Roof system and insulating element for flat or slightly pitched roofs

Abstract

The present invention relates to a roof system for flat or slightly pitched roofs of buildings with thermal and / or acoustic insulation, said system consisting of a structural support, a support board, optionally a vapour control layer, a waterproofing membrane and at least one insulating element which is a bonded mineral fibre product made of mineral fibres, preferably rock wool fibres, and a cured aqueous binder, wherein the uncured aqueous binder before curing comprises one or more components (i) in the form of oxidised lignin, one or more components (ii) in the form of crosslinkers, one or more components (iii) in the form of plasticisers, and wherein said insulating element has a bulk density of between 70 kg / m 3 and 250 kg / m 3 .

Description

[0001] Divisional application

[0002] This invention patent application is a divisional application of a prior PCT-included Chinese patent application with application number 202080100294.9, filed on April 3, 2020, entitled "Roofing System and Insulation Element for Flat or Flat-Pitched Roofs". The international application corresponding to the parent application has application number PCT / EP2020 / 059619. Technical Field

[0003] This invention relates to a roofing system for flat or pitched roofs of buildings with thermal and / or sound insulation, the system comprising structural supports, support plates, an optional vapor control layer, a waterproof membrane, and at least one insulating element, said insulating element being a bonded mineral fiber product made of mineral fibers (preferably rock wool fibers) and an adhesive. Furthermore, this invention relates to insulating elements for such roofing systems, said insulating elements being made of mineral fibers (preferably rock wool fibers) and an adhesive. Background Technology

[0004] Flat roofs and pitched roofs are well known in the prior art. For example, as membrane structure roofing systems, membrane structure roofing systems are generally classified into the following types according to the placement of the main insulation material: warm roofs, inverted warm roofs, roof gardens or green roofs, and cold roofs.

[0005] Today, membrane roofing systems are typically built as single-layer roofing systems, designed to protect flat or flat-sloped roofs from all-weather conditions that may occur during their design life.

[0006] A typical single-layer roof system includes: structural supports, support plates that provide continuous support, a vapor control layer (if required), insulation, a waterproof membrane, and transport-resistant or load-bearing finishes (if required for functional and / or aesthetic reasons).

[0007] Most flat and pitched roofs are now designed as so-called warm roofs. In these warm roofs, the primary insulation material is placed directly beneath the roof covering, i.e., the waterproof membrane. This keeps the support panels warm in cold weather and manages condensation without the need for ventilation. Optionally, a vapor control layer can be laid on the support panels to control water vapor entering the insulation material. This is a very reliable and cost-effective way to insulate membrane structure roofs to a high standard.

[0008] The three main options for attaching a single-layer roof system are mechanical fastening, adhesive / cold bonding, and ballasting, in which the insulation and membrane can be attached using the same or different methods.

[0009] The various systems described in the prior art can be used for roofing systems of flat or pitched roofs of buildings and utilize insulating elements made of bonded mineral fiber products.

[0010] In some cases, it is also known to use multiple layers of mineral fibers, such as glass fibers, as nonwoven fleece or a thin fabric on the insulating element, thereby sandwiching it between the insulating element and the waterproof membrane. A panel formed by several insulating elements arranged side-by-side can have a layer of nonwoven fleece or fabric spanning its entire area. The fleece or thin fabric can be adhered to the elements by an adhesive applied between the contact surfaces. The fleece or thin fabric holds the panel in place within the panel and can improve mechanical strength by enabling forces applied to one element to be transmitted to adjacent elements. The fleece or thin fabric has small pores, for example, an average pore size or distance between adjacent fibers of less than 0.5 mm, for example, as small as 0.1 mm.

[0011] Existing roofing systems use thin fabric and cloth-faced roofing panels or bitumen-coated roofing panels to provide a suitable surface for the bonding / adhesion of the insulating element layer to the waterproof membrane. These systems can be used, but they may have the disadvantage of adhesives diffusing into the insulating element layer. This diffusing adhesive significantly reduces the insulating and / or damping properties of the insulating layer. Furthermore, diffusing adhesive leads to higher adhesive consumption and uncontrolled adhesion strength, resulting in higher system costs.

[0012] Finally, this type of adhesive, which is usually an organic adhesive, reduces the fire resistance of the insulating element, especially in the case of the asphalt-coated roofing panels mentioned above.

[0013] For example, WO 98 / 31895 discloses a roofing system that includes a mineral fiber core and covers the mineral fiber core.

[0014] The system consists of a fabric panel formed by bonding a resin to a mineral fiber core, and a moisture-proof / waterproof sheet covering the fabric, which is bonded to the panel via an adhesive that penetrates into the mineral fiber core. While this composite roofing system is widely used on flat and pitched roofs, it has several drawbacks as mentioned earlier.

[0015] Another example of a roofing system is disclosed in WO 2013 / 034376. This roofing system includes an insulating element for thermal and / or sound insulation, the insulating element comprising two layers, wherein at least one layer is made of mineral fibers, particularly rock wool fibers, and the second layer is made of at least one fabric and is fixed to the main surface of the first layer by an adhesive, wherein the second layer is filled with a filler that imparts a certain degree of permeability to the second layer.

[0016] Since any load on a heated roof is transferred to the structure through the insulation material, rigid materials are required. This selection is important because different products offer different levels of support and require greater or lesser thicknesses to achieve the chosen thermal installation values. This must be considered when designing and planning roofing systems for flat or pitched roofs of buildings.

[0017] There are basically two types of barrier products:

[0018] - Porous materials, such as polyisocyanurate (PIR), expanded polystyrene (EPS), or extruded polystyrene (XPS);

[0019] - Fiber materials, such as mineral wool (MW), especially rock wool.

[0020] The latter type of mineral wool product is known for its excellent thermal and acoustic properties, as well as its mechanical strength and excellent fire resistance. This product is also referred to as bonded mineral fiber products made from mineral fibers and binders, and the corresponding requirements for such products are specified in European standard EN 13162:2015-04 “Thermal insulation products for buildings - Factory made mineral wool (MW) products”.

[0021] Mineral fiber or mineral wool products typically include man-made glass fiber (MMVF). 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, stone, or slag fiber, and most preferably stone fiber, which is bonded together by a cured thermosetting polymer adhesive material.

[0022] The preferred adhesive is phenolic resin, which can be produced economically and can be extended with urea before being used as an adhesive. However, existing and proposed regulations aimed at reducing or eliminating formaldehyde release have led to the development of formaldehyde-free adhesives, such as adhesive compositions based on polycarboxylated polymers and polyols or polyamines.

[0023] Another group of non-phenol-formaldehyde adhesives are products of addition / elimination reactions of aliphatic and / or aromatic anhydrides with alkanolamines. These adhesive compositions are water-soluble and exhibit excellent adhesive properties in terms of curing speed and curing density.

[0024] Because some of the raw materials used in the production of these adhesives are rather expensive chemicals, there has always been a need to provide formaldehyde-free adhesives, sometimes also called formaldehyde-free adhesives (NAF).

[0025] Another impact related to previously known aqueous adhesive compositions made from mineral fibers is that at least most of the raw materials used to produce these adhesives are derived from fossil fuels. The ongoing trend is that consumers prefer products made entirely or at least partially from renewable materials, thus creating a need for adhesives made from mineral wool that are at least partially made from renewable materials.

[0026] Another impact associated with previously known aqueous binder compositions for mineral fibers is their involvement of corrosive and / or harmful components. This necessitates protective measures for the machinery used in the production of mineral wool products to prevent corrosion, as well as safety measures for personnel operating such machinery. This leads to increased costs and health concerns, thus creating a need for mineral fiber products that use binder compositions with reduced levels of corrosive and / or harmful materials.

[0027] Meanwhile, many adhesives for mineral fiber products have been provided, which are largely based on renewable raw materials. In many cases, these adhesives, which are largely based on renewable resources, are also formaldehyde-free.

[0028] However, many of these adhesives remain relatively expensive because they are based on relatively costly base materials. Furthermore, to date, they have not provided sufficient strength performance for the final mineral fiber products.

[0029] Roofing systems for flat or pitched roofs have a construction life of 30 years or more, thus requiring durable materials. Since the loads on such roofs are transferred to the structure through the insulation, the bonded mineral fiber products need to withstand most load conditions, especially compressive loads, such as occasional light movement during construction, but particularly during subsequent maintenance for inspection purposes, and also the all-weather conditions that may be experienced over time, especially wind loads. Therefore, the mineral fiber insulation products used in roofing systems need a certain degree of strength, which is related to density, and this is why the density of such products is typically, for example, from 70 kg / m³. 3 Up to approximately 250 kg / m 3 The reason is that it provides a certain strength performance over time.

[0030] In terms of strength loss over time (i.e., due to aging), insulating elements made from bonded mineral fibers using the aforementioned phenolic resins or urea-modified phenolic resins are known to be excellent and have therefore been used for decades. The use of prior art formaldehyde-free or formaldehyde-free adhesives (NAF) has proven effective for bulk densities less than approximately 60 kg / m³. 3 Lightweight products are feasible for installation in cavities or spaces, such as those that will subsequently be covered and do not require the product to bear any load or provide any specific mechanical resistance. However, in cases where such insulating elements must withstand loads and mechanical stresses, these formaldehyde-free adhesives are considered crucial because they are relatively prone to aging and thus losing their strength over time. Summary of the Invention

[0031] Therefore, one object of the present invention is to provide a roofing system having mineral fiber elements suitable for such a roofing system, and to avoid using expensive and / or harmful materials in the adhesive and / or to avoid using expensive and / or harmful adhesives themselves.

[0032] Another object of the present invention is to provide mineral fiber elements suitable for roofing systems without using expensive and / or harmful materials in the adhesives and / or without using expensive and / or harmful adhesives themselves.

[0033] According to the present invention, the roofing system includes a mineral fiber insulating element with an adhesive, the adhesive comprising one or more components in the form of oxidized lignin, one or more components in the form of crosslinking agents, and one or more components in the form of plasticizers, and wherein the insulating element has a strength of 70 kg / m³. 3 Up to 250 kg / m 3 The packing density between them.

[0034] Furthermore, according to the present invention, the insulating element for the roof is made of mineral fibers, preferably rock wool fibers, and an adhesive, wherein the adhesive comprises one or more components in the form of oxidized lignin, one or more components in the form of crosslinking agents, and one or more components in the form of plasticizers, and wherein the insulating element has a strength of 70 kg / m³. 3 and 250 kg / m 3 The packing density between them.

[0035] It has been discovered that insulating elements made of mineral fibers and adhesives as described above can provide the mechanical stability required for use in roofing systems for flat or pitched roofs. These insulating elements are free of harmful adhesives and formaldehyde, and the adhesives used have high anti-aging properties, resulting in low strength loss during the service life of the roofing system. Furthermore, the amount of adhesive used can be reduced compared to formaldehyde-free adhesives used in the prior art, such as existing NAF adhesives.

