyl-functionalized silanes.

[0434] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, further comprises a component (v) in the form of one or more components selected from ammonia, amines, or any salts thereof.

[0435] It has been found that when oxylignin, which is not oxidized in the presence of ammonia, is used in component (i), it may be particularly useful to include ammonia, amines, or any of their salts as an additional component.

[0436] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, further comprises an additional component in the form of urea, particularly in an amount of 5 to 40% by weight, for example 10 to 30% by weight, or 15 to 25% by weight, based on the dry weight of component (i).

[0437] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, further comprises an additional component in the form of one or more carbohydrates selected from the group consisting of sucrose, reducing sugars, particularly dextrose, polysaccharides, and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, and 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, glucose syrup with DE = 95-99.

[0438] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, 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, for example 5 to less than 50% by weight, for example 10 to 40% by weight, for example 15 to 30% by weight, based on the dry weight of component (i).

[0439] In the context of this 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 a sugar-based binder. In the context of this 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 a non-sugar-based binder.

[0440] In one embodiment, the adhesive composition used according to the invention, preferably an aqueous adhesive composition, further comprises an additional component in the form of one or more surfactants, said surfactants being in the form of nonionic and / or ionic emulsifiers, such as polyoxyethylene (4) lauryl ether, soybean lecithin, sodium dodecyl sulfate.

[0441] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, comprises:

[0442] - Component (i) in the form of one or more amino-oxidized lignins, having a carboxylic acid group content of 0.05 to 10 mmol / g, for example 0.1 to 5 mmol / g, for example 0.20 to 1.5 mmol / g, for example 0.40 to 1.2 mmol / g, for example 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0443] - Component (ii) in the form of one or more crosslinking agents, selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents, and / or one or more crosslinking agents selected from the group consisting of: multifunctional organic amines, such as alkanolamines, diamines such as 1,6-hexanediamine, and triamines;

[0444] - Component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, particularly 150 to 4,000 g / mol, more specifically 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, particularly 4,000 to 15,000 g / mol, more specifically 8,000 to 12,000 g / mol; wherein preferably the adhesive composition, preferably the aqueous adhesive composition, comprises 1 to 40% by weight, for example 4 to 20% by weight, 6 to 12% by weight of component (ii) based on the dry weight of component (i), and the amount of component (iii) present is 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).

[0445] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, comprises:

[0446] - Component (i) in the form of one or more amino-oxidized lignins, having a carboxylic acid group content of 0.05 to 10 mmol / g, for example 0.1 to 5 mmol / g, for example 0.20 to 1.5 mmol / g, for example 0.40 to 1.2 mmol / g, for example 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0447] - Components (iia) in the form of one or more modifiers, selected from epoxidized oils based on fatty acid triglycerides.

[0448] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, comprises:

[0449] - Component (i) in the form of one or more amino-oxidized lignins, having a macromolecule with more than 1.5 groups / component (i), such as a macromolecule with more than 2 groups / component (i), such as a macromolecule with more than 2.5 groups / component (i) with an average carboxylic acid group content.

[0450] - Component (ii) in the form of one or more crosslinking agents, selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents, and / or one or more crosslinking agents selected from the group consisting of: multifunctional organic amines, such as alkanolamines, diamines such as 1,6-hexanediamine, and triamines;

[0451] - Component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, particularly 150 to 4,000 g / mol, more specifically 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, particularly 4,000 to 15,000 g / mol, more specifically 8,000 to 12,000 g / mol; wherein preferably the adhesive composition, preferably the aqueous adhesive composition, comprises 1 to 40% by weight, for example 4 to 20% by weight, 6 to 12% by weight of component (ii) based on the dry weight of component (i), and the amount of component (iii) present is 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).

[0452] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, comprises:

[0453] - Component (i) in the form of one or more amino-oxidized lignins, having a macromolecule with more than 1.5 groups / component (i), such as a macromolecule with more than 2 groups / component (i), such as a macromolecule with more than 2.5 groups / component (i) with an average carboxylic acid group content.

[0454] - Components (iia) in the form of one or more modifiers, selected from epoxidized oils based on fatty acid triglycerides.

[0455] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, consists essentially of the following components:

[0456] - Components in the form of one or more oxylignins (i);

[0457] - Components in the form of one or more crosslinking agents (ii);

[0458] - Components in the form of one or more plasticizers (iii);

[0459] - Components in the form of one or more coupling agents such as organofunctional silanes (iv);

[0460] - Optional components in the form of one or more compounds selected from ammonia, amines, or any salts thereof;

[0461] - Optional components in the form of urea;

[0462] - Optional components in the form of more reactive or non-reactive organosilicon;

[0463] -Optional hydrocarbon oil;

[0464] -One or more surfactants may be selected;

[0465] -water.

[0466] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, consists essentially of the following components:

[0467] - Components in the form of one or more oxylignins (i);

[0468] - Components (iia) in the form of one or more modifiers, selected from epoxidized oils based on fatty acid triglycerides;

[0469] - Components in the form of one or more coupling agents such as organically functional silanes (iv);

[0470] - Optional components in the form of one or more compounds selected from ammonia, amines, or any salts thereof;

[0471] - Optional components in the form of urea;

[0472] - Optional components in the form of more reactive or non-reactive organosilicon;

[0473] -Optional hydrocarbon oil;

[0474] -One or more surfactants may be selected;

[0475] -water.

[0476] Methods for producing mineral fiber products

[0477] The mineral fiber products of the present invention can be prepared by common methods of producing mineral fiber products by bonding mineral fibers with a binder composition. Therefore, the mineral fiber products of the present invention are preferably prepared by a method comprising the following steps: contacting the mineral fibers with an uncured and preferably aqueous binder composition containing one or more lignin oxides.

[0478] In a preferred embodiment, the uncured and preferably water-based adhesive composition comprises:

[0479] - Components in the form of one or more oxidized lignins (i);

[0480] - Components in the form of one or more crosslinking agents (ii);

[0481] - Optional components in the form of one or more plasticizers (iii).

[0482] Curing

[0483] The mineral fiber product precursor is cured by chemical and / or physical reactions of the binder components, such as the uncured binder composition in a web in which the mineral fibers come into contact with the binder composition.

[0484] In one embodiment, the curing is performed in a curing apparatus.

[0485] In one embodiment, the curing is carried out at a temperature of 100-300°C, for example 170-270°C, for example 180-250°C, for example 190-230°C.

[0486] In one embodiment, the curing is carried out in a conventional curing oven used for mineral wool production, the curing oven operating at temperatures of 150 to 300°C, for example 170 to 270°C, for example 180 to 250°C, for example 190 to 230°C.

[0487] In one embodiment, the curing process takes 30 seconds to 20 minutes, for example, 1 to 15 minutes, or for example, 2 to 10 minutes.

[0488] In a typical implementation, curing is carried out at a temperature of 150 to 250°C for 30 seconds to 20 minutes.

[0489] The curing process can begin immediately after the adhesive is applied to the fibers. Curing is defined as the process by which the adhesive composition undergoes a physical and / or chemical reaction (in the case of a chemical reaction, curing typically increases the molecular weight of the compounds in the adhesive composition) and thereby increases the viscosity of the adhesive composition, typically until the adhesive composition reaches a solid state.

[0490] In one embodiment, the curing process includes pressure drying. Pressure can be applied by blowing air or gas through / over the mixture of mineral fibers and binder.

[0491] The mineral fiber product of the present invention

[0492] This invention relates to mineral fiber products comprising mineral fibers in contact with the cured adhesive composition described above (i.e., in contact with a cured adhesive resulting from the curing of the adhesive composition described above, preferably an aqueous adhesive composition).

[0493] The mineral fibers used can be any of the following: man-made glass fiber (MMVF), glass fiber, ceramic fiber, basalt fiber, slag fiber, rock fiber, stone fiber, etc. These fibers can exist in the form of wool products such as asbestos products.

[0494] Fiber / melt composition

[0495] Man-made glass fiber (MMVF) can have any suitable oxide composition. The fiber can be glass fiber, ceramic fiber, basalt fiber, slag fiber, or rock or stone fiber. The fiber is preferably of the type commonly referred to as rock fiber, stone fiber, or slag fiber, and most preferably stone fiber.

[0496] Stone fibers typically contain the following oxides, expressed as a percentage by weight:

[0497] SiO2: 30-51

[0498] CaO: 8-30

[0499] MgO: 2-25

[0500] FeO (including Fe2O3): 2-15

[0501] Na₂O + K₂O: not exceeding 10

[0502] CaO + MgO: 10-30

[0503] In some preferred embodiments, the MMVF has the following elemental levels, calculated as oxides and expressed as a percentage by weight:

[0504] SiO2: at least 30, 32, 35, or 37; not exceeding 51, 48, 45, or 43.

[0505] Al2O3: at least 12, 16, or 17; not exceeding 30, 27, or 25

[0506] CaO: at least 8 or 10; not exceeding 30, 25 or 20

[0507] MgO: at least 2 or 5; not more than 25, 20 or 15

[0508] FeO (including Fe2O3): at least 4 or 5; not exceeding 15, 12 or 10

[0509] FeO+MgO: at least 10, 12, or 15; not exceeding 30, 25, or 20

[0510] Na₂O + K₂O: 0 or at least 1; not exceeding 10

[0511] CaO + MgO: at least 10 or 15; not exceeding 30 or 25

[0512] TiO2: 0 or at least 1; not exceeding 6, 4 or 2

[0513] TiO2+FeO: at least 4 or 6; not exceeding 18 or 12

[0514] B2O3: 0 or at least 1; not exceeding 5 or 3

[0515] P2O5: 0 or at least 1; not exceeding 8 or 5

[0516] Other: 0 or at least 1; not exceeding 8 or 5

[0517] The MMVF prepared by the method of the present invention preferably has the following composition (expressed in wt%):

[0518] SiO2: 35-50

[0519] Al2O3: 12-30

[0520] TiO2: Maximum 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: Maximum 3

[0528] B2O3: Maximum 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] Other: 0-2.0%

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

[0543] SiO2: 50-70

[0544] Al2O3: 10-30

[0545] CaO: not exceeding 27

[0546] MgO: not exceeding 12

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

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

[0549] B2O3: 3-12

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

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

[0552] The sprayed mineral fiber mesh is typically cured in a curing oven using a flow of hot air. This hot air flow can be introduced into the mineral fiber mesh from below, above, or from alternating directions in different regions along the length of the curing oven.

[0553] Typically, curing ovens operate at temperatures ranging from about 150°C to about 300°C, for example, 170 to 270°C, 180 to 250°C, or 190 to 230°C. The typical curing oven dwell time is from 30 seconds to 20 minutes, for example, 1 to 15 minutes, or 2 to 10 minutes, depending on factors such as product density.

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

[0555] If necessary, the mineral fiber web can be shaped before curing. The bonded mineral fiber product exiting the curing oven can be cut into the desired form, such as in a fuzzy form.

[0556] In a preferred embodiment, the mineral fiber product of the present invention is an insulation product. The mineral fiber product is preferably in the form of pre-formed tube sections, wire-reinforced gaskets, or sheets.

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

[0558] The mineral fiber products of this invention typically have a strength of 6-250 kg / m³. 3 Preferred weight: 20-200 kg / m 3 The density is within the range specified. 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] Uses of the mineral fiber products of this invention

[0560] The present invention relates to the use of mineral fiber products in high-temperature applications. Here, high-temperature applications refer to the use of mineral fiber products 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] Therefore, the present invention also relates to the use of mineral fiber products at temperatures of at least 300°C, preferably at least 400°C, for example at least 450°C, said mineral fiber products comprising mineral fibers bonded by a cured binder composition, wherein the uncured binder composition comprises one or more oxylignins. Typically, the use of the present invention is at temperatures not exceeding 700°C, preferably not exceeding 650°C.