[0036] In one embodiment, the insulating element may have any of the preferred features described for the roof system.

[0037] Preferably, the insulating element has a loss on ignition (LOI) in the range of 2 to 8 wt.%, more preferably 2 to 5 wt.%. The binder content is considered as the LOI and is determined according to European standard EN 13820:2003. The binder includes oil and other binder additives.

[0038] According to a preferred embodiment, the roof system is provided with an insulating element having a compressive strength of 50 to 130 kPa as measured according to European standard EN 826:2013.

[0039] According to another embodiment, the roof system is provided with insulation elements having a layered strength of 20 to 50 kPa as measured in accordance with European standard EN 1607:2013.

[0040] The insulating elements of this bonded mineral fiber product are known for their excellent fire resistance and are generally classified as Euroclass A1 according to European standard EN 13501-1:2018 unless otherwise treated or covered with a coating or finish.

[0041] In a preferred embodiment, the adhesive used for the insulating element according to the invention in the roofing system according to the invention is formaldehyde-free.

[0042] The term "formaldehyde-free" was defined to characterize formaldehyde release of less than 5 μg / m³ from materials made of mineral fibers and adhesives. 2 / h, preferably less than 3 μg / m 2 / h of isolation element. Preferably, the test is performed according to ISO 16000 for testing aldehyde release.

[0043] Component (i)

[0044] As a component (i), the adhesive contains one or more oxidized lignins.

[0045] Lignin, cellulose, and hemicellulose are the three main organic compounds in plant cell walls. Lignin can be considered the glue that holds cellulose fibers together. Lignin contains both hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, after cellulose, and is estimated to account for 20-30% of the total carbon in biomass, which contains more than 1 billion tons of carbon globally.

[0046] Figure 7 Fragments from possible lignin structures are shown.

[0047] There are at least four types of commercially available industrial lignins. These four types are shown in... Figure 9 The fifth possible class of lignin, namely biorefined lignin, differs slightly because it is described not by the extraction process but by the process source, such as biorefining; therefore, it can be similar to or different from any of the other classes mentioned. Each class differs from one another and is suited to different applications. Lignin is a complex, heterogeneous material, depending on its source, composed of up to three different phenylpropane monomers. Softwood lignin is primarily composed of coniferyl alcohols; see [link to relevant documentation]. Figure 8 As a result, they were more homogeneous than hardwood lignin with higher eugenol content, see [link to article]. Figure 8 The appearance and consistency of lignin vary greatly and are highly dependent on the processing method.

[0048] A summary of the properties of these industrial lignins is shown in Figure 10 In China, lignin sulfonates from the sulfite pulping process remain the largest commercially available source of lignin, with a capacity of 1.4 million tons. However, putting these aside, the sulfate process is currently the most commonly used pulping process and is gradually replacing the sulfite process. It is estimated that 78 million tons of lignin are produced annually through sulfate pulp production, 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 extracted from black liquor, which is the waste liquid from either the sulfate or kraft pulping process. Currently, three well-known processes are used to produce sulfate lignin: LignoBoost, LignoForce, and SLRP. These three processes are similar in that they all involve adding CO2 to lower the pH to 9–10, followed by acidification to further lower the pH to around 2. The final step involves some combination of washing, leaching, and filtration to remove ash and other contaminants. These three processes are at different stages of commercialization globally.

[0049] The sulfate process introduces thiol groups and stilbene while retaining some carbohydrates. Since lignin is precipitated from the mother liquor using sulfuric acid, sodium sulfate is also present as an impurity, but this can potentially be avoided by modifying the method of lignin separation. The sulfate process generates a large number of phenolic hydroxyl groups; when these groups are ionized (above pH ~10), the lignin becomes water-soluble.

[0050] Commercial lignin sulfates are typically higher in purity than lignin sulfonates. Their molecular weight ranges from 1000 to 3000 g / mol.

[0051] Alkali lignin is derived from sodium hydroxide pulping, a process primarily used for wheat straw, sugarcane bagasse, and flax. It exhibits high solubility and T... g In terms of properties, alkali lignin is similar to sulfate lignin. This process does not use sulfur and there is no covalently bonded sulfur. Ash levels are very low. Alkali lignin has low solubility in neutral and acidic media, but is completely soluble above pH 12.

[0052] The lignin sulfonate process introduces a large number of sulfonate groups, making lignin soluble in both water and acidic aqueous solutions. Lignosulfonates contain up to 8% sulfur as sulfonates, while sulfate lignin contains 1–2% sulfur, mostly bonded to the lignin. The molecular weight of lignin sulfonates ranges from 15,000 to 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 the large number of ionized sulfonate groups, makes lignin attractive as a surfactant, and it is commonly used in applications such as dispersing cement.

[0053] Another type of lignin becoming available is that produced through biorefining processes, in which carbohydrates are separated from lignin using chemical or biochemical processes to produce a carbohydrate-rich fraction. This remaining lignin is called biorefined lignin. Biorefining aims to produce energy and alternatives to products derived from fossil fuels and petrochemicals, as well as lignin. Lignin derived from this process is often considered a low-value product, or even waste, primarily used for thermal combustion, as low-grade animal feed, or otherwise disposed of.

[0054] The availability of organic solvent-based lignin is still under consideration at pilot-scale. This process involves extracting lignin using water along with various organic solvents (typically ethanol) and some organic acids. The advantage of this process is the higher purity of the lignin obtained, but it is significantly more expensive than other industrial lignins and is soluble in organic solvents but insoluble in water.

[0055] Previous attempts to use lignin as a base compound in adhesive compositions for mineral fibers have failed because it has proven difficult to find a suitable crosslinking agent that achieves the desired mechanical properties of cured mineral wool products while avoiding harmful and / or corrosive components. Currently, lignin is used to replace petroleum-derived chemicals, such as phenol in phenolic resins or asphalt in adhesive applications. It is also used as a cement and concrete additive, and in some applications as a dispersant.

[0056] Crosslinking of polymers is generally intended to provide improved properties such as mechanical properties, chemical properties, and heat resistance. Lignin is particularly rich in phenolic and aliphatic hydroxyl groups that react to lead to crosslinking structures. Different lignins also possess other available functional groups that may be used. The presence of these other groups depends largely on the source-dependent separation of lignin from cellulose and hemicellulose (thiols in sulfate lignin, sulfonates in lignin sulfonates, etc.).

[0057] It has been found that by using oxidized lignin, it is possible to prepare binder compositions for mineral fibers, which give the produced mineral fiber products excellent properties.

[0058] In one embodiment, component (i) is in the form of one or more oxidized sulfate lignins.

[0059] In one embodiment, component (i) is in the form of one or more oxidized alkali lignins.

[0060] In one embodiment, component (i) in one or more forms of oxidized lignin is in the form of one or more ammoniated lignins. For the purposes of this invention, the term "ammoniated lignin" should be understood as lignin oxidized by an oxidizing agent in the presence of ammonia. The term "ammoniated lignin" is abbreviated as AOL.

[0061] In an alternative embodiment, ammonia is partially or wholly replaced by alkali metal hydroxides, particularly sodium hydroxide and / or potassium hydroxide.

[0062] Hydrogen peroxide is a typical oxidizing agent used in the preparation of oxidized lignin.

[0063] In one embodiment, ammonia-oxidized lignin comprises one or more compounds selected from ammonia, amines, hydroxides, or any salts thereof.

[0064] In one embodiment, based on the dry weight of one or more oxidized lignin-form components, the one or more oxidized lignin-form components (i) have a carboxylic acid content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g.

[0065] In one embodiment, one or more oxidized lignin-form components (i) have an average carboxylic acid group content of more than 1.5 groups, such as more than 2 groups, or more than 2.5 groups per macromolecule of one or more oxidized lignin-form components (i).

[0066] The carboxylic acid group content of oxidized lignin is considered to play a significant role in the surprising advantages of the aqueous adhesive composition for mineral fiber elements according to the present invention. In particular, the carboxylic acid groups of oxidized lignin are believed to improve crosslinking properties, thereby giving the cured mineral fiber product better mechanical properties.

[0067] Component (ii)

[0068] The adhesive component (ii) is in the form of one or more crosslinking agents.

[0069] In one embodiment, component (ii) includes one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents in one embodiment.

[0070] β-Hydroxyalkylamide crosslinking agents are curing agents for acidic functional macromolecules. They provide a rigid, durable, corrosion-resistant, and solvent-resistant crosslinked polymer network. It is believed that β-hydroxyalkylamide crosslinking agents cure through esterification to form multiple ester bonds. The hydroxyl functionality of the β-hydroxyalkylamide crosslinking agent should ideally be at least 2 on average, preferably greater than 2, and more preferably 2 to 4, to obtain optimal curing response.

[0071] Crosslinking agents containing oxazoline groups are polymers containing one or more oxazoline groups in each molecule. Typically, crosslinking agents containing oxazoline groups can be readily obtained by polymerizing oxazoline derivatives. Patent US 6,818,699B2 discloses this process.

[0072] In one embodiment, component (ii) is an epoxidized oil based on fatty acid triglycerides.

[0073] It is worth noting that epoxidized oils based on fatty acid triglycerides are not considered harmful, and therefore the use of these compounds in the adhesive compositions according to the invention does not make these compositions unsafe to handle.

[0074] In one embodiment, component (ii) is a molecule having three or more epoxy groups.

[0075] In one embodiment, component (ii) is one or more flexible oligomers or polymers, such as low-T g Acrylic-based polymers, such as low-T g Vinyl-based polymers, such as low-T g Polyethers contain reactive functional groups, such as carbodiimide, anhydride, oxazoline, amino, and epoxy groups.

[0076] In one embodiment, component (ii) is selected from crosslinking agents involved in the curing reaction, such as hydroxyalkylamides, alkanolamines, and reaction products of polycarboxylic acids. Reaction products of alkanolamines and polycarboxylic acids can be found in US 6,706,853B1.

[0077] Without wishing to be bound by any particular theory, it is believed that the highly advantageous properties of the aqueous adhesive compositions used with the present invention are attributable to the interaction between oxidized lignin, used as component (i), and the aforementioned crosslinking agent. The presence of carboxylic acid groups in the oxidized lignin is believed to enable the oxidized lignin to crosslink very effectively.

[0078] In one embodiment, component (ii) is one or more crosslinking agents selected from polyfunctional organic amines, such as alkanolamines, diamines (e.g., hexamethyldiamine), and triamines.

[0079] In one embodiment, component (ii) is one or more crosslinking agents selected from polyethyleneimine, polyethyleneamine, and aliphatic amines.

[0080] In one embodiment, component (ii) is one or more fatty amides.

[0081] In one embodiment, component (ii) is one or more crosslinking agents selected from dimethoxyacetaldehyde, glycolaldehyde, and glyoxylic acid.

[0082] In one embodiment, component (ii) is one or more crosslinking agents selected from polyester polyols, such as polycaprolactone.

[0083] In one embodiment, component (ii) is one or more crosslinking agents selected from starch, modified starch, and CMC.

[0084] In one embodiment, component (ii) is one or more crosslinking agents in the form of aliphatic multifunctional carbodiimide.

[0085] In one embodiment, component (ii) is one or more crosslinking agents selected from melamine-based crosslinking agents, such as a crosslinking agent based on hexa(methylmethoxy)melamine (HMMM).

[0086] Examples of such compounds are Picassian XL 701, 702, 725 (Stahl Polymers), ZOLDINE® XL-29SE (Angus Chemical Company), CX300 (DSM), and Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).

[0087] Component (ii) may also be any mixture of the above compounds.

[0088] In one embodiment, the adhesive composition used with the present invention comprises a component (ii) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, such as 6 to 12 wt.-%, based on the dry weight of the first component.

[0089] Component (iii)

[0090] Component (iii) is in the form of one or more plasticizers.

[0091] In one embodiment, component (iii) is in the form of one or more plasticizers selected from 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, lactide, acrylic-based polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides, such as urea / urea, or any mixture thereof.

[0092] In one embodiment, component (iii) is in the form of one or more plasticizers selected from carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactide, compounds having a lignin-like structure, such as vanillin, acetylsalicylic acid, and solvents used as coalescing agents, such as alcohol ethers, polyvinyl alcohol.

[0093] In one embodiment, component (iii) is in the form of one or more non-reactive plasticizers selected from polyethylene glycol, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or other esters, and solvents used as coalescing agents, such as alcohol ethers, acrylic polymers, and polyvinyl alcohol.

[0094] In one embodiment, component (iii) is one or more reactive plasticizers selected from carbonate esters, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactide, dicarboxylic acids or tricarboxylic acids, such as adipic acid, or lactic acid, and / or vanillic acid and / or ferulic acid, polyurethane dispersions, acrylic acid-based polymers having free carboxyl groups, and compounds having a lignin-like structure, such as vanillin, acetylsuccinone.

[0095] In one embodiment, component (iii) is in the form of one or more plasticizers selected from fatty alcohols, monohydroxy alcohols, such as pentanol and stearyl alcohol.

[0096] In one embodiment, component (iii) includes one or more plasticizers selected from polyethylene glycol and polyethylene glycol ether.

[0097] Another particularly surprising aspect of the invention is that the use of plasticizers with boiling points above 100°C, especially 140–250°C, greatly improves the mechanical properties of the mineral fiber products according to the invention, although, given their boiling points, these plasticizers are likely to evaporate at least partially during the curing of the aqueous adhesives in contact with the mineral fibers.

[0098] In one embodiment, component (iii) comprises one or more plasticizers with boiling points above 100°C, such as 110–280°C, more preferably 120–260°C, and even more preferably 140–250°C.

[0099] The effectiveness of these plasticizers in the aqueous adhesive compositions according to the invention is believed to be related to their effect on improving the flowability of oxidized lignin during the curing process. The increased flowability of lignin or oxidized lignin during the curing process is believed to promote effective crosslinking.

[0100] In one embodiment, component (iii) comprises one or more polyethylene glycols with an average molecular weight of 150 to 50,000 g / mol, particularly 150 to 4,000 g / mol, more particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, and more preferably 200 to 400 g / mol.

[0101] In one embodiment, component (iii) comprises one or more polyethylene glycols with an average molecular weight of 4,000 to 25,000 g / mol, particularly 4,000 to 15,000 g / mol, and more particularly 8,000 to 12,000 g / mol.

[0102] In one embodiment, component (iii) is capable of forming covalent bonds with components (i) and / or (ii) during the curing process. Such a component does not evaporate and remains part of the composition, but will be effectively modified to avoid introducing undesirable side effects, such as water absorption, into the cured product. Non-limiting examples of such components are caprolactone and acrylic-based polymers having free carboxyl groups.

[0103] In one embodiment, component (iii) is selected from fatty alcohols, monohydroxy alcohols, such as pentanol and stearyl alcohol.

[0104] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from alkoxylates, such as ethoxylates, such as butanol ethoxylates, such as butoxytriethylene glycol.

[0105] In one embodiment, component (iii) is selected from one or more propylene glycols.

[0106] In one embodiment, component (iii) is selected from one or more ethylene glycol esters.

[0107] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from bisacrylate, acetate, benzoate, cyclobenzoate, citrate, stearate, sorbate, sebate, azelaic acid ester, butyrate, and valerate.

[0108] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from phenol derivatives, such as alkyl or aryl substituted phenols.

[0109] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from silanols and siloxanes.

[0110] In one embodiment, component (iii) is selected from one or more plasticizers, the plasticizers being selected from sulfates, such as alkyl sulfates, sulfonates, such as alkyl aryl sulfonates, such as alkyl sulfonates, phosphates, such as tripolyphosphates; such as tributyl phosphate.

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

[0112] In one embodiment, component (iii) is selected from one or more plasticizers, which are selected from monomeric amides, such as acetamide, benzamide, fatty acid amides, such as tallowamide.

[0113] In one embodiment, component (iii) is selected from one or more plasticizers, which are selected from quaternary ammonium compounds, such as trimethylglycine and distearate dimethylammonium chloride.

[0114] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from vegetable oils, such as castor oil, palm oil, flaxseed oil, tall oil, and soybean oil.

[0115] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from hydrogenated oils and acetylated oils.

[0116] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0117] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from alkyl polysaccharides, glucosamide, aminoglucosamide, sucrose esters, and dehydrated sorbitol esters.

[0118] Surprisingly, it has been found that the inclusion of plasticizers in the aqueous adhesive compositions according to the invention greatly improves the mechanical properties of the mineral fiber products according to the invention.

[0119] The term plasticizer refers to substances added to materials to make them softer, more flexible (by lowering the glass transition temperature Tg) and easier to process.

[0120] Component (iii) may also be any mixture of the above compounds.

[0121] In one embodiment, based on the dry weight of component (i), the amount of component (iii) present is 0.5 to 50 wt.-%, preferably 2.5 to 25 wt.-%, more preferably 3 to 15 wt.-%.

[0122] In another embodiment of the adhesive used with the present invention, an aqueous adhesive composition comprising component (i) and alternative component (iia) is described below.

[0123] In one embodiment, the aqueous adhesive composition for mineral fibers comprises:

[0124] - One or more components in the form of oxidized lignin (i);

[0125] - Components in the form of one or more modifiers (iia).

[0126] Excellent adhesive properties can also be achieved through a two-component system comprising one or more components in the form of oxidized lignin (i) and one or more components in the form of modifiers (iia), as well as any other components mentioned above and below.

[0127] In the embodiments, component (iia) is a modifier in the form of one or more compounds selected from epoxidized oils based on fatty acid triglycerides.

[0128] In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from molecules having three or more epoxy groups.

[0129] In one embodiment, component (iia) is a modifier in the form of one or more flexible oligomers or polymers, such as low-T g Acrylic-based polymers, such as low-T g Vinyl-based polymers, such as low-T g Polyethers contain reactive functional groups, such as carbodiimide, anhydride, oxazoline, amino, and epoxy groups.

[0130] In one embodiment, component (iia) is one or more modifiers selected from polyethyleneimine, polyethyleneamine, and fatty amines.

[0131] In one embodiment, component (iia) is one or more modifiers selected from aliphatic multifunctional carbodiimides.

[0132] Component (iia) can also be any mixture of the above compounds.

[0133] Without wishing to be bound by any particular theory, the superior adhesive properties obtained by the mineral fiber adhesive composition comprising components (i) and (iia) and optional other components are at least partly attributable to the effect of the modifier used as component (iia) acting at least partly as a plasticizer and crosslinking agent.

[0134] In one embodiment, the aqueous adhesive composition comprises component (iia) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, such as 6 to 12 wt.-%, based on the dry weight of component (i).

[0135] Other components

[0136] In some embodiments, the aqueous adhesive composition used with the present invention contains other components.

[0137] In one embodiment, the aqueous adhesive composition used with the present 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 hypophosphoric acid, and / or ammonium salts, such as ammonium salts of sulfuric acid, aminosulfonic acid, nitric acid, boric acid, hypophosphoric acid and / or phosphoric acid. The presence of such a catalyst can improve the curing properties of the aqueous adhesive composition used with the present invention.

[0138] In one embodiment, the aqueous binder composition used with the present invention comprises a catalyst selected from Lewis acids, which can accept electron pairs from a donor compound to form a Lewis adduct, such as ZnCl2, Mg(ClO4)2, Sn[N(SO2-n-C8F] 17 )2]4.

[0139] In one embodiment, the aqueous binder composition used with the present invention comprises a catalyst selected from metal chlorides, such as KCl, MgCl2, ZnCl2, FeCl3, and SnCl2.

[0140] In one embodiment, the aqueous binder composition used with the present invention comprises a catalyst selected from organometallic compounds, such as titanate-based catalysts and tin-based catalysts.

[0141] In one embodiment, the aqueous adhesive composition used with the present invention comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, and copper ions.

[0142] In one embodiment, the aqueous adhesive composition used with the present invention further comprises one or more other components in the form of silanes (iv).

[0143] In one embodiment, the aqueous adhesive composition used with the present invention comprises other components (iv) in the form of one or more coupling agents, such as organofunctional silanes.

[0144] In one embodiment, component (iv) is selected from organofunctional silanes, such as primary or secondary amino-functionalized silanes, epoxy-functionalized silanes, such as polymeric or oligomeric epoxy-functionalized silanes, methacrylate-functionalized silanes, alkyl and aryl-functionalized silanes, urea-functionalized silanes, or vinyl-functionalized silanes.

[0145] In one embodiment, the aqueous adhesive composition used with the present invention further comprises one or more components (v) selected from ammonia, amines, or any salts thereof.

[0146] It has been found that when oxidized lignin is used in component (i), it is particularly useful as other component (v) that contains ammonia, amines or their salts, which are not oxidized in the presence of ammonia.

[0147] In one embodiment, the aqueous adhesive composition used with the present invention also contains other components in the form of urea, particularly in amounts of 5 to 40 wt.-%, such as 10 to 30 wt.-%, or 15 to 25 wt.-%, based on the dry weight of component (i).