[0562] Typically, it is preferred to heat the mineral fiber product to 600°C to release less than 1000 μg isocyanate (ICA) / g sample, more preferably less than 750 μg isocyanate (ICA) / g sample, for example less than 500 μg isocyanate (ICA) / g sample, for example less than 250 μg isocyanate (ICA) / g sample, for example less than 100 μg isocyanate (ICA) / g sample. The method for determining the total ICA release is described below.

[0563] In a preferred embodiment of the invention, the mineral fiber product is used as an insulation product, more preferably as a thermal insulation material for heat pipes.

[0564] Regarding the application of the invention, the pipeline is preferably operated at a high operating 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 not exceeding 650°C.

[0565] The pipeline is preferably a metal pipeline. Specifically, the pipeline is used to transport media, such as gases, steam, or fluids. The media transported through the pipeline are typically high-temperature media having the aforementioned minimum operating temperature.

[0566] Mineral fiber products used for purposes of this invention may have all the features described above for mineral fiber products of this invention, and therefore refer to the description.

[0567] The method for conveying the medium of the present invention

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

[0569] a) Covering pipes with mineral fiber products used as thermal insulation materials, and

[0570] b) The medium is transported through the pipeline.

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

[0572] Typically, it is preferred to heat the mineral fiber product to a temperature of 600°C to release less than 1000 μg isocyanate (ICA) / g sample, for example less than 750 μg isocyanate (ICA) / g sample, for example less than 500 μg isocyanate (ICA) / g sample, for example less than 250 μg isocyanate (ICA) / g sample, for example less than 100 μg isocyanate (ICA) / g sample. The method for determining the total ICA release is described below.

[0573] In a preferred embodiment, the medium being transported 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, and more preferably does not exceed 650°C.

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

[0575] The mineral fiber products used in the method of the present invention may have all the features described above for the mineral fiber products of the present invention, and therefore refer to the description thereon.

[0576] The pipe with heat insulation material of the present invention

[0577] The present invention also relates to pipes covered or wrapped with mineral fiber products as insulation materials, wherein the mineral fiber products comprise mineral fibers bonded by a cured adhesive composition, and the uncured adhesive composition comprises one or more oxylignins.

[0578] Typically, it is preferred to heat the mineral fiber product to a temperature of 600°C to release less than 1000 μg isocyanate (ICA) / g sample, for example less than 750 μg isocyanate (ICA) / g sample, for example less than 500 μg isocyanate (ICA) / g sample, for example less than 250 μg isocyanate (ICA) / g sample, for example less than 100 μg isocyanate (ICA) / g sample. The method for determining the total ICA release is described below.

[0579] The mineral fiber product used to cover the pipes of the present invention may have all the features described above for the mineral fiber product of the present invention, and therefore refer to the description thereon.

[0580] Oxidized lignin, a component of the mineral fiber binder composition of the present invention, preferably an aqueous binder composition, which can be used as alternatives A and B above, and a method for preparing such oxidized lignin, are also described.

[0581] Below, we describe oxidized lignins that can be used as components in binder compositions and their preparation.

[0582] Method I for preparing lignin

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

[0584] Contact the following components:

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

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

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

[0588] Component (a)

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

[0590] In one embodiment of the method of the present invention, component (a) comprises one or more sulfate lignins, one or more alkali lignins, one or more lignin sulfonate lignins, one or more organic solvent lignins, one or more lignins derived from a biorefining process of lignin cellulose raw materials, or any mixture thereof.

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

[0592] Component (b)

[0593] In one embodiment of the invention, component (b) comprises ammonia, one or more amino components, and / or any salts thereof. Not wishing to be bound by any particular theory, the inventors believe that replacing the alkali metal hydroxides used in previously known lignin oxidation methods with ammonia, one or more amino components, and / or any salts thereof plays a significant role in improving the properties of oxidized lignin prepared according to the method of the present invention.

[0594] The inventors have surprisingly discovered that lignin oxidized by an oxidant in the presence of ammonia or amine contains a significant amount of nitrogen as part of the lignin oxide structure. Not wishing to be bound by any particular theory, the inventors believe that the improved fire resistance of lignin oxide, when used in products in which lignin oxide prepared by the method of the present invention is included in a binder composition, is at least in part due to the nitrogen content of the lignin oxide structure.

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

[0596] Not wishing to be bound by any particular theory, the inventors believe that the improved stability of the derivatized lignin prepared according to the present invention is 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 methods.

[0597] However, in the method of the present invention, it may be advantageous for component (b) to contain a considerable amount of alkali metal and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide, in addition to ammonia, one or more amino components and / or any of their salts.

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

[0599] Component (c)

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

[0601] In one embodiment, component (c) comprises one or more oxidants, which are in the form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogenated oxidants, or any mixture thereof.

[0602] In the initial step of the oxidation, the active free radical from the oxidant typically abstracts a proton from the phenolic group, as this bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize free radicals through mediation, multiple pathways are opened to continue (but also terminate) the reaction and yield a variety of intermediates and final products. Because of this complexity (and the conditions of choice), the average molecular weight can either increase or decrease, and in the inventors' experiments, they have typically observed a modest increase in the average molecular weight of approximately 30%.

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

[0604] Hydrogen peroxide is perhaps 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 because they lead to the following reactions that result in free radical formation:

[0605]

[0606] The inventors have discovered that the derivatized lignin prepared by the method of the present invention contains an increased amount of carboxylic acid groups due to the oxidation process. Not wishing to be bound by any particular theory, the inventors believe that the content of carboxylic acid groups in the oxidized lignin prepared by the method of the present invention plays an important role in the desired reactivity properties of the derivatized lignin prepared by the method of the present invention.

[0607] Another advantage of the oxidation method is that the oxidized lignin is more hydrophilic. Higher hydrophilicity can improve solubility in water and promote adhesion to polar substrates such as mineral fibers.

[0608] Other components

[0609] In one embodiment, the method of the present invention comprises additional components, particularly component (d) in the form of an oxidation catalyst, such as one or more transition metal catalysts, such as ferric sulfate, or catalysts containing manganese, palladium, selenium, or tungsten.

[0610] Such an oxidation catalyst can increase the reaction rate, thereby improving the properties of oxidized lignin prepared by the method of the present invention.

[0611] The mass ratio of the components

[0612] Those skilled in the art will use the components (a), (b), and (c) in relative amounts to achieve the desired degree of lignin oxidation.

[0613] In one implementation scheme

[0614] - Component (a) contains one or more lignins,

[0615] - Component (b) contains ammonia,

[0616] - Component (c) contains one or more oxidants in the form of hydrogen peroxide.

[0617] 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, for example 0.1 to 0.3 parts by weight, for example 0.15 to 0.25 parts by weight, based on the dry weight of lignin, and the amount of hydrogen peroxide is 0.025 to 1.0 parts by weight, for example 0.05 to 0.2 parts by weight, for example 0.075 to 0.125 parts by weight, based on the dry weight of lignin.

[0618] method

[0619] There is more than one possibility for contacting the components (a), (b), and (c) to achieve the desired oxidation reaction.

[0620] In one implementation, the method includes the following steps:

[0621] - The step of providing a component (a) in the form of an aqueous solution and / or dispersion of one or more lignins, wherein the aqueous solution has a lignin content of 1 to 50% by weight, for example 5 to 25% by weight, for example 15 to 22% by weight, for example 18 to 20% by weight, based on the total weight of the aqueous solution;

[0622] - A pH adjustment step performed by adding a component (b) of an aqueous solution containing ammonia, one or more amine components and / or any of their salts;

[0623] - An oxidation step performed by adding a component (c) containing an oxidant.

[0624] In one embodiment, the pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH value of ≥9, for example ≥10, for example ≥10.5.

[0625] 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.

[0626] In one embodiment, the pH adjustment step is performed such that the temperature is allowed to rise to ≥25°C and then controlled within the range of 25 to 50°C, for example 30 to 45°C, for example 35 to 40°C.

[0627] In one embodiment, during the oxidation step, the temperature is allowed to rise by ≥35°C and then controlled within the range of 35 to 150°C, for example 40 to 90°C, or for example 45 to 80°C.

[0628] In one embodiment, the oxidation step is carried out for a period of 1 second to 48 hours, for example 10 seconds to 36 hours, for example 1 minute to 24 hours, for example 2 to 5 hours.

[0629] Method II for preparing oxylignin

[0630] Oxidized lignin, which can be used as a component of the binder in this invention, can be prepared by a method comprising the following steps:

[0631] Contact the following components:

[0632] - A component (a) containing one or more lignins,

[0633] - A component containing ammonia and / or one or more amine components and / or any of their salts and / or bases and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide (b),

[0634] - Component (c) containing one or more oxidizing agents,

[0635] - Components in the form of one or more plasticizers (d).

[0636] Component (a)

[0637] Component (a) contains one or more lignins.

[0638] In one embodiment of the method of the present invention, component (a) comprises one or more sulfate lignins, one or more alkali lignins, one or more lignin sulfonate lignins, one or more organic solvent lignins, one or more lignins derived from a biorefining process of lignin cellulose raw materials, or any mixture thereof.

[0639] In one embodiment, component (a) comprises one or more sulfate lignins.

[0640] Component (b)

[0641] In one embodiment of the invention, component (b) comprises ammonia, one or more amino components and / or any salts thereof, and / or alkalis and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide.

[0642] "Ammonia-oxidized lignin" should be understood as lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.

[0643] In one embodiment, component (b) comprises ammonia and / or any of its salts.

[0644] Without wishing to be bound by any particular theory, the inventors believe that the improved stability of the derivatized lignin prepared according to the present invention using ammonia and / or any of its salts as component (b) is 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.

[0645] However, in this embodiment of the method of the invention, it may be advantageous for component (b) to contain a considerable amount of alkali metal and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide, in addition to ammonia, one or more amino components and / or any of their salts.

[0646] In embodiments in which component (b) comprises alkali metal and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide as components other than ammonia, one or more amino components and / or any of their salts, the amount of the alkali metal and / or alkaline earth metal hydroxides is typically small, for example, 5 to 70 parts by weight, such as 10 to 20 parts by weight, based on ammonia.

[0647] Component (c)

[0648] In the method of the present invention, component (c) comprises one or more oxidizing agents.

[0649] In one embodiment, component (c) comprises one or more oxidants, which are in the form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogenated oxidants, or any mixture thereof.

[0650] In the initial step of the oxidation, the active free radical from the oxidant typically abstracts a proton from the phenolic group, as this bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize free radicals through mediation, multiple pathways are opened to continue (but also terminate) the reaction and yield a variety of intermediates and final products. Because of this complexity (and the conditions of choice), the average molecular weight can either increase or decrease, and in the inventors' experiments, they have typically observed a modest increase in the average molecular weight of approximately 30%.

[0651] In one embodiment, component (c) comprises hydrogen peroxide.

[0652] Hydrogen peroxide is perhaps 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 because they lead to the following reactions that result in free radical formation:

[0653]

[0654] The inventors have discovered that the derivatized lignin prepared by the method of the present invention contains an increased amount of carboxylic acid groups due to the oxidation process. Not wishing to be bound by any particular theory, the inventors believe that the content of carboxylic acid groups in the oxidized lignin prepared by the method of the present invention plays an important role in the desired reactivity properties of the derivatized lignin prepared by the method of the present invention.