[0148] In one embodiment, the aqueous adhesive composition used with the present invention further comprises one or more other components in the form of carbohydrates selected from sucrose, reducing sugars, particularly glucose, polycarbohydrates and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, and more preferably glucose syrup with a glucose equivalent value of DE = 30 to less than 100, such as DE = 60 to less than 100, such as DE = 60 to 99, such as DE = 85 to 99, such as glucose syrup with DE = 95 to 99.

[0149] In one embodiment, the aqueous adhesive composition used with the present invention further comprises one or more other components in the form of carbohydrates selected from sucrose and reducing sugars, in an amount of 5 to 50 wt.-% based on the dry weight of component (i), for example 5 to less than 50 wt.-%, for example 10 to 40 wt.-%, for example 15 to 30 wt.-%.

[0150] In the context of adhesives used in conjunction with this invention, adhesive compositions with a sugar content of 50 wt.% or more based on the total dry weight of the adhesive components are considered sugar-based adhesives. Adhesive compositions with a sugar content of less than 50 wt.% based on the total dry weight of the adhesive components are considered non-sugar-based adhesives.

[0151] In one embodiment, the aqueous adhesive composition used with the present invention further comprises other components 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, such as soybean lecithin, such as sodium dodecyl sulfate.

[0152] In one embodiment, the aqueous adhesive composition used with the present invention includes

[0153] - One or more components (i) in the form of amino-oxidized lignin, having a carboxylic acid content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0154] - Component (ii) in the form of one or more crosslinking agents, said crosslinking agent being selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents and / or being selected from one or more crosslinking agents of polyfunctional organic amines, such as alkanolamines, diamines (such as hexamethyldiamine), and triamines;

[0155] - 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 particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, more preferably 150 to 300 g / mol, or 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, more particularly 8,000 to 12,000 g / mol; wherein preferably, the aqueous adhesive composition comprises, based on the dry weight of component (i), 1 to 40 wt.-%, for example 4 to 20 wt.-%, 6 to 12 wt.-%, of component (ii), and based on the dry weight of component (i), the presence of component (iii) is 0.5 to 50 wt.-%, preferably 2.5 to 25 wt.-%, more preferably 3 to 15 wt.-%.

[0156] In one embodiment, the aqueous adhesive composition used with the present invention includes

[0157] - One or more components (i) in the form of amino-oxidized lignin, having a carboxylic acid content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0158] - Component (ii) in the form of one or more modifiers, said modifiers being selected from epoxidized oils based on fatty acid triglycerides.

[0159] In one embodiment, the aqueous adhesive composition used with the present invention includes

[0160] - One or more components in the form of ammonia-oxidized lignin (i), having an average carboxylic acid group content of more than 1.5 groups per macromolecule of the first component, such as more than 2 groups, such as more than 2.5 groups;

[0161] - Component (ii) in the form of one or more crosslinking agents, said crosslinking agent being selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents and / or being selected from one or more crosslinking agents of polyfunctional organic amines, such as alkanolamines, diamines (such as hexamethyldiamine), and triamines;

[0162] - 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 particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, more preferably 150 to 300 g / mol, or 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, more particularly 8,000 to 12,000 g / mol; wherein preferably, the aqueous adhesive composition comprises, based on the dry weight of component (i), 1 to 40 wt.-%, for example 4 to 20 wt.-%, 6 to 12 wt.-%, of component (ii), and based on the dry weight of component (i), the presence of component (iii) is 0.5 to 50 wt.-%, preferably 2.5 to 25 wt.-%, more preferably 3 to 15 wt.-%.

[0163] In one embodiment, the aqueous adhesive composition used with the present invention includes

[0164] - One or more components (i) in the form of ammonia-oxidized lignin, having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups;

[0165] - A component (iia) in the form of one or more modifiers, said modifiers being selected from epoxidized oils based on fatty acid triglycerides.

[0166] In one embodiment, the aqueous adhesive composition used with the present invention comprises essentially the following components:

[0167] - One or more components in the form of oxidized lignin (i);

[0168] - Components in the form of one or more crosslinking agents (ii);

[0169] - Components in the form of one or more plasticizers (iii);

[0170] - Components in the form of one or more coupling agents (iv), such as organofunctional silanes;

[0171] - Optional components in the form of compounds selected from ammonia, amines, or any salts thereof;

[0172] - Optional urea form of the component;

[0173] - Optional components in more reactive or non-reactive silicone forms;

[0174] - Optional hydrocarbon oil;

[0175] - Optional one or more surfactants;

[0176] - water.

[0177] In one embodiment, the aqueous adhesive composition used with the present invention comprises essentially the following components:

[0178] - One or more components in the form of oxidized lignin (i);

[0179] - A component (iia) in the form of one or more modifiers, said modifiers being selected from epoxidized oils based on fatty acid triglycerides;

[0180] - Components in the form of one or more coupling agents (iv), such as organofunctional silanes;

[0181] - Optional components in the form of compounds selected from ammonia, amines, or any salts thereof;

[0182] - Optional urea form of the component;

[0183] - Optional components in more reactive or non-reactive silicone forms;

[0184] - Optional hydrocarbon oil;

[0185] - Optional one or more surfactants;

[0186] - water.

[0187] Preparation of ammonia-oxidized lignin (AOL) resin

[0188] 3267 kg of water was added to a 6000 L reactor, followed by 287 kg of ammonia (24.7%). Then, 1531 kg of lignin UPM BioPiva 100 was slowly added over 30–45 min. The mixture was heated to 40 °C and held at that temperature for 1 hour. After 1 hour, the insoluble lignin was examined. This can be done by examining the solution on a glass plate or a Hegman gauge. Undissolved lignin appears as small particles in a brown binder. During the dissolution step, the color of the lignin solution changes from brown to a glossy black.

[0189] After the lignin is completely dissolved, add 1 liter of foam inhibitor (Skumdaemper 11-10 from NCA-Verodan). Maintain the temperature of the mixture at 40°C.

[0190] 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 portion of the hydrogen peroxide is added at a rate of 200 liters per hour, and then the rate is increased to 300 liters per hour.

[0191] During the addition of hydrogen peroxide, the temperature in the reaction mixture is controlled by heating or cooling to ensure that the final reaction temperature reaches 65°C.

[0192] 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.

[0193] Final adhesive preparation

[0194] An adhesive was formulated from the above-mentioned AOL resin by adding 270 kg of polyethylene glycol 200 and 433 kg of 31% Primid XL-552 aqueous solution.

[0195] The Primid XL-522 has the following structure:

[0196]

[0197] The final adhesive analysis showed the following data

[0198] Solid content: 18.9% pH: 9.7

[0199] Viscosity: 25.5 mPa·s

[0200] Density: 1.066 kg / l

[0201] Oxidized lignin and mineral fiber aqueous adhesive compositions according to the present invention can be used as components in the compositions. Method for preparing this oxidized lignin

[0202] The following describes oxidized lignin, which can be used as a component in adhesive compositions, and its preparation.

[0203] Method I for preparing oxidized lignin

[0204] Oxidized lignin, which can be used as a component of the adhesive used in this invention, can be prepared by a method comprising contacting the following components.

[0205] - A component containing one or more lignins (a)

[0206] - A component comprising ammonia, one or more amine components, and / or any salts thereof (b)

[0207] - A component (c) containing one or more oxidizing agents.

[0208] Component (a)

[0209] Component (a) includes one or more lignins.

[0210] In one embodiment of the method according to the 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 lignocellulose raw materials, or any mixture thereof.

[0211] In one embodiment, component (a) comprises one or more sulfate lignins.

[0212] Component (b)

[0213] 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 alkali metal hydroxides used in previously known lignin oxidation processes with ammonia, one or more amino components, and / or any salts thereof plays an important role in the improved properties of oxidized lignin prepared according to the method of the invention.

[0214] The inventors have unexpectedly discovered that lignin oxidized by an oxidizing agent in the presence of ammonia or amine contains a significant amount of nitrogen as part of the structure of oxidized lignin. Without wishing to be bound by any particular theory, the inventors believe that when oxidized lignin prepared according to the method of the present invention is used in a product, the improved fire resistance of the oxidized lignin is at least partially attributable to the nitrogen content in the structure of the oxidized lignin, in which the oxidized lignin is contained in an adhesive composition.

[0215] In one embodiment, component (b) includes ammonia and / or any salt thereof.

[0216] 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 thus can be easily evaporated from the final product or removed and reused. In contrast, it has proven difficult to remove residual amounts of alkali metal hydroxides used in previously known oxidation processes.

[0217] Nevertheless, in the method according to the invention, it may be advantageous for component (b) to include, in addition to ammonia, one or more amino components, and / or any salts thereof, a small amount of alkali metal and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0218] In addition to ammonia, one or more amino components, and / or any salts thereof, component (b) also includes an alkali and / or alkaline earth metal hydroxide, such as sodium hydroxide and / or potassium hydroxide, in embodiments where the alkali metal and / or alkaline earth metal hydroxide is a component. The amount of alkali metal and / or alkaline earth metal hydroxide is typically small, based on ammonia, for example, 5 to 70 parts by weight, or 10 to 20 parts by weight of alkali metal and / or alkaline earth metal hydroxide.

[0219] Component (c)

[0220] In the method according to the invention, component (c) includes one or more oxidizing agents.

[0221] In one embodiment, component (c) comprises one or more oxidants in the form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogenated oxidants, or any mixture thereof.

[0222] In the initial step of oxidation, the active free radical from the oxidant typically extracts a proton from the phenolic group because this bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize free radicals through stable anatomy, multiple pathways have emerged to continue (but can also terminate) the reaction, yielding a variety of intermediates and final products. Because of this complexity (and the conditions of choice), the average molecular weight can increase and decrease, and in their experiments, the inventors typically observed a modest increase in average molecular weight of approximately 30%.

[0223] In one embodiment, component (c) includes hydrogen peroxide.

[0224] Hydrogen peroxide is perhaps the most commonly used oxidant due to its low cost, high efficiency, and relatively small environmental impact. When using hydrogen peroxide in the absence of a catalyst, alkaline conditions and temperature are important due to the following reactions that lead to the formation of free radicals:

[0225]

[0226]

[0227] The inventors have discovered that, as a result of the oxidation process, the derivatized lignin prepared by the method according to the present invention contains an increased number of carboxylic acid groups. Not wishing to be bound by any particular theory, the inventors believe that the carboxylic acid group content of the oxidized lignin prepared in the process according to the present invention plays an important role in the desired reactivity properties of the derivatized lignin prepared by the method according to the present invention.

[0228] Another advantage of the oxidation process is that oxidized lignin is more hydrophilic. Higher hydrophilicity can improve solubility in water and help it adhere to polar substrates such as mineral fibers.