[0655] Another advantage of the oxidation method is that the oxidized lignin is more hydrophilic. Higher hydrophilicity can improve solubility in water and promote adhesion to polar substrates such as mineral fibers.

[0656] Component (d)

[0657] Component (d) contains one or more plasticizers.

[0658] In one embodiment of the 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, 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 having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides such as urea / urea, or any mixture thereof.

[0659] The inventors have discovered 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 method for producing lignin oxide very efficient.

[0660] In one embodiment of the 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 polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides such as urea / urea, or any mixture thereof.

[0661] In one embodiment of the invention, component (d) comprises one or more plasticizers selected from the group consisting of polyethylene glycol, polyvinyl alcohol, urea, or any mixture thereof.

[0662] Other components

[0663] In one embodiment, the method of the present invention comprises additional components, particularly component (v) in the form of an oxidation catalyst, such as one or more transition metal catalysts, such as ferric sulfate, or catalysts containing manganese, palladium, selenium, or tungsten.

[0664] Such an oxidation catalyst can increase the reaction rate, thereby improving the properties of the oxidized lignin prepared by the method.

[0665] The mass ratio of the components

[0666] Those skilled in the art will use the components (a), (b), (c), and (d) in relative amounts to achieve the desired degree of lignin oxidation.

[0667] In one embodiment, the method of the present invention is carried out such that the method includes

[0668] - A component (a) containing one or more lignins,

[0669] - Component (b) containing ammonia,

[0670] - A component (c) containing one or more oxidants in the form of hydrogen peroxide.

[0671] - A component (d) containing one or more plasticizers selected from polyethylene glycol.

[0672] The mass ratio of lignin, ammonia, hydrogen peroxide, and polyethylene glycol is such that the amount of ammonia is 0.01 to 0.5 parts by weight, for example 0.1 to 0.3 parts by weight, or 0.15 to 0.25 parts by weight of ammonia (25% by weight aqueous solution), based on the dry weight of lignin; and the amount of hydrogen peroxide (30% by weight aqueous solution) is 0.025 to 1.0 parts by weight, for example 0.07 to 0.50 parts by weight, or 0.15 to 0.30 parts by weight of hydrogen peroxide, based on the dry weight of lignin; and the amount of polyethylene glycol is 0.03 to 0.60 parts by weight, for example 0.07 to 0.50 parts by weight, or 0.10 to 0.40 parts by weight of polyethylene glycol, based on the dry weight of lignin.

[0673] For the purposes of this invention, "dry weight of lignin" is preferably defined as the weight of lignin in the provided form.

[0674] method

[0675] There is more than one possibility for contacting the components (a), (b), (c) and (d) to achieve the desired oxidation reaction.

[0676] In one implementation, the method includes the following steps:

[0677] - The step of providing a component (a) in the form of an aqueous solution and / or dispersion of one or more lignins, wherein the aqueous solution has a lignin content of 5 to 90% by weight, for example 10 to 85% by weight, for example 15 to 70% by weight, based on the total weight of the aqueous solution;

[0678] - pH adjustment step by adding component (b);

[0679] - The step of adding component (d);

[0680] - An oxidation step performed by adding a component (c) containing an oxidant.

[0681] In one embodiment, the pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH value of ≥9, for example ≥10, for example ≥10.5.

[0682] 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.

[0683] In one embodiment, the pH adjustment step is performed such that the temperature is allowed to rise to ≥25°C and then controlled within the range of 25 to 50°C, for example 30 to 45°C, for example 35 to 40°C.

[0684] In one embodiment, during the oxidation step, the temperature is allowed to rise to ≥35°C and then controlled within the range of 35 to 150°C, for example 40 to 90°C, or for example 45 to 80°C.

[0685] In one embodiment, the oxidation step is carried out for a period of 1 second to 24 hours, for example 1 minute to 12 hours, for example 10 minutes to 8 hours, for example 5 minutes to 1 hour.

[0686] The inventors have discovered that the method of the present invention allows for the production of reaction mixtures with high dry matter content, and thus high production volumes are possible in the method of the present invention, which allows the reaction products in the form of oxidized lignin to be used as components in industrially produced products such as mineral fiber products.

[0687] In one embodiment, the method of the invention is carried out such that the dry matter content of the reaction mixture is 20 to 80 wt%, for example 40 to 70 wt%.

[0688] In one embodiment, the method of the invention is carried out such that the viscosity of the lignin oxide has a value of 100 cP to 100,000 cP, for example, 500 cP to 50,000 cP, for example, 1,000 cP to 25,000 cP.

[0689] For the purposes of this invention, viscosity is dynamic viscosity and is defined as the resistance of a liquid / paste to changes in shape or to the movement of adjacent portions relative to each other. Viscosity is measured in centipoises (cP), which is equivalent to 1 mPa·s (millipascal-second). Viscosity is measured using a viscometer at 20°C. For the purposes of this invention, dynamic viscosity can be measured at 20°C using a cone-plate Wells Brookfield viscometer.

[0690] In one embodiment, the method of the invention is carried out such that the method includes a rotor-stator device.

[0691] In one embodiment, the method of the invention is carried out such that it is performed as a continuous or semi-continuous process.

[0692] Apparatus for performing the method

[0693] The present invention also relates to apparatus for performing the methods described above.

[0694] In one embodiment, the apparatus for performing the method includes:

[0695] Rotor-stator assembly,

[0696] - Premixing equipment for components (a), (b), and (d)

[0697] - One or more inlets for water, components (a), (b), (c), and (d),

[0698] - One or more outlets of oxylignin.

[0699] In one embodiment, the device is constructed such that the inlet for the premix of components (a), (b), and (d) is located in the rotor-stator device and the device further includes a chamber having an inlet for component (c) and an outlet for oxylignin.

[0700] A rotor-stator apparatus is a device for processing materials, comprising a stator constructed as an inner cone with a toothed ring. The stator mates with a rotor having arms projecting from a hub. Each of these arms has 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 further outward, undergoing intense shearing, mixing, and redistribution. The upright rotor arms and the underlying container chamber of the apparatus allow for permanent rearrangement of the material from the inside out and provide multiple processing options for dry and / or highly viscous substances, making the apparatus highly useful for thorough mixing, kneading, fibrillation, disintegration, and similar processes important in industrial production. The upright arrangement of the housing facilitates the return of material from the periphery to the center of the apparatus.

[0701] In one embodiment, the rotor-stator device used in the method of the present invention comprises a stator having a gear ring and a rotor having teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator device is characterized by a guide funnel protruding between the arms of the rotor, which concentrates the incoming material flow from above into a central region of the container. The outer surface of the guide funnel defines an annular gap that restricts the material flow. At the rotor, a feed screw is provided for feeding into the working area of ​​the device. The guide funnel retains the product in the active area of ​​the device, and the feed screw generates increased material pressure at the center.

[0702] For further details regarding the rotor-stator device used in one embodiment of the method of the present invention, refer to US2003 / 0042344 A1, which is incorporated herein by reference.

[0703] In one embodiment, the method is implemented such that it uses a rotor-stator device. In this embodiment, the mixing and reaction of the components are carried out in the same rotor-stator device.

[0704] In one embodiment, the method is implemented 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.

[0705] This method can be divided into two steps:

[0706] 1. Preparation of lignin (a) + (b) + (d), and

[0707] 2. Oxidation of lignin.

[0708] Typically, two different types of rotor / stator motors are used:

[0709] 1. Suitable for open rotor / stator motors used to mix lignin powder in water at very high concentrations (30 to 50 wt%). The mixing intensity is relatively low, but specialized auxiliary equipment (inlet funnel, screw, etc.) is required to handle highly viscous materials. Low circumferential speed (maximum 15 m / s). This machine can be used as an intermittent or continuous system.

[0710] 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 rapid chemical reactions. The machine should be used continuously.

[0711] In the open rotor / stator system, a highly concentrated lignin / water concentrate (45 to 50 wt%) is prepared. The lignin powder is slowly added to warm water (30 to 60°C) in which appropriate amounts of ammonia and / or alkali metal base are added. This can be done in batches, or the material can be added intermittently / continuously to create a continuous stream for the next step.

[0712] The resulting material should be maintained at a temperature of approximately 60 degrees Celsius to keep the viscosity as low as possible and thus keep the material pumpable. The hot lignin / water material with 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.

[0713] In one embodiment, the oxidation is carried out in a continuous, online reaction within a closed rotor / stator system. An aqueous solution of ammonia and / or an alkali metal base is metered into the rotor / stator chamber at the highest turbulence / shear point using a metering pump. This ensures a rapid oxidation reaction. The oxidized material (AOL) exits the online reactor and is collected in a suitable tank.

[0714] reaction products

[0715] The inventors have surprisingly discovered that the prepared lignin oxides have very desirable reactive properties, while exhibiting improved fire resistance when used in products in which they are contained in binder compositions, and showing improved long-term stability compared to previously known lignin oxides.

[0716] The oxidized lignin also exhibited improved hydrophilicity.

[0717] An important parameter for the reactivity of the prepared lignin oxide is the content of carboxylic acid groups in the lignin oxide.

[0718] In one embodiment, the prepared lignin oxidase has a carboxylic acid group content of 0.05 to 10 mmol / g, for example 0.1 to 5 mmol / g, for example 0.20 to 2.0 mmol / g, for example 0.40 to 1.5 mmol / g, for example 0.45 to 1.0 mmol / g, based on the dry weight of component (a).

[0719] Another way to describe the content of carboxylic acid groups is to use the average content of carboxylic acid groups per lignin macromolecule calculated according to the following formula:

[0720]

[0721] In one embodiment, the prepared oxylignin has an average carboxylic acid group content of macromolecules with more than 1.5 groups / component(a), such as macromolecules with more than 2 groups / component(a), such as macromolecules with more than 2.5 groups / component(a).

[0722] Method III for the Preparation of Lignin Oxide

[0723] Oxidized lignin, which can be used as a component of the binder in this invention, can be prepared by a method comprising the following steps:

[0724] Contact the following components:

[0725] - A component (a) containing one or more lignins,

[0726] - A component containing ammonia and / or one or more amine components and / or any of their salts and / or bases and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide (b),

[0727] - Component (c) containing one or more oxidizing agents,

[0728] - Optional components (d) in the form of one or more plasticizers,

[0729] And allows for a mixing / oxidation step, in which an oxidized mixture is produced, followed by an oxidation step, in which the oxidized mixture is allowed to continue reacting for a residence time of 1 second to 10 hours, for example 10 seconds to 6 hours, for example 30 seconds to 2 hours.

[0730] Components (a), (b), (c) and (d) are as defined above in Method II for the Preparation of Oxygenated Lignin.

[0731] In one embodiment of the invention, the method includes a premixing step in which the components are brought into contact with each other.

[0732] In the premixing step, the following components may be brought into contact with each other:

[0733] - Component (a) and component (b), or

[0734] - Components (a), (b), and (c), or

[0735] - Components (a), (b), and (d), or

[0736] - Components (a), (b), (c), and (d).

[0737] In one embodiment of the invention, the premixing step can be performed as a separate step, and the mixing / oxidation step can be performed after the premixing step. In this embodiment of the invention, it is particularly advantageous to contact components (a) and (b), and optionally component (d), with each other in the premixing step. Component (c) is then added to the premix produced in the premixing step in the subsequent mixing / oxidation step.