[0229] Other components

[0230] In one embodiment, the method according to the invention includes other 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.

[0231] Such an oxidation catalyst can increase the reaction rate, thereby improving the properties of oxidized lignin prepared according to the method of the present invention.

[0232] Component mass ratio

[0233] Those skilled in the art will use components (a), (b), and (c) in relative amounts to achieve the desired degree of oxidation for lignin.

[0234] In one embodiment,

[0235] - Component (a) contains one or more lignins

[0236] - Component (b) contains ammonia

[0237] - Component (c) contains one or more oxidants in the form of hydrogen peroxide.

[0238] 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, or 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, or 0.075 to 0.125 parts by weight, based on the dry weight of lignin.

[0239] process

[0240] There is more than one possibility to bring components (a), (b), and (c) into contact to achieve the desired oxidation reaction.

[0241] In one embodiment, the method includes the following steps:

[0242] - The step of providing component (a) in the form of an aqueous solution and / or dispersion of one or more lignins, wherein the lignin content of the aqueous solution is 1 to 50 wt.-%, for example 5 to 25 wt.-%, for example 15 to 22 wt.-%, for example 18 to 20 wt.-% based on the total weight of the aqueous solution;

[0243] - By adding component (b) in a pH adjustment step, said component (b) comprises an aqueous solution of ammonia, one or more amine components and / or any salt thereof;

[0244] - An oxidation step by adding component (c), wherein component (c) comprises an oxidizing agent.

[0245] In one embodiment, a pH adjustment step is performed so that the pH of the resulting aqueous solution and / or dispersion is ≥9, for example ≥10, for example ≥10.5.

[0246] In one embodiment, a pH adjustment step is performed so that the pH of the resulting aqueous solution and / or dispersion is in the range of 10.5 to 12.

[0247] In one embodiment, a pH adjustment step is performed to allow the temperature to rise to ≥25°C, and then controlled within the range of 25–50°C, such as 30–45°C, or 35–40°C.

[0248] 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, such as 40 to 90°C, or 45 to 80°C.

[0249] In one embodiment, the oxidation step is performed for a period of 1 second to 48 hours, such as 10 seconds to 36 hours, such as 1 minute to 24 hours, such as 2 to 5 hours.

[0250] Method II for preparing oxidized lignin

[0251] Oxidized lignin, which can be used as a component of the adhesive used in this invention, can be prepared by a method comprising contacting the following components.

[0252] - A component containing one or more lignins (a)

[0253] - Components containing ammonia and / or one or more amine components, and / or any salts thereof, and / or alkali metal and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide (b)

[0254] - A component containing one or more oxidizing agents (c)

[0255] - Components in the form of one or more plasticizers (d).

[0256] Component (a)

[0257] Component (a) includes one or more lignins.

[0258] In one embodiment of the method according to the 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 lignocellulose raw materials, or any mixture thereof.

[0259] In one embodiment, component (a) comprises one or more sulfate lignins.

[0260] Component (b)

[0261] In one embodiment of the invention, component (b) comprises ammonia, one or more amino components, and / or any salts thereof, and / or alkali metal and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0262] "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.

[0263] In one embodiment, component (b) includes ammonia and / or any salt thereof.

[0264] Without wishing to be bound by any particular theory, the inventors believe that, in the case that component (b) is ammonia and / or any salt thereof, the improved stability of the derivatized lignin prepared according to the present invention is at least in part attributable to the fact that ammonia is a volatile compound, and thus can be evaporated from the final product or easily removed and reused.

[0265] Nevertheless, in this embodiment of the method according to the invention, it may be advantageous that, in addition to ammonia, one or more amino components, and / or any salts thereof, component (b) also includes a small amount of alkali metal and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0266] In addition to ammonia, one or more amino components, and / or any salts thereof, component (b) also includes an alkali and / or alkaline earth metal hydroxide, such as sodium hydroxide and / or potassium hydroxide, in embodiments where the alkali metal and / or alkaline earth metal hydroxide is a component. The amount of alkali metal and / or alkaline earth metal hydroxide is typically small, based on ammonia, for example, 5 to 70 parts by weight, or 10 to 20 parts by weight of alkali metal and / or alkaline earth metal hydroxide.

[0267] Component (c)

[0268] In the method according to the invention, component (c) includes one or more oxidizing agents.

[0269] In one embodiment, component (c) comprises one or more oxidants in the form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogenated oxidants, or any mixture thereof.

[0270] In the initial step of oxidation, the active free radical from the oxidant typically extracts a proton from the phenolic group because this bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize free radicals through stable anatomy, multiple pathways have emerged to continue (but can also terminate) the reaction, yielding a variety of intermediates and final products. Because of this complexity (and the conditions of choice), the average molecular weight can increase and decrease, and in their experiments, the inventors typically observed a modest increase in average molecular weight of approximately 30%.

[0271] In one embodiment, component (c) includes hydrogen peroxide.

[0272] Hydrogen peroxide is perhaps the most commonly used oxidant due to its low cost, high efficiency, and relatively small environmental impact. When using hydrogen peroxide in the absence of a catalyst, alkaline conditions and temperature are important due to the following reactions that lead to the formation of free radicals:

[0273]

[0274]

[0275] The inventors have discovered that, as a result of the oxidation process, the derivatized lignin prepared by the method according to the present invention contains an increased number of carboxylic acid groups. Not wishing to be bound by any particular theory, the inventors believe that the carboxylic acid group content of the oxidized lignin prepared in the process according to the present invention plays an important role in the desired reactivity properties of the derivatized lignin prepared by the method according to the present invention.

[0276] Another advantage of the oxidation process is that oxidized lignin is more hydrophilic. Higher hydrophilicity can improve solubility in water and help it adhere to polar substrates such as mineral fibers.

[0277] Component (d)

[0278] Component (d) includes one or more plasticizers.

[0279] 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, lactide, acrylic-based polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides, such as urea / urea, or any mixture thereof.

[0280] The inventors have discovered that a component (d) containing one or more plasticizers reduces the viscosity of the reaction mixture, which makes the method for producing oxidized lignin highly efficient.

[0281] 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-based polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides, such as urea / urea, or any mixture thereof.

[0282] In one embodiment of the invention, component (d) comprises one or more plasticizers selected from polyethylene glycol, polyvinyl alcohol, urea, or any mixture thereof.

[0283] Other components

[0284] In one embodiment, the method according to the invention includes other components, particularly component (v) in the form of an oxidation catalyst, such as one or more transition metal catalysts, such as ferric sulfate, such as catalysts containing manganese, palladium, selenium, or tungsten.

[0285] Such an oxidation catalyst can increase the reaction rate, thereby improving the performance of the oxidized lignin prepared by the method.

[0286] Component mass ratio

[0287] Those skilled in the art will use components (a), (b), (c), and (d) in relative amounts to achieve the desired degree of oxidation of lignin.

[0288] In one embodiment, the method according to the invention is performed such that the method includes...

[0289] - Component (a) contains one or more lignins

[0290] - Component (b) contains ammonia

[0291] - Component (c) contains one or more oxidants in the form of hydrogen peroxide.

[0292] - Component (d) contains one or more plasticizers selected from polyethylene glycol.

[0293] 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, or 0.15 to 0.25 parts by weight of ammonia (25 wt% aqueous solution), based on the dry weight of lignin; the amount of hydrogen peroxide (30 wt% 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.

[0294] For the purposes of this invention, "dry weight of lignin" is preferably defined as the weight of the lignin in the supplied form.

[0295] process

[0296] There is more than one possibility to bring components (a), (b), (c) and (d) into contact to achieve the desired oxidation reaction.

[0297] In one embodiment, the method includes the following steps:

[0298] - The step of providing component (a) in the form of an aqueous solution and / or dispersion of one or more lignins, wherein the lignin content of the aqueous solution is 5 to 90 wt.-%, for example 10 to 85 wt.-%, for example 15 to 70 wt.-% based on the total weight of the aqueous solution;

[0299] - By adding component (b) to the pH adjustment step;

[0300] - The step of adding component (d);

[0301] - An oxidation step by adding component (c), wherein component (c) comprises an oxidizing agent.

[0302] In one embodiment, a pH adjustment step is performed so that the pH of the resulting aqueous solution and / or dispersion is ≥9, for example ≥10, for example ≥10.5.

[0303] In one embodiment, a pH adjustment step is performed so that the pH of the resulting aqueous solution and / or dispersion is in the range of 9.5 to 12.

[0304] In one embodiment, a pH adjustment step is performed to allow the temperature to rise to ≥25°C, and then controlled within the range of 25–50°C, such as 30–45°C, or 35–40°C.

[0305] 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, such as 40 to 90°C, or 45 to 80°C.

[0306] In one embodiment, the oxidation step is performed for a period of 1 second to 24 hours, such as 1 minute to 12 hours, such as 10 minutes to 8 hours, such as 5 minutes to 1 hour.

[0307] The inventors have discovered that the process according to the invention allows for the production of reaction mixtures with high dry matter content, thus enabling high production volumes in the process according to the invention. This allows the reaction products in the form of oxidized lignin to be used as components in industrially mass-produced products such as mineral fiber products.

[0308] In one embodiment, the method according to 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.%.

[0309] In one embodiment, the method according to the invention is performed such that the viscosity of the oxidized lignin has a value of 100 cP to 100,000 cP, for example, a value of 500 cP to 50,000 cP, for example, a value of 1,000 cP to 25,000 cP.

[0310] For the purposes of this invention, viscosity is dynamic viscosity, defined as the resistance of a liquid / paste to changes in shape or 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.

[0311] In one embodiment, the method according to the invention is performed such that the method includes a rotor-stator assembly.

[0312] In one embodiment, the method according to the invention is performed such that it is carried out as a continuous or semi-continuous process.

[0313] Equipment for performing the method

[0314] The present invention also relates to an apparatus for performing the above-described method.

[0315] In one embodiment, the apparatus for performing the method includes:

[0316] - Rotor-stator assembly,

[0317] - A premixing device for components (a), (b), and (d)

[0318] - One or more inlets for water, components (a), (b), (c), and (d),

[0319] - One or more outlets of oxidized lignin.

[0320] In one embodiment, the device is constructed such that the inlets of the premix of components (a), (b), and (d) lead to the rotor-stator assembly, and the device further includes a chamber having an inlet for component (c) and an outlet for oxidized lignin.

[0321] A rotor-stator device is a apparatus for processing materials, comprising a stator configured as an inner cone with a gear ring. The stator cooperates with a rotor having arms projecting from the hub. Each of these arms has teeth that mesh with the teeth on the gear ring of the stator. With each rotation of the rotor, the material to be processed is conveyed outwards, undergoing intense shearing, mixing, and redistribution. The rotor arms and adjacent container chambers of the vertical device allow for permanent rearrangement of the material from the inside out and provide multiple processing options for dried and / or highly viscous substances, making the device extremely practical for thorough mixing, kneading, fibrillation, pulverization, 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 device.