[0738] In another embodiment of the invention, the premixing step may correspond to the mixing / oxidation step. In this embodiment of the invention, components such as component (a), component (b), and component (c) are mixed while the oxidation process is initiated. The subsequent residence time can be performed in the same apparatus used for the mixing / oxidation step. This embodiment of the invention is particularly advantageous if component (c) is air.

[0739] The inventors have discovered that the oxidation rate can be controlled very effectively by performing an oxidation step, preferably in which the reaction mixture is not further mixed, after the mixing / oxidation step. Furthermore, the cost of performing the method is reduced because the oxidation step following the mixing / oxidation step requires less complex equipment.

[0740] Another advantage is the exceptional stability of the produced lignin oxide. Another surprising advantage is the excellent adjustability of the viscosity of the produced lignin oxide. Yet another surprising advantage is the ability to achieve very high concentrations of lignin oxide.

[0741] In one embodiment, the residence time is selected to allow the oxidation reaction to reach the desired degree of completion, preferably complete completion.

[0742] System I for performing Method III

[0743] In one implementation, the system for performing the method includes:

[0744] -At least one rotor-stator assembly,

[0745] - One or more inlets for water and components (a) and (b),

[0746] -One or more outlets of the rotor-stator assembly,

[0747] - At least one reaction device, particularly at least one reaction tube, is arranged downstream of at least one or more outlets in the process flow direction.

[0748] In one embodiment, the system includes one or more inlets for component (c) and / or component (d).

[0749] In one embodiment, the system includes a premixing device.

[0750] The premixing device may include one or more inlets for water and / or component (a) and / or component (b) and / or component (c) and / or component (d).

[0751] In one embodiment of the invention, the premixing device includes inlets for water and components (a) and (b).

[0752] In the premixing step, component (c) may also be mixed with the three components mentioned above (water, component (a), and component (b)). The premixing device may then also have an inlet for component (c). If component (c) is air, the premixing device may be formed as an open mixing container, in which case component (c) has already come 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).

[0753] In one embodiment, the system is constructed such that the inlets for components (a), (b), and (d) are inlets for a premixing device, particularly an open rotor-stator device, wherein the system further comprises an additional rotor-stator device having an inlet for component (c) and an outlet for lignin oxidation.

[0754] The premixing step and the mixing / oxidation step can be performed simultaneously. In this case, the premixing device and the mixing / oxidation device are a single device, i.e., a rotor-stator device.

[0755] In one embodiment, a rotor-stator device used in the method of the present invention comprises a stator having a gear ring and a rotor having teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator device is characterized by a guide funnel protruding between the arms of the rotor, which concentrates the incoming material flow from above into a central region of the container. The outer surface of the guide funnel defines an annular gap that restricts the material flow. At the rotor, a feed screw is provided for feeding into the working area of ​​the device. The guide funnel retains the product in the active area of ​​the device, and the feed screw generates increased material pressure at the center.

[0756] System II for performing Method III

[0757] In one implementation, the system for performing the method includes:

[0758] - One or more inlets for water, components (a) and (b),

[0759] -At least one mixing and oxidation unit with one or more outlets, and

[0760] - At least one mixer / heat exchanger is arranged downstream of at least one or more outlets in the process flow direction, wherein the mixer / heat exchanger includes temperature control devices.

[0761] In one embodiment, the system includes one or more additional inlets for component (c) and / or component (d).

[0762] In one embodiment, the system includes a premixing device.

[0763] The premixing device may include one or more inlets for water and / or component (a) and / or component (b) and / or component (c) and / or component (d).

[0764] In one embodiment, the premixing device includes inlets for water as well as for components (a) and (b).

[0765] In the premixing step, component (c) may also be mixed with the three components mentioned above (water, component (a), and component (b)). The premixing device may then also have an inlet for component (c). If component (c) is air, the premixing device may be formed as an open mixing container, in which case component (c) has already come 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).

[0766] In one embodiment, the system is constructed in such a way that the inlets for components (a), (b), and (d) are inlets for an open rotor-stator device, thereby the system also includes a mixer / heat exchanger having an inlet for component (c) and an outlet for lignin oxide.

[0767] The premixing step and the mixing / oxidation step can be performed simultaneously. In this case, the premixing device and the mixing / oxidation device are a single device.

[0768] In one embodiment, a rotor-stator device used in the method of the present invention comprises a stator having a gear ring and a rotor having teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator device is characterized by a guide funnel protruding between the arms of the rotor, which concentrates the incoming material flow from above into a central region of the container. The outer surface of the guide funnel defines an annular gap that restricts the material flow. At the rotor, a feed screw is provided for feeding into the working area of ​​the device. The guide funnel retains the product in the active area of ​​the device, and the feed screw generates increased material pressure at the center.

[0769] Of course, other equipment can also be used as premixing equipment. Moreover, the premixing step can be carried out in a mixing and oxidation apparatus.

[0770] In one embodiment, the mixing and oxidation device is a static mixer. A static mixer is a device with no moving parts used for the continuous mixing of fluid materials. One design of a static mixer is a plate mixer, while another common type consists of mixing elements contained within a cylindrical (tube) or square housing.

[0771] In one embodiment, the mixer / heat exchanger is constructed as a multi-tube heat exchanger with mixing elements. The mixing elements are preferably stationary devices through which the mixture must flow, thereby achieving mixing through the flow. The mixer / heat exchanger can be constructed as a plug flow reactor.

[0772] Example I

[0773] Example IA - Lignin oxidation by hydrogen peroxide in aqueous ammonia solution:

[0774] The amounts of each component used according to Example IA are provided in Tables IA 1.1 and IA 1.2.

[0775] Although lignin sulfate is soluble in water at higher pH values, it is known that the viscosity of the solution increases significantly at certain weight percentages. This viscosity increase is generally attributed to a combination of strong hydrogen bonds and the π-electron interactions of the numerous aromatic rings present in lignin. For lignin sulfate, a sudden increase in viscosity has been observed at approximately 21-22 wt% in water, and 19 wt% lignin sulfate was used in the examples presented.

[0776] Ammonia solution was used as the base in the pH adjustment step. The amount was fixed at 4% by weight, based on the total weight of the reaction. The pH at the start of oxidation after the pH adjustment step was 10.7.

[0777] Table IA2 shows the results of CHNS elemental analysis before and after the oxidation of sulfate lignin. Prior to analysis, the sample was heat-treated at 160°C to remove adsorbed ammonia. The analysis indicates that a certain amount of nitrogen becomes part of the oxidized lignin structure during the oxidation process.

[0778] During intermittent experimental testing, it was determined that adding the full amount of hydrogen peroxide over short time intervals was beneficial for oxidation, as opposed to adding the peroxide in multiple small portions over long periods. In this embodiment, 2.0 wt% H₂O₂ was used based on the total reaction weight.

[0779] The oxidation is an exothermic reaction, and a temperature increase is observed after the addition of the peroxide. In this embodiment, the temperature is maintained at 60°C during the three-hour reaction process.

[0780] After oxidation, through 31 The amount of lignin functional groups per gram of sample was increased, as determined by P NMR and water titration. 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphosphazenecyclopentane (TMDP) was used as the phosphorylation reagent, and cholesterol was used as an internal standard. 31 Sample preparation for P NMR. NMR spectra of sulfate lignin before and after oxidation were obtained, and the results are summarized in Table IA3.

[0781] The change in COOH groups was determined by water titration and using the following formula:

[0782]

[0783] Where V 2s and V 1s It is the final volume of the sample, while V 2b and V 1b It is the empty volume. C 酸 In this example, it is 0.1 M HCl, and m sThis is the weight of the sample. The values ​​obtained from water titration before and after oxidation are shown in Table IA4.

[0784] The average COOH functionality can also be quantified by the saponification value, which represents the number of milligrams of KOH required to saponify 1 gram of lignin. This method can be found in AOCS Official Method Cd 3-25.

[0785] 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 for the calculation of the average carboxylic acid group content per lignin macromolecule, and these results are shown in Table IA5.

[0786] Example IB - Scale-up of lignin oxidation in ammonia via hydrogen peroxide to pilot-scale

[0787] Lignin oxidation using hydrogen peroxide is an exothermic process, and a significant temperature rise can be observed even on laboratory scales upon the addition of peroxide. This is a natural concern when scaling up chemical processes because the heat generated is related to the cubic dimension (volume), while cooling typically increases only with the square of the dimension (area). Furthermore, due to the high viscosity of the binder intermediates, process equipment must be carefully selected or designed. Therefore, scale-up is meticulously planned and carried out in several steps.

[0788] The first scale-up step used a specialized stainless steel mixer with highly efficient mechanical mixing to scale up from 1L (laboratory scale) to 9L. This scale-up resulted only in a slightly higher final temperature than that obtained on a laboratory scale, thanks to effective air cooling of the reactor and the slow addition of hydrogen peroxide.

[0789] The next scale-up step was carried out in a closed 200L reactor equipped with a high-efficiency water jacket and a high-efficiency propeller agitator. The scale-up was 180L this time, and hydrogen peroxide was added in two steps, approximately 30 minutes apart. The scale-up proceeded relatively smoothly, although considerable foaming was a problem, partly due to the high reactor fill level. To control foaming, a small amount of food-grade defoamer was sprayed onto the foam. Crucially, external water cooling was used to achieve a controllable temperature and a final temperature below 70°C.

[0790] The pilot-scale reaction was carried out in an 800L reactor equipped with a water-cooled jacket and a two-blade propeller agitator. 158 kg of lignin (UPM LignoBoos t™ BioPiva 100) with a dry matter content of 67 wt% was de-lumped and suspended in 224 kg of water, and stirred to form a homogeneous suspension. While continuing stirring, 103 kg of 25% ammonia water was pumped into the reactor and stirred for another 2 hours to form a dark, viscous lignin solution.

[0791] Add 140 kg of 7.5 wt% hydrogen peroxide at 20-25 °C to the stirred lignin solution over 15 minutes. Carefully monitor the temperature and foam level during and after the addition of hydrogen peroxide, and add cooling water to the cooling jacket to maintain an acceptable foam level and a temperature rise below 4 °C / min, with a final temperature below 70 °C. After the temperature rise stops, stop cooling and re-stir the product mixture for 2 hours before transferring it to a delivery container.

[0792] Based on the scale-up operation described above, 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, with only the last portion requiring removal through 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 clearer reaction process.

[0793] The tests on the scaled-up batches of material showed that the produced lignin oxide had the same properties as the batches of material produced in the laboratory.

[0794] Table IA 1.1 - Quantity of materials used in the form of supply:

[0795]

[0796] Table IA 1.2 - Amount of active material used:

[0797]

[0798] Table IA 2 - Elemental analysis of sulfate lignin before and after oxidation:

[0799]

[0800] Table IA 3 - Through 31 Distribution of sulfate lignin functional groups before and after oxidation obtained by P NMR:

[0801]

[0802] Table IA 4 - COOH group content determined by water titration (unit: mmol / g):

[0803]

[0804] Table IA 5 - Number-average molar mass (Mn) and weight-average molar mass (Mw) determined by size exclusion chromatography (in g / mol), and the average carboxylic acid group content per lignin macromolecule before and after oxidation.

[0805]

[0806] Example II

[0807] In the following examples, several oxylignins were prepared.

[0808] The following properties were determined for the oxidized lignin:

[0809] Solid content of components:

[0810] The content of each component in a given lignin oxidase solution is based on the anhydrous mass of the component or as described below.

[0811] Sulfate lignin from UPM in BioPivalOO TM Supplied in dry powder form. 25% NH4OH is supplied by Sigma-Aldrich and used as provided. 30% H2O2 (CAS No. 7722-84-1) is supplied by Sigma-Aldrich and used as provided or diluted with water. PEG 200 is supplied by Sigma-Aldrich, assumed to be anhydrous for simplicity, 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) is supplied by Sigma-Aldrich, assumed to be anhydrous for simplicity, and used as is. Urea (CAS No. 57-13-6) is supplied by Sigma-Aldrich and used as provided or diluted with water. Glycerin (CAS No. 56-81-5) was supplied by Sigma-Aldrich and is assumed to be anhydrous and used as is for simplicity.

[0812] Oxidized lignin solids content

[0813] The content of lignin oxide after heating to 200℃ for 1 hour is called the "dry solids content" and is expressed as a percentage of the remaining weight after heating.

[0814] Disc-shaped asbestos samples (5 cm in diameter; 1 cm in height) were cut from the asbestos and heat-treated at 580°C for at least 30 minutes to remove all organic matter. The solids content of the binder mixture was measured by distributing a sample (approximately 2 g) of the binder mixture onto the heat-treated asbestos discs in a foil container. The foil containers containing the asbestos discs were weighed immediately before and after the addition of the binder mixture. Two asbestos discs loaded with this binder mixture were produced in foil containers and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the samples were weighed and the dry solids content was calculated as the average of the two results.

[0815] COOH group content

[0816] The change in COOH group content was also determined by water titration and using the following formula:

[0817]

[0818] Where V 2s and V 1s It is the final volume of the sample, while V 2b and V 1b This is the volume of the blank sample. In this example, C acid is 0.1M HCl, and m... s,g This is the weight of the sample.

[0819] Methods for producing oxylignin:

[0820] 1) Mix water and lignin in a three-necked glass-bottom flask in a water bath at room temperature (20-25°C), the flask being connected to a condenser and a temperature recording device during stirring. Stir for 1 hour.

[0821] 2) Add ammonia all at once during stirring.

[0822] 3) If the slight exothermic reaction with ammonia does not raise the temperature, then raise the temperature to 35°C by heating.

[0823] 4) Measure pH.

[0824] 5) Add plasticizer PEG200 and stir for 10 minutes.

[0825] 6) After the lignin has completely dissolved for about 1 hour, slowly add 30% H2O2 all at once.

[0826] 7) The temperature in the glass-bottom flask was increased by adding H2O2 to the exothermic reaction - if the reaction temperature was below 60°C, the temperature was increased to 60°C and the sample was placed at 60°C for 1 hour.

[0827] 8) Then remove the round-bottom flask from the water bath and cool it to room temperature.

[0828] 9) Take out the sample for determination of dry solids content, COOH, viscosity, density and pH.

[0829] Oxidized Lignin Composition

[0830] Below, the entry numbers for the lignin oxidase examples correspond to the entry numbers used in Table II.

[0831] Example IIA

[0832] 71.0 g of lignin UPM Biopiva 100 was dissolved in 149.0 g of water at 20 °C. 13.3 g of 25% NH4OH was added and the mixture was stirred with a magnetic stirrer for 1 hour. Subsequently, 16.8 g of 30% H2O2 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, thus stopping the reaction. The COOH content, dry solids content, pH, viscosity, and density of the resulting material were analyzed.

[0833] Example IIE

[0834] 71.0 g of lignin UPM Biopiva 100 was dissolved in 88.8 g of water at 20 °C. 13.3 g of 25% NH4OH was added and the mixture was stirred with a magnetic stirrer for 1 hour. 22.8 g of PEG 200 was added and stirred for 10 minutes, followed by the slow addition of 16.7 g of 30% H2O2 while stirring. The temperature was raised to 60 °C in a water bath. After 1 hour of oxidation, the water bath was cooled, thus stopping the reaction. The COOH content, dry solids content, pH, viscosity, and density of the resulting material were analyzed.

[0835] Example IIC

[0836] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 g of water at 20 °C. 13.3 g of 25% NH4OH was added and the mixture was stirred with a magnetic stirrer for 1 hour. Subsequently, 16.6 g of 30% H2O2 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, thus stopping the reaction. The COOH content, dry solids content, pH, viscosity, and density of the resulting material were analyzed.

[0837] Example IIF

[0838] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 g of water at 20 °C. 13.3 g of 25% NH4OH was added and the mixture was stirred with a magnetic stirrer for 1 hour. 19.0 g of PEG 200 was added and stirred for 10 minutes, followed by the slow addition of 16.6 g of 30% H2O2 while stirring. The temperature was raised to 60 °C in a water bath. After 1 hour of oxidation, the water bath was cooled, thus stopping the reaction. The COOH content, dry solids content, pH, viscosity, and density of the resulting material were analyzed.

[0839]

[0840] Example III:

[0841] Mix 8.5 liters of hot water (50°C) and 1.9 liters of NH4OH (24.7%), and then slowly add 9.0 kg of lignin (UPM biopiva 100) to it over 10 minutes with high-speed stirring (660 rpm, 44 Hz).

[0842] The temperature rises due to high shear stress. After 30 minutes, 4 liters of hot water are added, and the material is stirred for another 15 minutes, followed by the addition of the remaining 5 liters of hot water. The sample is then removed for analysis of undissolved lignin and pH measurements using a Hegman Scale.

[0843] The premixture was then transferred to a rotor-stator assembly and a reaction apparatus, where it was oxidized using H2O2 (17.5 vol%). The reaction apparatus used in this example at least partially comprises reaction tubes and a reaction vessel. The premixture was administered at a rate of 150 l / h, and the H2O2 at a rate of 18 l / h.

[0844] In this example, a Cavitron CD1000 rotor-stator unit was used for the mixing / oxidation step. The rotor-stator unit operated at 250 Hz (55 m / s circumferential 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.

[0845] The temperature of the premix is ​​62°C, and the oxidation step raises the temperature to 70°C.

[0846] The COOH group content, dry solids content, pH, viscosity, and residual H2O2 of the final product were analyzed.

[0847] Table III:

[0848]

[0849] Example IV:

[0850] 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 over 15 minutes with high-speed stirring. The sample was removed for analysis of undissolved lignin and pH measurement using the Hegman Scale.

[0851] The premix was then transferred to a static mixer and a mixer / heat exchanger, where it was oxidized using H2O2 (35 vol%). The premix was administered at a dose of 600 L / h, and the H2O2 at a dose of 17.2 L / h. The residence time in the mixer / heat exchanger was 20 minutes.

[0852] The temperature of the mixture is raised to 95°C during the oxidation step.

[0853] The COOH group content, dry solids content, pH, viscosity, and residual H2O2 of the final product were analyzed.

[0854] Based on this AOL, a binder was prepared by mixing 49.3 g AOL (19.0% solids content), 0.8 g primid XL552 (100% solids content), and 2.4 g PEG200 (100% solids content) with 0.8 g water to produce a 19% solids content; the binder was then used to test mechanical properties in a strip test.

[0855] strip test

[0856] The mechanical strength of the binder was tested in a strip test. For each binder, 16 strips were made from a mixture of the binder and asbestos balls produced from asbestos spinning.

[0857] A sample of the binder solution (16.0 g) with a dry solids content of 15% was thoroughly mixed with asbestos balls (80.0 g). The resulting mixture was then filled into four slots of a heat-resistant silicone mold to create strips (4x5 slots per mold; top slot dimensions: length = 5.6 cm, width = 2.5 cm; bottom slot dimensions: length = 5.3 cm, width = 2.2 cm; slot height = 1.1 cm). The mixture placed in the slots was then pressed with a flat metal strip of appropriate size to produce a flat strip surface. Sixteen strips were prepared in this manner from each binder. The resulting strips were then cured at 200°C for 1 hour. After cooling to room temperature, the strips were carefully removed from the container. Five of the strips were aged in a water bath at 80°C for 3 hours.

[0858] After drying for 1-2 days, the aged strip and 5 unaged strips were subjected to a 3-point bending test on a Bent Tram machine (test speed: 10.0 mm / min; fracture level: 50%; nominal strength: 30 N / mm). 2 Support distance: 40 mm; Maximum deviation: 20 mm; Nominal e-modulus: 10000 N / mm 2 To study their mechanical strength, the strips were placed in a machine with the "top surface" (i.e., the surface with dimensions of length = 5.6 cm and width = 2.5 cm) facing upwards.

[0859]

[0860] Experimental part of alternative plan A Example

[0861] In the following embodiments, several mineral wool products containing binders falling within the scope of the present invention were prepared and compared with mineral wool products containing binders of the prior art.

[0862] Unless otherwise specified, percentage (%) values ​​refer to weight percentages.

[0863] The following properties were tested separately for mineral wool products containing the binder of this invention and mineral wool products containing binders of the prior art:

[0864] Determination of isocyanate (ICA) release:

[0865] The amount of ICA released from mineral fiber products containing cured binder compositions can be measured according to Procedure I below. The same Procedure I can also be used to analyze the amount of NH3 and / or HCN released.

[0866] Program I

[0867] Samples of mineral wool products have been analyzed using thermal testing. The thermal testing system consisted of a temperature-adjustable tube furnace equipped with quartz glass tubes, which were connected to a GASMET DX4000FTIR (Fourier Transform Infrared Spectrometer) analyzer via heat-traced transducers. The tubes in the furnace were quartz tubes (23 mm in diameter, 800 mm in length, and 2.0 mm in thickness), with tapered internally threaded glass connectors at both ends: NS24 / 29. The tube furnace used was from Nabertherm, model R30 / 500 / 12-B170.

[0868] The GASMET analyzer is equipped with an internal pump that provides the required amount of gas for proper analysis. The quartz glass tube is open to the surrounding environment to ensure that an appropriate amount of carrier gas, along with the gas released from the test sample, enters the analyzer.

[0869] The mineral wool product was homogenized by crushing. Approximately 2g of sample was weighed and evenly distributed in a porcelain crucible and placed into the quartz tube at a pre-conditioned 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 1L / min at 25°C.

[0870] Before any test run, leaks in the system and the cleanliness of the quartz tube are tested by analyzing the compressed air passing through the system. Cleanliness is only accepted when the test gas is at 0 ppm. Values ​​above 0 ppm will trigger the cleaning of the quartz tube.

[0871] All sample points were repeated three times to ensure high reliability of the measurements.

[0872] After loading the samples, GASMEIT data sampling was initiated. The sampling frequency was adjusted to 5 seconds, followed by approximately 2 seconds of processing, resulting in an average duration of 6.77 seconds for each sample point.

[0873] GASMET's accuracy is 8cm -1 .

[0874] Samples were monitored during data collection to observe the burn-out time of each released species. Data collection was stopped when all species had significantly decreased. Samples collected at 250°C and 350°C were stopped after the time (average duration) shown in Table A, although not all releases decreased to zero (but very close), while samples collected at 450°C and 600°C burned to near-zero values ​​much faster (sometimes only a few minutes).

[0875] The spectra were analyzed using Calcmet software, and the system had been pre-calibrated for each species.

[0876] The release amounts for each sample are compiled, and data are cut off when all release amounts for each species (ICA or any other species to be measured) approach zero. An integral (approximate numerical integral) is then performed below the curve by summing the contributions of each measurement.