[0322] In one embodiment, the rotor-stator device used in the method according to the 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 features a guide funnel protruding between the arms of the rotor, the guide funnel concentrating 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 throttles the material flow. At the rotor, a feed screw is provided for feeding into the working area of ​​the device. The guide funnel holds the product within the active area of ​​the device, and the feed screw generates an increased material pressure at the center.

[0323] For further details regarding the rotor-stator arrangement used in one embodiment of the method, please refer to US 2003 / 0042344A1, which is incorporated herein by reference.

[0324] In one embodiment, the method is performed such that a rotor-stator assembly is used. In this embodiment, the mixing and reaction of the components are carried out within the same rotor-stator assembly.

[0325] In one embodiment, the method is carried out such that it uses two or more rotor-stator devices, wherein at least one rotor-stator device is used for mixing the components, and at least one rotor-stator device is used for reacting the components.

[0326] This process can be divided into two steps:

[0327] 1. Preparation of lignin (a) + (b) + (d)

[0328] 2. Oxidation of lignin

[0329] Generally, two different types of rotor-stator machines are used:

[0330] 1. Open rotor / stator machine, suitable for mixing lignin powder in water at very high concentrations (30–50 wt.%). Mixing is not very vigorous, but special auxiliary devices (inlet funnel, screw, etc.) are available to handle highly viscous materials. Circumferential speed is low (maximum 15 m / s). This machine can be used as a batch or continuous system.

[0331] 2. In-line rotor / stator machine, which has much higher shear force (circumferential speed up to 55 m / s) and creates favorable conditions for very rapid chemical reactions, and the machine will be used continuously.

[0332] In an open rotor- / stator system, a high-concentration (45–50 wt.-%) lignin / water mixture is prepared. Lignin powder is slowly added to warm water (30–60°C) to which an appropriate amount of ammonia and / or bases have been added. This can be done in batches or intermittently / continuously to create a continuous flow of material to the next step.

[0333] The resulting material should be maintained at a temperature of around 60°C to keep its viscosity as low as possible so that it can be pumped. Then, using a suitable pump, such as a screw pump or other positive displacement pump, the hot lignin / water mixture with a pH of 9–12 is transferred to the oxidation step.

[0334] In one embodiment, oxidation takes place in a continuous in-line reaction within a closed rotor- / stator system. An aqueous solution of ammonia and / or bases is dispensed into the rotor- / stator chambers at the point of highest turbulence / shear using a feed pump. This ensures a rapid oxidation reaction. The oxide feed (AOL) exits the in-line reactor and is collected in a suitable tank.

[0335] reaction products

[0336] The inventors unexpectedly discovered that the prepared oxidized lignins have very desirable reactive properties, and when used in products as part of a binder composition, they exhibit improved fire resistance and improved long-term stability compared to previously known oxidized lignins.

[0337] Oxidized lignin also exhibits improved hydrophilicity.

[0338] An important parameter for the reactivity of the prepared oxidized lignin is the content of carboxylic acid groups in the oxidized lignin.

[0339] In one embodiment, based on the dry weight of component (a), the prepared oxidized lignin has a carboxylic acid group content of 0.05–10 mmol / g, for example 0.1–5 mmol / g, for example 0.20–2.0 mmol / g, for example 0.40–1.5 mmol / g, for example 0.45–1.0 mmol / g.

[0340] Another way to describe the carboxylic acid group content is to use the average carboxylic acid group content per lignin macromolecule according to the following formula:

[0341]

[0342] In one embodiment, the prepared oxidized lignin has an average carboxylic acid group content of more than 1.5 groups, such as more than 2 groups, or more than 2.5 groups per macromolecule of component (a).

[0343] Method III for preparing oxidized lignin

[0344] Oxidized lignin, which can be used as a component of the adhesive used in this invention, can be prepared by a method comprising contacting the following components.

[0345] - A component (a) containing one or more lignins,

[0346] - Components containing ammonia and / or one or more amine components, and / or any salts thereof, and / or alkali metal and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide (b),

[0347] - Component (c) containing one or more oxidizing agents,

[0348] - Component (d) may be in one or more plasticizer forms.

[0349] It also allows 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, such as 10 seconds to 6 hours, such as 30 seconds to 2 hours.

[0350] Components (a), (b), (c) and (d) are as defined above according to Method II for the Preparation of Oxidized Lignin.

[0351] In one embodiment of the invention, the process includes a premixing step that brings the components into contact with each other.

[0352] In the premixing step, the following components can be brought into contact with each other:

[0353] - Component (a) and component (b), or

[0354] - Component (a) and component (b) and component (c), or

[0355] - Component (a) and component (b) and component (d), or

[0356] - Component (a), component (b), component (c), and component (d).

[0357] In embodiments of the invention, the premixing step can be performed as a separate step, with the mixing / oxidation step following the premixing step. In this embodiment, it is particularly advantageous to bring components (a) and (b), and optionally component (d), into contact with each other during the premixing step. In the subsequent mixing / oxidation step, component (c) is then added to the premix produced in the premixing step.

[0358] In another example of the invention, the premixing step may correspond to the mixing / oxidation step. In this embodiment of the invention, components, such as components (a), (b), and (c), are mixed, and the oxidation process is started simultaneously. The subsequent residence time can be performed in the same apparatus used for the mixing / oxidation step. This implementation of the invention is particularly advantageous if component (c) is air.

[0359] The inventors have discovered that by allowing the mixing / oxidation step to be followed by an oxidation step, preferably without further mixing of the reaction mixture in the oxidation step, the oxidation rate can be controlled in a very efficient manner. Furthermore, since the oxidation step following the mixing / oxidation step requires less complex equipment, the cost of carrying out the method is reduced.

[0360] Another advantage is the exceptional stability of the resulting oxidized lignin. Another surprising advantage is the excellent adjustability of the viscosity of the resulting oxidized lignin. Yet another surprising advantage is the ability to achieve very high concentrations of oxidized lignin.

[0361] In one embodiment, the residence time is selected to allow the oxidation reaction to reach the desired degree of completion, preferably complete completion.

[0362] System I for performing Method III

[0363] In one embodiment, the system for performing the method includes:

[0364] - At least one rotor-stator assembly,

[0365] - Inlets for one or more water and components (a) and (b),

[0366] - One or more outlets of the rotor-stator assembly,

[0367] - 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.

[0368] In one embodiment, the system includes inlets for one or more components (c) and / or components (d).

[0369] In one embodiment, the system includes a premixing device.

[0370] 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).

[0371] In one embodiment of the invention, the premixing device includes inlets for water and components (a) and (b).

[0372] In the premixing step, component (c) can also be mixed with the three mentioned ingredients (water, component (a), and component (b)). The premixing device can then have an inlet for another component (c). If component (c) is air, the premixing device can be formed as an open mixing container, such that in this case, component (c) has already come into contact with the other components (water, component (a), and component (b)) through the opening of the container. Additionally, in this embodiment of the invention, the premixing device may optionally include an inlet for component (d).

[0373] In one embodiment, the system is constructed such that the inlets of components (a), (b), and (d) are inlets of a premixing device, particularly an open rotor-stator device, wherein the system further includes an additional rotor-stator device having an inlet of component (c) and an outlet for oxidized lignin.

[0374] 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 unit, namely, a rotor-stator unit.

[0375] In one embodiment, a rotor-stator device used in the method according to the invention includes a stator with a gear ring and a rotor with teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator device features a guide funnel protruding between the arms of the rotor, the guide funnel concentrating 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 throttles the material flow. At the rotor, a feed screw is provided for feeding into the working area of ​​the device. The guide funnel holds the product within the active area of ​​the device, and the feed screw generates an increased material pressure at the center.

[0376] System II for performing Method III

[0377] In one embodiment, the system for performing the method includes:

[0378] - One or more inlets for water, components (a) and (b),

[0379] - At least one mixing and oxidation device having one or more outlets, and

[0380] - At least one mixer / heat exchanger, the mixer / heat exchanger being arranged downstream of at least one or more outlets in the process flow direction, wherein the mixer / heat exchanger includes a temperature control device.

[0381] In one embodiment, the system includes inlets for one or more additional components (c) and / or components (d).

[0382] In one embodiment, the system includes a premixing device.

[0383] 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).

[0384] In one embodiment, the premixing device includes inlets for water and components (a) and (b).

[0385] In the premixing step, component (c) can also be mixed with the three mentioned ingredients (water, component (a), and component (b)). The premixing device can then have an inlet for another component (c). If component (c) is air, the premixing device can be formed as an open mixing container, such that in this case, component (c) has already come into contact with the other components (water, component (a), and component (b)) through the opening of the container. Additionally, in this embodiment of the invention, the premixing device may optionally include an inlet for component (d).

[0386] In one embodiment, the system is constructed such that the inlets of components (a), (b), and (d) are inlets of an open rotor-stator assembly, wherein the system further includes a mixer / heat exchanger having an inlet of component (c) and an outlet for oxidized lignin.

[0387] The premixing step and the mixing / oxidation step can be performed simultaneously. In this case, the premixing unit and the mixing / oxidation unit are a single unit.

[0388] In one embodiment, a rotor-stator device used in the method according to the invention includes a stator with a gear ring and a rotor with teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator device features a guide funnel protruding between the arms of the rotor, the guide funnel concentrating 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 throttles the material flow. At the rotor, a feed screw is provided for feeding into the working area of ​​the device. The guide funnel holds the product within the active area of ​​the device, and the feed screw generates an increased material pressure at the center.

[0389] Of course, other devices can also be used as premixing devices. Furthermore, the premixing step can be carried out in mixing and oxidation equipment.

[0390] In one embodiment, the mixing and oxidation device is a static mixer. A static mixer is a device used for the continuous mixing of fluid materials without moving parts. 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.

[0391] In one embodiment, the mixer / heat exchanger is configured as a multi-tube heat exchanger with mixing elements. The mixing elements are preferably stationary devices through which the mixture must flow, wherein mixing occurs as a result of said flow. The mixer / heat exchanger may be configured as a plug flow reactor.

[0392] Example I

[0393] Example IA - Lignin oxidation using hydrogen peroxide in ammonia solution:

[0394] The amounts of ingredients used according to example IA are provided in Tables IA 1.1 and 1A 1.2.