[0877] The release rate is calculated by taking into account weight, solids content, and duration. Results are given in units of "ppm isocyanate / g solids content / second". Regarding "g solids content", solids content (LOI) refers to the amount of organic material (loss on ignition) in the mineral fiber product.

[0878] Example of ICA release measurement:

[0879] ICA release of the sample product at 450°C: The total integral below the curve is 6134 ppm ICA, with a cutoff time of 503 seconds, a sample weight of 2.215 g, and a solids content (by weight) of 2.3%. This yields: 6134 ppm ICA / (2.3% · 503 seconds · 2.215 g) = 239 ppm ICA / (g solids content · seconds)

[0880] Determination of solid content (loss on ignition (LOI))

[0881] The amount of organic material (loss on ignition) was determined as the weight loss of the sample obtained by burning off the organic material at 590°C. Typically, the organic material is a binder and impregnating oil. This was done according to the specifications in EN 13820. The binder content was taken as LOI. The binder includes oil and other binder additives, if present.

[0882] Determination of maximum operating temperature

[0883] The maximum operating temperature of mineral fiber products is determined according to the maximum operating temperature plate test of standard EN 14706:2012.

[0884] Determination of the solid content of adhesives

[0885] The amount of adhesive after curing is called "adhesive solids content".

[0886] Disc-shaped asbestos samples (5 cm in diameter; 1 cm in height) were cut from the asbestos and heat-treated at 580°C for at least 30 minutes to remove all organic matter. The solids content of the binder mixture was measured by distributing a sample (approximately 2 g) of the binder mixture onto the heat-treated asbestos discs in a foil container. The foil containers containing the asbestos discs were weighed immediately before and after the addition of the binder mixture. Two asbestos discs loaded with this binder mixture were produced in foil containers and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the samples were weighed and the binder solids content was calculated as the average of the two results.

[0887] Unless otherwise specified, the following reagents are used in the form of receipt:

[0888] Lignin UPM BioPiva 100: Sulfated lignin supplied by UPM, designated BioPiva 100. TM Dry powder.

[0889] PEG 200: Supplied by Sigma-Aldrich, assumed to be anhydrous for simplicity, and used as is.

[0890] Primid XL552: A hydroxyalkylamide crosslinking agent supplied by EMS-CHEMIE AG.

[0891] Momentive VS142: VS-142 is a water-based oligomeric amino silane supplied by Moment ive.

[0892] Preparation of Ammonia-Oxidized Lignin (AOL) Resin

[0893] Add 3267 kg of water to a 6000 L reactor, followed by 287 kg of ammonia (24.7%). Then, slowly add 1531 kg of lignin UPM BioPiva100 over 30 to 45 minutes. Heat the mixture to 40°C and maintain this temperature for 1 hour. After 1 hour, examine the undissolved lignin. This can be done by examining the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in a brown binder. During the dissolution process, the color of the lignin solution changes from brown to glossy black.

[0894] After the lignin is completely dissolved, add 1 liter of defoamer (obtained from...). of 11-10). The batch temperature should be maintained at 40℃.

[0895] Then begin adding 307.5 kg of 35% hydrogen peroxide. The hydrogen peroxide is added at a rate of 200-300 liters per hour. The first half of the hydrogen peroxide is added at a rate of 200 liters per hour, and then the addition rate is increased to 300 liters per hour.

[0896] During the addition of hydrogen peroxide, the temperature of the reaction mixture is controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[0897] After reacting at 65°C for 15 minutes, the reaction mixture was cooled to below 50°C. This yielded a resin with a COOH value of 1.2 mmol / g solids.

[0898] Preparation of the final binder (the uncured binder composition suitable for preparing the mineral fiber products of the present invention)

[0899] The binder was prepared from the above-mentioned AOL resin by adding 270 kg of polyethylene glycol 200 (PEG 200) and 433 kg of 31% Primid XL-552 in water.

[0900] The final analysis of the adhesive revealed the following data:

[0901] Solid content: 18.9%

[0902] pH: 9.7

[0903] Viscosity: 25.5 mPa·s

[0904] Density: 1.066 kg / l

[0905] Comparative Example 1

[0906] This adhesive is made of urea-modified phenolic resin PUF-resol.

[0907] Phenolic resin was prepared by reacting 606 kg of 37% formaldehyde aqueous solution and 189 kg of phenol in the presence of 25.5 kg of 46% potassium hydroxide aqueous solution at a reaction temperature of 84 °C and a heating rate of approximately 1 °C / min to the reaction temperature. The reaction was continued at 84 °C until the resin's acid tolerance was 4 and most of the phenol was converted. Urea (241 kg) was then added and the mixture was cooled.

[0908] Acid tolerance (AT) indicates the factor by which a given volume of binder can be diluted with acid without causing the mixture to become cloudy (binder precipitation). Sulfuric acid is used to determine the stopping criteria in binder production, and an acid tolerance below 4 indicates that the binder reaction has ended.

[0909] To measure AT, a titrant was prepared by diluting 2.5 ml of concentrated sulfuric acid (>99%) with 1 L of deionized water. The 5 ml binder under study was then titrated with this titrant at room temperature while keeping the binder in motion by hand shaking; a magnetic stirrer and magnetic rod could be used if desired. Titration continued until a slight turbidity appeared in the binder, which did not disappear when the binder was shaken.

[0910] Acid tolerance (AT) is calculated by dividing the amount of acid (mL) used for titration by the amount of sample (mL):

[0911] AT = (Titration volume used (mL)) / (Sample volume (mL))

[0912] The obtained urea-modified phenolic resin was used to prepare an adhesive by adding 25% ammonia (90 L) and ammonium sulfate (13.2 kg), followed by water (1300 kg).

[0913] Add 18% dextrose (127.5 kg) based on the dry matter of the binder to the above mixture. Then measure the binder solids content as described above, and dilute the mixture with the required amount of water and silane for mechanical testing.

[0914] A mineral fiber product is prepared comprising 100 mm thick mineral wool bonded using a binder composition of the prior art. The density of the mineral fiber product is 145 kg / m³. 3 The loss on ignition was 2.4%. Due to the 0.1% mineral oil, the cured binder composition constituted 2.3% of the mineral fiber product.

[0915] The prepared mineral fiber products were tested as described in Procedure I. The results are given in Table A below.

[0916] Comparative Example 2

[0917] A mixture of 75.1% aqueous glucose syrup (19.98 kg, therefore equivalent in potency to 15.0 kg glucose syrup), 50% aqueous hypophosphite (0.60 kg, therefore equivalent in potency to 0.30 kg / 4.55 mol hypophosphite), 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. Then, 28% ammonia (0.80 kg, therefore equivalent in potency to 0.22 kg / 13.15 mol ammonia) was added dropwise until pH = 7.9. The binder solids content was then measured (21.2%). To obtain a suitable binder composition (a solution with 15% binder solids content, 0.5% silane in the binder solids), the binder mixture was diluted with water (0.403 kg / kg binder mixture) and a 10% aqueous silane solution (0.011 kg / kg binder mixture, Momentive VS-142). The final binder mixture has a pH of 7.9.

[0918] Prepare a thickness of 100 mm and a density of 145 kg / m³ 3 The mineral fiber product has an LOI of 2.5%. It is prepared using the common methods described above for preparing the mineral fiber product.

[0919] The prepared mineral fiber products were tested as described in Procedure I. The results are given in Table A below.

[0920] Example 1

[0921] Add 3267 kg of water to a 6000 L reactor, followed by 861 kg of ammonia (24.7%). Then, slowly add 1531 kg of lignin UPM BioPiva100 over 30 to 45 minutes. Heat the mixture to 40°C and maintain this temperature for 1 hour. After 1 hour, examine the undissolved lignin. This can be done by examining the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in a brown binder. During the dissolution process, the color of the lignin solution changes from brown to glossy black.

[0922] After the lignin is completely dissolved, add 1 liter of defoamer (obtained from...). of 11-10). The batch temperature should be maintained at 40℃.

[0923] Then begin adding 307.5 kg of 35% hydrogen peroxide. The hydrogen peroxide is added at a rate of 200-300 liters per hour. The first half of the hydrogen peroxide is added at a rate of 200 liters per hour, and then the addition rate is increased to 300 liters per hour.

[0924] During the addition of hydrogen peroxide, the temperature of the reaction mixture is controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[0925] After reacting at 65°C for 15 minutes, the reaction mixture was cooled to below 50°C. This yielded a resin with a COOH value of 1.1 mmol / g solids.

[0926] Preparation of final adhesive

[0927] The binder was prepared from the above-mentioned AOL resin by adding 270 kg of polyethylene glycol 200 and 396 kg of 31% Primid XL-552 in water.

[0928] The final analysis of the adhesive revealed the following data:

[0929] Solid content: 18.9%

[0930] pH: 10.2

[0931] Viscosity: 25.5 mPa·s

[0932] Density: 1.066 kg / l.

[0933] The mineral fiber product of the present invention is prepared by using a 100mm bonded mineral wool and the resulting binder composition to obtain a lignin-based cured binder composition. The commonly used method for producing mineral fiber products described above in the description section is used. The density of the mineral fiber product is 145 kg / m³. 3 The loss on ignition is 2.3%. The cured binder composition accounts for 2.2% of the mineral fiber product. The binder composition used, as described above, includes 0.1% mineral oil.

[0934] The prepared mineral fiber products were tested as described in Procedure I. The results are given in Table A below.

[0935] Example 2

[0936] Add 3267 kg of water to a 6000 L reactor, followed by 287 kg of ammonia (24.7%). Then, slowly add 1531 kg of lignin UPM BioPiva100 over 30 to 45 minutes. Heat the mixture to 40°C and maintain this temperature for 1 hour. After 1 hour, examine the undissolved lignin. This can be done by examining the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in a brown binder. During the dissolution process, the color of the lignin solution changes from brown to glossy black.

[0937] After the lignin is completely dissolved, add 1 liter of defoamer (obtained from...). of 11-10). The batch temperature should be maintained at 40℃.

[0938] Then begin adding 307.5 kg of 35% hydrogen peroxide. The hydrogen peroxide is added at a rate of 200-300 liters per hour. The first half of the hydrogen peroxide is added at a rate of 200 liters per hour, and then the addition rate is increased to 300 liters per hour.

[0939] During the addition of hydrogen peroxide, the temperature of the reaction mixture is controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[0940] After reacting at 65°C for 15 minutes, the reaction mixture was cooled to below 50°C. This yielded a resin with a COOH value of 1.2 mmol / g solids.

[0941] Preparation of final adhesive

[0942] The binder was prepared from the above-mentioned AOL resin by adding 270 kg of polyethylene glycol 200 and 433 kg of 31% Primid XL-552 in water.

[0943] The final analysis of the adhesive revealed the following data:

[0944] Solid content: 18.9%

[0945] pH: 9.7

[0946] Viscosity: 25.5 mPa·s

[0947] Density: 1.066 kg / l.

[0948] This binder composition is used with 100mm mineral wool to produce a density of 145kg / m³. 3A mineral wool product with a thickness of 100 mm and a loss on ignition of 2.4% was produced. The common methods for producing mineral fiber products described above in the description section were used. The material was used as described in Procedure I. The results are given in Table A below.

[0949] Heat release in Examples 1 and 2 and Comparative Examples 1 and 2

[0950] 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 were tested at temperatures of 250°C, 350°C, 450°C, and 600°C, respectively, according to Procedure I described above.

[0951] The results are shown in Table A below. The output values ​​given are the average release amounts for each species, in ppm / g solids / s (ppm / g solids·s).

[0952] Table A

[0953]

[0954] The release rates of the mineral wool products from the four tests have been obtained, allowing us to rank the release rates of the systems relative to each other.

[0955] Overall, the release rate of Comparative Example 1 was significantly higher than that of Comparative Example 2, as well as Examples 1 and 2. Examples 1 and 2 showed substantially the same release rate for all species at all temperatures, regardless of the chemical composition of the binder used in these mineral wool products.

[0956] The results show that Comparative Example 1 exhibits the highest levels of released substances (ICA, NH3, and HCN). Comparative Example 1 releases the highest amount of ICA. The ICA release rate of Comparative Example 2 is higher than that of Examples 1 and 2. Examples 1 and 2 have approximately the same release rate at all temperatures.

[0957] Regarding ammonia, Comparative Example 1 showed the highest level of NH3 release. The NH3 release rate of Comparative Example 2 was comparable to that of Examples 1 and 2.

[0958] Compared to Examples 2 and 3, the HCN release rates in Comparative Examples 1 and 2 increased (by increasing the temperature). Again, Comparative Example 1 showed the highest level of emissions.

[0959] Maximum operating temperature test of Example 1 and Comparative Example 1

[0960] The performance of the products in Example 1 and Comparative Example 1 was tested according to the following test method: maximum operating temperature plate test; EN 14706:2012, to demonstrate the thermal stability of the mineral wool products at high temperatures. Both products underwent multiple tests.

[0961] The measurement and testing results of the product in Example 1 are as follows:

[0962]

[0963] Therefore, the highest operating temperature value measured in Example 1 was ST(+) = 650℃ ± 10℃. This value is consistent with the selected test temperature ST(+) = 650℃, but it is at the upper limit of the exothermic reaction.

[0964] The measurement and testing results of the product in Comparative Example 1 are as follows:

[0965]

[0966] Therefore, the highest operating temperature measured was ST(+) = 650℃ ± 10℃. This value does not match the selected test temperature ST(+) = 650℃, because it has reached the upper limit of the exothermic reaction.

[0967] The product in Example 1 meets the requirements of EN 14706:2012 for exothermic reactions during the maximum operating temperature plate test. The product in Comparative Example 1 does not meet the standard for exothermic reactions during the test because the half-height temperature of the test sample rose above the temperature set point during the test. Both products meet all other test standards of EN14706:2012 for the maximum operating temperature plate test.

[0968] Experimental part of alternative plan B

[0969] Example

[0970] In the following embodiments, several mineral wool products containing binders falling within the scope of the present invention were prepared and compared with mineral wool products containing binders of the prior art.

[0971] Unless otherwise specified, percentage (%) values ​​refer to weight percentages.

[0972] The following properties were tested separately for mineral wool products containing the binder of this invention and mineral wool products containing binders of the prior art:

[0973] Determination of isocyanate (ICA) release:

[0974] The total amount of ICA released from mineral fiber products containing cured binder compositions can be measured according to Procedure II below. The same Procedure II can also be used to analyze the total amount of HCN released.

[0975] Program II

[0976] Samples of mineral wool products have been analyzed using thermal testing. The thermal testing system consisted of a temperature-adjustable tube furnace equipped with quartz glass tubes, which were connected to a GASMET DX4000FTIR (Fourier Transform Infrared Spectrometer) analyzer via a heat-traced transfer tube. The tubes in the furnace were quartz tubes (23 mm in diameter, 800 mm in length, and 2.0 mm in thickness), with tapered internally threaded glass connectors at both ends: NS24 / 29. The tube furnace used was from Naber thermom, model R30 / 500 / 12-B170.

[0977] The GASMET analyzer is equipped with an internal pump that provides the required amount of gas for proper analysis. The quartz glass tube is open to the surrounding environment to ensure that an appropriate amount of carrier gas, along with the gas released from the test sample, enters the analyzer.

[0978] The mineral wool product was homogenized by crushing. Approximately 2g of sample was weighed and evenly distributed in a porcelain crucible and placed into the quartz tube at a pre-conditioned 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 3L / min at 25°C.

[0979] Before any test run, leaks in the system and the cleanliness of the quartz tube are tested by analyzing the air passing through the system. Cleanliness is only accepted when the test gas is at 0 ppm. Values ​​above 0 ppm will trigger the cleaning of the quartz tube.

[0980] All sample points were repeated three times to ensure high reliability of the measurements.

[0981] After loading the samples, GASMET data sampling was initiated. The sampling frequency was adjusted to 30 seconds, followed by approximately 2 seconds of processing, resulting in an average duration of 32 seconds for each sample point.

[0982] GASMET's accuracy is 8cm -1 .

[0983] Samples were monitored during data collection to observe the burn-out time of all released species. Data collection was stopped when the responses of all species had dropped to zero or reached a stable near-zero level. Samples collected at 250°C and 350°C burned to near-zero values ​​after approximately one hour, while samples collected at 450°C and 600°C burned to near-zero values ​​much faster (sometimes within minutes).

[0984] The spectra were analyzed using Calcmet software, and the system had been pre-calibrated for each species.

[0985] The release of each sample was processed individually by measuring the exact elapsed time from the start of release by the species until it dropped to zero or near zero. The integral below the curve was obtained by summing the contributions of each measurement (approximate numerical integration).

[0986] The total release was calculated by taking into account the sample weight, molar volume at 0°C and 1 atm, applied gas flow rate, and molecular weight of the released species. Results are given in micrograms per gram of sample.

[0987] Example:

[0988] ICA release of the sample product at 250°C: recorded at a flow rate of 3 L / min, the average ICA release from a 1.501 g sample over 34 minutes was 2.35 ppm. This yields: 2.35 ppm ICA · 43.03 g / mol / 22.4 L · 34 min · 3 L / min / 1.501 g = 306 μg / g sample.

[0989] Determination of solid content (loss on ignition (LOI))

[0990] The amount of organic material (loss on ignition) was determined as the weight loss of the sample obtained by burning off the organic material at 590°C. Typically, the organic material is a binder and impregnating oil. This was done according to the specifications in EN 13820. The binder content was taken as LOI. The binder includes oil and other binder additives, if present.

[0991] Determination of maximum operating temperature

[0992] The maximum operating temperature of mineral fiber products is determined according to the maximum operating temperature plate test of standard EN 14706:2012.

[0993] Determination of the solid content of adhesives

[0994] The amount of adhesive after curing is called "adhesive solids content".

[0995] Disc-shaped asbestos samples (5 cm in diameter; 1 cm in height) were cut from the asbestos and heat-treated at 580°C for at least 30 minutes to remove all organic matter. The solids content of the binder mixture was measured by distributing a sample (approximately 2 g) of the binder mixture onto the heat-treated asbestos discs in a foil container. The foil containers containing the asbestos discs were weighed immediately before and after the addition of the binder mixture. Two asbestos discs loaded with this binder mixture were produced in foil containers and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the samples were weighed and the binder solids content was calculated as the average of the two results.

[0996] Unless otherwise specified, the following reagents are used in the form of receipt:

[0997] Lignin UPM BioPiva 100: Sulfated lignin supplied by UPM, designated BioPiva 100. TM Dry powder.

[0998] PEG 200: Supplied by Sigma-Aldrich, assumed to be anhydrous for simplicity, and used as is.

[0999] Primid XL552: A hydroxyalkylamide crosslinking agent supplied by EMS-CHEMIE AG.

[1000] Momentive VS142: VS-142 is a water-based oligomeric amino silane supplied by Moment ive.

[1001] Preparation of Ammonia-Oxidized Lignin (AOL) Resin

[1002] Add 3267 kg of water to a 6000 L reactor, followed by 287 kg of ammonia (24.7%). Then, slowly add 1531 kg of lignin UPM BioPiva100 over 30 to 45 minutes. Heat the mixture to 40°C and maintain this temperature for 1 hour. After 1 hour, examine the undissolved lignin. This can be done by examining the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in a brown binder. During the dissolution process, the color of the lignin solution changes from brown to glossy black.

[1003] After the lignin is completely dissolved, add 1 liter of defoamer (obtained from...). of 11-10). The batch temperature should be maintained at 40℃.

[1004] Then begin adding 307.5 kg of 35% hydrogen peroxide. The hydrogen peroxide is added at a rate of 200-300 liters per hour. The first half of the hydrogen peroxide is added at a rate of 200 liters per hour, and then the addition rate is increased to 300 liters per hour.

[1005] During the addition of hydrogen peroxide, the temperature of the reaction mixture is controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[1006] After reacting at 65°C for 15 minutes, the reaction mixture was cooled to below 50°C. This yielded a resin with a COOH value of 1.2 mmol / g solids.

[1007] Preparation of the final binder (the uncured binder composition suitable for preparing the mineral fiber products of the present invention)

[1008] The binder was prepared from the above-mentioned AOL resin by adding 270 kg of polyethylene glycol 200 (PEG 200) and 433 kg of 31% Primid XL-552 in water.

[1009] The final analysis of the adhesive revealed the following data:

[1010] Solid content: 18.9%

[1011] pH: 9.7

[1012] Viscosity: 25.5 mPa·s

[1013] Density: 1.066 kg / l

[1014] Comparative Example 3

[1015] This adhesive is made of urea-modified phenolic resin PUF-resol.

[1016] Phenolic resin was prepared by reacting 606 kg of 37% formaldehyde aqueous solution and 189 kg of phenol in the presence of 25.5 kg of 46% potassium hydroxide aqueous solution at a reaction temperature of 84 °C and a heating rate of approximately 1 °C / min to the reaction temperature. The reaction was continued at 84 °C until the resin's acid tolerance was 4 and most of the phenol was converted. Urea (241 kg) was then added and the mixture was cooled.

[1017] Acid tolerance (AT) indicates the factor by which a given volume of binder can be diluted with acid without causing the mixture to become cloudy (binder precipitation). Sulfuric acid is used to determine the stopping criteria in binder production, and an acid tolerance below 4 indicates that the binder reaction has ended.

[1018] To measure AT, a titrant was prepared by diluting 2.5 ml of concentrated sulfuric acid (>99%) with 1 L of deionized water. The 5 ml binder under study was then titrated with this titrant at room temperature while keeping the binder in motion by hand shaking; a magnetic stirrer and magnetic rod could be used if desired. Titration continued until a slight turbidity appeared in the binder, which did not disappear when the binder was shaken.

[1019] Acid tolerance (AT) is calculated by dividing the amount of acid (mL) used for titration by the amount of sample (mL):

[1020] AT = (Titration volume used (mL)) / (Sample volume (mL))

[1021] The obtained urea-modified phenolic resin was used to prepare an adhesive by adding 25% ammonia (90 L) and ammonium sulfate (13.2 kg), followed by water (1300 kg).

[1022] Add the dry matter based on the above binder and 18% dextrose (127.5 kg) to the above mixture.

[1023] 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.

[1024] Mineral fiber products in the form of tubular components are prepared, with a thickness of 40 mm (inner diameter of 219 mm) and a strength of 100 kg / m³. 3 The density and loss on ignition are 3.1%. Common methods for producing mineral fiber products, as described above, are employed.

[1025] The prepared mineral fiber products were tested as described in Procedure II. The results are given in Table B below.

[1026] Comparative Example 4

[1027] This adhesive is made of urea-modified phenolic resin PUF-resol.