[0395] Although sulfate lignin is soluble in water at higher pH values, it is known that the viscosity of the solution increases significantly at certain weight percentages. This increase in viscosity is generally attributed to the combination of strong hydrogen bonds and π-electron interactions among the numerous aromatic rings present in lignin. For sulfate lignin, a sudden increase in viscosity has been observed at approximately 21–22 wt.% in water; the example given used 19 wt.% sulfate lignin.

[0396] Ammonia solution was used as the base in the pH adjustment step. Its amount was fixed at 4 wt.% based on the total reaction weight. The pH was 10.7 after the pH adjustment step and at the start of oxidation.

[0397] Table IA2 shows the results of CHNS elemental analysis of sulfate lignin before and after oxidation. Prior to analysis, the samples were heat-treated at 160°C to remove adsorbed ammonia. Analysis indicates that a certain amount of nitrogen becomes part of the structure of oxidized lignin during the oxidation process.

[0398] During batch testing, it was determined that, contrary to adding small amounts of hydrogen peroxide over longer periods, it was beneficial for oxidation to add the full amount over shorter time intervals. In this example, 2.0 wt.% H2O2 was used based on the total weight of the reaction.

[0399] Oxidation is an exothermic reaction, and a temperature rise is observed upon the addition of the peroxide. In this example, the temperature was maintained at 60°C during the 3-hour reaction period.

[0400] After oxidation, through 31 P NMR and water titration were used to determine the increase in the amount of lignin functional groups per gram of sample. 31 Sample preparation for P NMR was performed using 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxophosphazenecyclopentane (TMDP) as the phosphorylating agent and cholesterol as the internal standard. NMR spectra of sulfate lignin before and after oxidation were obtained, and the results are summarized in Table IA3.

[0401] The change in the COOH group was determined by water titration using the following formula:

[0402]

[0403] 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. C acid In this case, it is 0.1M HCl, m sThis is the weight of the sample. The values ​​obtained by water titration before and after oxidation are shown in Table IA4.

[0404] The average COOH functionality can also be quantified using the saponification value, which represents the number of milligrams of KOH required to saponify 1 g of lignin. This method can be found in AOCS Official Method Cd 3-25.

[0405] The average components were 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 280 nm UV detector. 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.

[0406] Example IB - Scale up the oxidation of lignin in ammonia using hydrogen peroxide to a pilot-scale.

[0407] Lignin oxidation using hydrogen peroxide is an exothermic process; even on a laboratory scale, a significant temperature rise is observed upon the addition of peroxide. This is a natural concern when scaling up chemical processes, as the heat generated is related to the cube of the size (volume), while cooling typically increases only with the square of the size (area). Furthermore, due to the high viscosity of the viscous intermediates, process equipment must be carefully selected or designed. Therefore, the aforementioned scaling-up is carefully designed and carried out in several steps.

[0408] The first scale-up step was carried out using a specialized stainless steel stirrer, employing highly efficient mechanical stirring from 1 L (laboratory scale) to 9 L. This scale-up only resulted in a final temperature slightly higher than that obtained on the laboratory scale, thanks to the reactor's efficient air cooling and the slow addition of hydrogen peroxide.

[0409] The next scale-up step was carried out in a closed 200 L reactor equipped with a high-efficiency water jacket and a high-efficiency propeller agitator. This time the scale-up was 180 L, and hydrogen peroxide was added in two steps at approximately 30-minute intervals. The scale-up proceeded relatively well, although considerable foaming was a problem, partly due to the high reactor packing. To control foaming, a small amount of food-grade defoamer was sprayed onto the foam. Crucially, controlled temperature and a final temperature below 70°C were achieved using external water cooling.

[0410] The pilot-scale reaction was carried out in an 800 L reactor equipped with a water-cooled jacket and a two-bladed propeller agitator. 158 kg of lignin (UPM LignoBoost™ BioPiva 100) with a dry matter content of 67 wt.% was deagglomerated and suspended in 224 kg of water, stirred to form a homogeneous suspension. While continuing stirring, 103 kg of 25% ammonia was pumped into the reactor, and stirring was continued for 2 hours to form a dark, viscous lignin solution. Within 15 minutes, 140 kg of 7.5 wt.% hydrogen peroxide was added to the stirred lignin solution at 20–25 °C. Temperature and foam levels were carefully monitored during and after the addition of hydrogen peroxide, and cooling water was added to the cooling jacket to maintain acceptable foam levels and a temperature rise below 4 °C / min, and a final temperature below 70 °C.

[0411] After the temperature rise is stopped, the cooling is shut off, and the product mixture is stirred for another 2 hours before being transferred to a transport container. Based on this scale-up operation, it can be concluded that even though the reaction is exothermic, most of the heat of reaction is actually offset 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 scaling up and process intensification using continuous reactors, such as in-line mixers, tubular reactors, or CSTR-type reactors. This will ensure good temperature control and a more defined reaction process.

[0412] Large-scale testing showed that the produced oxidized lignin had properties consistent with those of batches produced in the laboratory.

[0413] Table IA 1.1

[0414] The amount of material used in their supply form:

[0415]

[0416] Table IA 1.2

[0417] Amount of active material used:

[0418]

[0419] Table IA 2

[0420] Elemental analysis of sulfate lignin before and after oxidation:

[0421]

[0422] Table IA 3

[0423] pass 31Distribution of sulfate lignin functional groups before and after oxidation obtained by P-NMR:

[0424]

[0425] Table IA 4

[0426] COOH group content, in mmol / g, determined by water titration:

[0427]

[0428] Table IA 5

[0429] The number-average molar mass (Mn) and weight-average molar mass (Mw) in g / mol were determined by size exclusion chromatography, and the average carboxylic acid group content of each lignin macromolecule before and after oxidation were also measured.

[0430]

[0431] Example II

[0432] In the following examples, several oxidized lignins were prepared.

[0433] The following properties were determined for oxidized lignin:

[0434] Solid content of components:

[0435] The content of each component in a given oxidized lignin solution is based on the anhydrous mass of each component or as described below.

[0436] Sulfate lignin from UPM with BioPiva100 TM Provided as a dry powder. NH4OH 25% is supplied by Sigma-Aldrich and used as a pre-filled product. H2O2, 30% (Cas no. 7722-84-1) is supplied by Sigma-Aldrich and used as a pre-filled product or diluted with water. PEG 200 is supplied by Sigma-Aldrich and is assumed to be anhydrous for simplicity and is used accordingly. 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 and is assumed to be anhydrous for simplicity and is used accordingly. Urea (Cas no. 57-13-6) is supplied by Sigma-Aldrich and is used as a pre-filled product or diluted with water. Glycerol (Cas no 56-81-5) was supplied by Sigma-Aldrich and is assumed to be anhydrous for simplicity, and is used accordingly.

[0437] Oxidized lignin solids

[0438] The content of oxidized lignin after heating to 200°C for 1 hour is called "dry solids" and is expressed as a percentage of the remaining weight after heating.

[0439] Disc-shaped rock wool samples (5 cm in diameter and 1 cm in height) were cut from the rock wool and heat-treated at 580°C for at least 30 minutes to remove all organic matter. The solids of the binder mixture were measured by distributing a sample (approximately 2 g) of the binder mixture onto the heat-treated rock wool discs in a foil container. The foil container containing the rock wool discs was weighed before and immediately after the addition of the binder mixture. Two such rock wool discs containing the binder mixture were prepared in the foil container and then heated at 200°C for 1 hour. After cooling and holding at room temperature for 10 minutes, the samples were weighed, and the average of the two results was calculated as the dry solids content.

[0440] COOH group content

[0441] The change in COOH group content was also determined by water titration using the following formula:

[0442]

[0443] 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. C acid In this case, it is 0.1M HCl, m s,g This is the weight of the sample.

[0444] Methods for producing oxidized lignin:

[0445] 1) Mix water and lignin in a three-necked glass-bottom flask connected to a condenser and a temperature recording device in a water bath at room temperature (20–25°C) with stirring. Stir for 1 h.

[0446] 2) Add 1 part ammonia during the stirring process.

[0447] 3) If the slight exothermic reaction with ammonia does not raise the temperature, then raise the temperature to 35°C by heating.

[0448] 4) Measure pH.

[0449] 5) Add plasticizer PEG200 and stir for 10 min.

[0450] 6) After the lignin has completely dissolved in about 1 hour, slowly add 1 part of 30% H2O2.

[0451] 7) The exothermic reaction of adding H2O2 raises the temperature in the glass-bottom flask - if the reaction temperature is below 60°C, raise the temperature to 60°C and keep the sample at 60°C for 1 hour.

[0452] 8) Then remove the round-bottom flask from the water bath and cool it to room temperature.

[0453] 9) Take out the sample to determine the dry solids content, COOH, viscosity, density, and pH.

[0454] Oxidized Lignin Composition

[0455] Below, the entry numbers for the examples of oxidized lignin correspond to the entry numbers used in Table II.

[0456] Example IIA

[0457] 71.0 g of lignin UPM Biopiva 100 was dissolved in 149.0 g of water at 20 °C, and 13.3 g of 25% NH4OH was added. The mixture was stirred with a magnetic stirrer for 1 h, followed by the slow addition of 16.8 g of 30% H2O2 while stirring. The temperature was raised to 60 °C in a water bath. After oxidation for 1 h, the water bath was cooled to stop the reaction. The COOH content, dry solids content, pH, viscosity, and density of the resulting material were analyzed.

[0458] Example IIE

[0459] 71.0 g of lignin UPM Biopiva 100 was dissolved in 88.8 g of water at 20 °C, and 13.3 g of 25% NH4OH was added. The mixture was stirred with a magnetic stirrer for 1 hour. 22.8 g of PEG 200 was added and stirred for 10 min, 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 oxidation for 1 hour, the water bath was cooled to stop the reaction. The COOH content, dry solids content, pH, viscosity, and density of the resulting material were analyzed.

[0460] Example IIC

[0461] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 g of water at 20 °C, and 13.3 g of 25% NH4OH was added. The mixture was stirred with a mechanical stirrer for 1 h, 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 oxidation for 1 h, the water bath was cooled to stop the reaction. The COOH content, dry solids content, pH, viscosity, and density of the resulting material were analyzed.

[0462] Example IIF

[0463] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 g of water at 20 °C, and 13.3 g of 25% NH4OH was added. The mixture was stirred with a mechanical stirrer for 1 h. 19.0 g of PEG 200 was added and stirred for 10 min, 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 oxidation for 1 h, the water bath was cooled to stop the reaction. The COOH, dry solids, pH, viscosity, and density of the resulting material were analyzed.

[0464]

[0465] Example III:

[0466] Mix 8.5 liters of hot water (50°C) and 1.9 liters of NH4OH (24.7%), then slowly add 9.0 kg of lignin (UPM biopiva 100) over 10 minutes with high stirring (660 rpm, 44 Hz).