[1028] Phenolic resin was prepared by reacting 606 kg of 37% formaldehyde aqueous solution and 189 kg of phenol in the presence of 25.5 kg of 46% potassium hydroxide aqueous solution at a reaction temperature of 84 °C and a heating rate of approximately 1 °C / min to the reaction temperature. The reaction was continued at 84 °C until the resin's acid tolerance was 4 and most of the phenol was converted. Urea (241 kg) was then added and the mixture was cooled.

[1029] Acid tolerance (AT) indicates the factor by which a given volume of binder can be diluted with acid without causing the mixture to become cloudy (binder precipitation). Sulfuric acid is used to determine the stopping criteria in binder production, and an acid tolerance below 4 indicates that the binder reaction has ended.

[1030] To measure AT, a titrant was prepared by diluting 2.5 ml of concentrated sulfuric acid (>99%) with 1 L of deionized water. The 5 ml binder under study was then titrated with this titrant at room temperature while keeping the binder in motion by hand shaking; a magnetic stirrer and magnetic rod could be used if desired. Titration continued until a slight turbidity appeared in the binder, which did not disappear when the binder was shaken.

[1031] Acid tolerance (AT) is calculated by dividing the amount of acid (mL) used for titration by the amount of sample (mL):

[1032] AT = (Titration volume used (mL)) / (Sample volume (mL))

[1033] The obtained urea-modified phenolic resin was used to prepare an adhesive by adding 25% ammonia (90 L) and ammonium sulfate (13.2 kg), followed by water (1300 kg).

[1034] Add the dry matter based on the above binder and 18% dextrose (127.5 kg) to the above mixture.

[1035] 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.

[1036] Prepare a mineral fiber product in the form of a filament-reinforced pad, with a thickness of 100 mm and a strength of 100 kg / m². 3 The density and loss on ignition are 0.3%. Common methods for producing mineral fiber products, as described above, are employed.

[1037] The prepared mineral fiber products were tested as described in Procedure II. The results are given in Table B below.

[1038] Example 3

[1039] Add 3267 kg of water to a 6000 L reactor, followed by 861 kg of ammonia (24.7%). Then, slowly add 1531 kg of lignin UPM BioPiva100 over 30 to 45 minutes. Heat the mixture to 40°C and maintain this temperature for 1 hour. After 1 hour, examine the undissolved lignin. This can be done by examining the solution on a glass plate or a Hegman gauge. Undissolved lignin can be seen as small particles in a brown binder. During the dissolution process, the color of the lignin solution changes from brown to glossy black.

[1040] After the lignin is completely dissolved, add 1 liter of defoamer (obtained from...). of 11-10). The batch temperature should be maintained at 40℃.

[1041] Then begin adding 307.5 kg of 35% hydrogen peroxide. The hydrogen peroxide is added at a rate of 200-300 liters per hour. The first half of the hydrogen peroxide is added at a rate of 200 liters per hour, and then the addition rate is increased to 300 liters per hour.

[1042] During the addition of hydrogen peroxide, the temperature of the reaction mixture is controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[1043] After reacting at 65°C for 15 minutes, the reaction mixture was cooled to below 50°C. This yielded a resin with a COOH value of 1.1 mmol / g solids.

[1044] Preparation of final adhesive

[1045] The binder was prepared from the above-mentioned AOL resin by adding 270 kg of polyethylene glycol 200 and 396 kg of 31% Primid XL-552 in water.

[1046] The final analysis of the adhesive revealed the following data:

[1047] Solid content: 18.9%

[1048] pH: 10.2

[1049] Viscosity: 25.5 mPa·s

[1050] Density: 1.066 kg / l.

[1051] Mineral fiber products in the form of filament-reinforced pads are prepared, with a thickness of 80 mm and a strength of 100 kg / m². 3 The density and loss on ignition are 0.3%. Common methods for producing mineral fiber products, as described above, are employed.

[1052] The prepared mineral fiber products were tested as described in Procedure II. The results are given in Table B below.

[1053] Heat release in Examples 3 and 3-4

[1054] According to Procedure II described above, the isocyanate (ICA) and HCN release characteristics of the mineral fiber products of Example 3 and Comparative Examples 3 to 4 were tested at temperatures of 250°C, 350°C, 450°C and 600°C, respectively.

[1055] The results are shown in Table B below. The output values ​​given are average values ​​of the release amount of each species, expressed in micrograms per gram of sample (μg / g sample).

[1056] Table B

[1057]

[1058]

[1059] Having obtained the release amounts of the three types of mineral wool products tested, we were able to relative rank the total release amounts of the system.

[1060] Overall, the total release amount of Comparative Example 3 was significantly higher than that of Comparative Example 4, and especially higher than that of Example 3.

[1061] The results show that Comparative Example 3 exhibits the highest levels of released substances (ICA and HCN) to date, which can be seen from the relatively high LOI content of the tested products.

[1062] The total ICA and HCN release in Comparative Example 4 were still higher than those in Example 3, even though the LOI content was similar in both.

[1063] Maximum operating temperature test in Example 3

[1064] The performance of the product in Example 3 was tested according to the following test methods: maximum operating temperature plate test; EN14706:2012, to demonstrate the thermal stability of the mineral wool product at high temperatures. The product underwent multiple tests.

[1065] The highest operating temperature of Example 3 was measured to be ST(+) = 660℃ ± 10℃. This value is consistent with the selected test temperature ST(+) = 660℃.

Claims

1. The use of mineral fiber products as thermal insulation materials for heat pipes, said mineral fiber products comprising mineral fibers bonded by a cured adhesive composition, wherein the uncured adhesive composition comprises: - Components in the form of one or more oxidized lignins (i), and - Components in the form of one or more cross-linking agents (ii).

2. The use according to claim 1, wherein the mineral fiber product is in the form of a pre-formed tube segment, a wire-reinforced pad, or a thick plate.

3. The use as claimed in claim 1 or claim 2, wherein the use is operated at a temperature of at least 300°C, preferably at least 400°C, more preferably at least 450°C and / or up to 700°C.

4. The use of any of the preceding claims, wherein the conduit operates at a high operating temperature of at least 400°C, preferably at least 450°C and / or up to 700°C.

5. The use of any one of the preceding claims, wherein the pipe is a metal pipe.

6. The use of any one of the preceding claims, wherein a medium such as gas, steam or fluid is conveyed in the pipeline.

7. The use according to any one of the preceding claims, wherein heating the mineral fiber product to a temperature of 600°C releases less than 1500 ppm isocyanate (ICA) / g solids content / second, or wherein heating the mineral fiber product containing the cured binder composition to a temperature of 600°C releases less than 1000 μg isocyanate (ICA) / g sample.

8. The use according to any one of the preceding claims, wherein heating the mineral fiber product to 600°C releases less than 2500 ppm NH3 / gram content / second, for example less than 2000 ppm NH3 / gram content / second, for example less than 1500 ppm NH3 / gram content / second, and / or wherein heating the mineral fiber product to 600°C releases less than 2000 ppm HCN / gram content / second, for example less than 1500 ppm HCN / gram content / second, for example less than 1000 ppm HCN / gram content / second.

9. The use of any one of the preceding claims, wherein the uncured adhesive composition comprises: - Components in the form of one or more plasticizers (iii).

10. The use of any one of the preceding claims, wherein the one or more oxidized lignins are oxidation products of lignin selected from the group consisting of: sulfate lignin, alkali lignin, lignin sulfonate lignin, organic solvent lignin, lignin from a biorefining process of lignin cellulose raw materials, or any mixture thereof.

11. The use of any one of the preceding claims, wherein the one or more oxidized lignins are in the form of one or more ammoniated lignins.

12. The use according to any one of the preceding claims, wherein the one or more oxylignins have a carboxylic acid group content of 0.05 to 10 mmol / g, for example 0.1 to 5 mmol / g, for example 0.20 to 1.5 mmol / g, for example 0.40 to 1.2 mmol / g, for example 0.45 to 1.0 mmol / g, based on the dry weight of the one or more oxylignins.

13. The use of any one of the preceding claims, wherein the component (ii) is in the form of one or more crosslinking agents selected from: a) β-hydroxyalkylamide crosslinking agent and / or oxazoline crosslinking agent, and / or b) Multifunctional organic amines, such as alkanolamines, diamines such as 1,6-hexanediamine, triamines, and / or c) Epoxidized oils based on fatty acid triglycerides or one or more flexible oligomers or polymers, such as low-T g Acrylic polymers, such as low-T g Vinyl polymers, such as low-T g Polyethers containing reactive functional groups such as carbodiimide groups, acid anhydride groups, oxazoline groups, amino groups, epoxy groups, and / or d) Molecules having three or more epoxy groups, and / or e) One or more crosslinking agents selected from the group consisting of polyethyleneimine, polyvinylamine, fatty amines; and / or f) One or more crosslinking agents in the form of fatty amides; and / or g) One or more crosslinking agents selected from the group consisting of: dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid; and / or h) One or more crosslinking agents selected from polyester polyols such as polycaprolactone; and / or i) One or more crosslinking agents selected from the group consisting of starch, modified starch, CMC; and / or j) One or more crosslinking agents in the form of aliphatic polyfunctional carbodiimides; and / or k) One or more crosslinking agents selected from melamine-based crosslinking agents such as hexa(methylmethoxy)melamine (HMMM)-based crosslinking agents.

14. The use according to any one of claims 9-13, wherein component (iii) is included in the uncured adhesive composition in the form of one or more plasticizers selected from the group consisting of: polyethylene glycol, polyethylene glycol ethers, polyethers, hydrogenated sugars, 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 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, monohydroxy alcohols such as pentanol, stearyl alcohol; and / or - One or more plasticizers selected from the group consisting of: alkoxides such as ethoxides, for example, butanol ethoxides such as butoxytriethylene glycol; 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 adipate, acetate, benzoate, cyclobenzoate, citrate, stearate, sorbate, sebate, azelaate, butyrate, valerate; and / or - One or more plasticizers selected from the group consisting of: phenol derivatives, such as 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 such as alkyl sulfates, sulfonates such as alkyl aryl sulfonates, alkyl and / or - Sulfonates, phosphate esters such as tripolyphosphate; 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, such as acetamide, benzamide, fatty acid amides such as tallowamide; and / or - One or more plasticizers selected from the group consisting of quaternary ammonium compounds such as trimethylglycine, distearate dimethylammonium chloride; and / or - One or more plasticizers selected from the group consisting of: vegetable oils, such as castor oil, palm oil, linseed oil, soybean oil; 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 methyl esters; and / or - One or more plasticizers selected from the group consisting of: alkyl polyglucosides, glucosamides, aminoglucosamides, sucrose esters, and sorbitol esters; and / or - One or more plasticizers selected from the group consisting of polyethylene glycol and polyethylene glycol ether.

15. The use of any of the preceding claims, wherein the mineral fiber product meets a maximum operating temperature condition of at least 600°C, preferably at least 650°C, according to the maximum operating temperature plate test of EN 14706:2012.

16. A pipe covered with a mineral fiber product as an insulation material, wherein the mineral fiber product comprises mineral fibers bonded by a cured adhesive composition, and the uncured adhesive composition comprises: - Components in the form of one or more oxidized lignins (i), and - Components in the form of one or more cross-linking agents (ii).

17. The pipe of claim 16, wherein the mineral fiber product is in the form of a pre-formed pipe section or a wire-reinforced gasket.

18. The conduit of claim 16 or claim 17, wherein the conduit is as defined in any one of claims 4-6.

19. The pipe of any one of claims 16-18, wherein the mineral fiber product is as defined in any one of claims 7-15.

Images