[0467] High shear forces caused the temperature to rise. After 30 minutes, 4 liters of hot water were added, and the material was stirred for another 15 minutes, followed by the addition of the remaining 5 liters of hot water. The sample was removed, and undissolved lignin was analyzed using a Hegman scale and pH measurement.

[0468] The premix was then transferred to the rotor-stator unit and the reaction apparatus, where it was oxidized using H2O2 (17.5 vol. -%). The reaction apparatus used in this case at least partially consisted of reaction tubes and a reaction vessel. The premix was added at a rate of 150 l / h, and H2O2 was added at a rate of 18 l / h.

[0469] 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.

[0470] The temperature of the premix is ​​62°C, and the oxidation step raises the temperature to 70°C.

[0471] The COOH group content, dry solids content, pH, viscosity and residual H2O2 of the final product were analyzed.

[0472] Table III:

[0473]

[0474] Example IV:

[0475] 484 L of hot water (70 °C) and 47.0 L of NH4OH (24.7%) were mixed, and then 224.0 kg of lignin (UPM biopiva 100) was slowly added over 15 minutes with high stirring. The sample was removed, and undissolved lignin was analyzed using a Hegman scale and pH measurement.

[0476] 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 fed at a rate of 600 l / h, and H2O2 was added at a rate of 17.2 l / h. The residence time in the mixer / heat exchanger was 20 minutes.

[0477] During the oxidation step, the temperature of the mixture is raised to 95°C.

[0478] The COOH group content, dry solids content, pH, viscosity and residual H2O2 of the final product were analyzed.

[0479] Adhesive prepared based on AOL: 49.3 g AOL (19.0% solids), 0.8 g hydroxyalkylamide XL552 (100% solids) and 2.4 g PEG200 (100% solids) were mixed with 0.8 g water to obtain 19% solids; then used in bar tests to test mechanical properties.

[0480] Bar testing

[0481] The mechanical strength of the adhesive was tested in the bar test. For each adhesive, 16 bars were made from a mixture of the adhesive and rock wool balls produced from rock wool spinning.

[0482] A sample of the adhesive solution containing 15% dry solids (16.0 g) was thoroughly mixed with rock wool balls (80.0 g). The resulting mixture was then filled into four slots in a heat-resistant silicone template to create rods (4 × 5 slots per template; slot top dimensions: length = 5.6 cm, width = 2.5 cm; slot bottom 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 rod of appropriate size to produce a uniform rod surface. Sixteen rods of each adhesive were prepared in this manner. The resulting rods were then cured at 200°C for 1 hour. After cooling to room temperature, the rods were carefully removed from the container. Five rods were aged in an 80°C water bath for 3 hours.

[0483] After drying for 1–2 days, a 3-point bending test was performed on the rail bending machine (test speed: 10.0 mm / min; fracture level: 50%; nominal strength: 30 N / mm). 2 Support distance: 40 mm; Maximum deflection: 20 mm; Nominal elastic modulus: 10000 N / mm 2 The mechanical strength of aged bars and five unaged bars was studied by fracturing them in the machine. The bars were placed with the "top face" (i.e., the face with dimensions of length = 5.6 cm and width = 2.5 cm) facing upwards.

[0484] Attached Figure Description

[0485] The invention will now be further described with reference to the accompanying drawings, in which the following figures are illustrated:

[0486] Figure 1 A portion of a first embodiment of a roofing system for a flat roof is shown in sectional view;

[0487] Figure 2 A portion of a second embodiment of a roofing system for flat roofs is shown in sectional view;

[0488] Figure 3 A diagram is shown illustrating the layering strength of the insulation element used in the roof system compared to that of an insulation element according to the prior art;

[0489] Figure 4 A diagram is shown illustrating the delamination strength of an insulation element used in an aged roof system compared to the delamination strength of an aged insulation element according to the prior art.

[0490] Figure 5 A graph is shown illustrating the compressive strength of the insulation element used in the roof system compared to the compressive strength of insulation elements according to the prior art;

[0491] Figure 6 A graph is shown illustrating the compressive strength of an insulation element used in an aged roof system compared to the compressive strength of an aged insulation element according to the prior art.

[0492] Figure 7 Fragments of possible lignin structures are shown;

[0493] Figure 8 Different lignin precursors and common inter-unit bonds are shown;

[0494] Figure 9 This shows four types of industrial lignins available on the market;

[0495] Figure 10 An overview of the properties of industrial lignin is shown. Detailed Implementation

[0496] Figure 1 A first embodiment of a portion of a flat roof 1 is shown, the flat roof 1 including a structural support 2, a vapor control layer 3, an insulating element 4, and a covering waterproof membrane 20. The insulating element 4 is an adhesive mineral fiber product made of mineral fibers and an adhesive.

[0497] The waterproof membrane 20 is attached to the insulating element 4 by an adhesive 9, which may be a component of the membrane 20. The adhesive 9 may be a bituminous adhesive, activated by a burner typically used in roofing projects, i.e., the membrane 20 is sprayed onto the insulating element 4 by a flame. The dashed lines in the insulating element 4 indicate the area 10 to which the molten bituminous adhesive 9 spreads before hardening and attaching the membrane 20 to the insulating element 4.

[0498] Figure 2 A second embodiment of a flat roof 1 according to the present invention is shown, the flat roof 1 including a structural support 2, a vapor control layer 3, an insulating element 4, and a waterproof membrane (not shown but related to...). Figure 1 (Equivalent). The insulating element 4 includes a first layer 5 and a second layer 6. The first layer 5 includes rock wool fibers and an adhesive, and the second layer 6 is made of glass wool fabric with an elastic modulus of 573 MPa. The tensile strength of the glass wool is 71 N.

[0499] The first layer 5 is represented by one or more thin layers having a fiber orientation that is primarily perpendicular to the main surface 7 of the second layer 6. The thin layers, and thus the first layer 5, have a density of 110 kg / m³. 3 The density and typical thickness of 150 mm. Before the second layer 6 is fixed to the surface 8 of the first layer 5 by adhesive 9, the mineral fibers are bonded together by an adhesive cured in a curing oven. In this particular embodiment, adhesive 9 can be selected from melamine-urea-formaldehyde, preferably a two-component adhesive, water-based acrylic adhesive, phenolic powder adhesive, water-based neoprene foam, polyamide-based powder adhesive, polyurethane adhesive, preferably a two-component adhesive, polyurethane moisture-curing adhesive, or a sealant-modified adhesive, preferably a one-component moisture-curing adhesive. However, preferably, in this particular embodiment, adhesive 9 is equivalent to the adhesive composition used to bond the mineral fibers of the insulating element 4.

[0500] All these adhesives 9 establish a good bond with the mineral fibers, and all these adhesives 9 are able to form a nearly closed layer in the thin layer area and the fabric area, thereby enhancing the insulating element 4 in the direction parallel to the main surface 7 of the thin layer.

[0501] Adhesive 9 is partially disposed in region 10 near the main surface 8 of the first layer 5 (which faces the second layer 6) and partially disposed in region 11 near the main surface 7 of the second layer 6 (which faces the first layer 5), so that adhesive 9 connects the first layer 5 and the second layer 6 in such a way that a force perpendicular to the second layer 6 can be compensated by the tensile strength of the second layer 6 combined with the deflection of adhesive 9 and / or the fibers of the first layer 5. This force perpendicular to the second layer 6, for example 80 kPa, results in a limited deformation of less than 5% in the insulating element 4 (the first layer 5 and the second layer 6), thus the deformation associated with the 150 mm thickness of the first layer 5 is no greater than 7.5 mm. The thickness of the second layer 6 is approximately no greater than 1 mm, and therefore can be ignored in this calculation. A sufficient amount of adhesive 9 is disposed between the fibers of the first layer 5, thereby surrounding the fibers and forming a layer of adhesive 9 anchored in the first layer 5.

[0502] As an acrylic adhesive, apply 80 g / m² between layers 5 and 6. 2 The amount of liquid adhesive used is arranged to distribute adhesive 9. A sufficient amount of adhesive 9 diffuses in the first layer 5 and the second layer 6. Thus, adhesive 9 forms a layer connecting the first layer 5 and the second layer 6, and is anchored in the two layers 5 and 6.

[0503] The adhesive used in insulating element 4 comprises one or more first components in the form of ammonia-oxidized lignin. According to... Figure 3 The graph shows the absolute value of the delamination strength of the insulating element 4 according to the invention (curve C2), compared with the absolute value of the delamination strength of the insulating element containing one of the assignee's existing formaldehyde-free adhesives shown in curve A2, and the absolute value of the delamination strength of the insulating element containing a conventional phenol-urea-formaldehyde adhesive shown in curve B2.

[0504] Delamination strength was measured according to EN 1607:2013, and the first initial measurement was performed on unaged samples immediately or shortly after the production of insulating element 4. The corresponding average results of this initial test and a representative number of samples are shown at time '0' on the x-axis of the graph. The time '0' corresponds to '0' days after the accelerated aging test was started according to the description below.

[0505] To determine the resistance of mineral fiber products to moisture and heat during the service life of a building, these mechanically-oriented mineral fiber products are subjected to accelerated aging. Resistance to aging is defined as the product's ability to retain its original mechanical properties and is calculated as a percentage of the original strength after aging. The testing procedure follows the so-called Nordtest method NTBuild 434:1995.05, extended to 28 days.

[0506] The purpose of this method is to accelerate the aging of the insulating material due to increased temperature and heat. It is applicable to all insulating materials manufactured as insulating panels. This method is not predictive; that is, it is not used to assess service life. However, a prerequisite for satisfactory performance is that the aging induced by this method does not lead to significant changes in the properties of the material under study. Over 20 years of experience with the Nordtest method has proven that it can provide reliable data to ensure satisfactory mechanical properties, especially for mineral fiber products used as insulating elements in roofing systems.

[0507] According to this method, a representative number of test specimens were exposed to heat and humidity for 7, 14, and 28 days in a climate chamber at 70 ± 2 °C and 95 ± 5% relative humidity (RH). Subsequently, the specimens were placed at 23 ± 2 °C and 50 ± 5% RH for at least 24 hours and dried before being prepared for mechanical property testing, such as measuring delamination strength according to EN 1607:2013 or measuring compressive strength according to EN 826:2013, as further described below.

[0508] Then, relative anti-aging properties were calculated as a percentage of the initial absolute value measured at time '0'. Results for accelerated aging at 7, 14, and 28 days were recorded and illustrated.

[0509] Regarding what is given here Figures 3-6 For example, insulation element 4 is a bonded mineral fiber roofing product commercially available from the assignee or affiliates, manufactured using the different adhesive types mentioned and tested for their mechanical properties. The product provides 145 kg / m². 3 The target density is approximately 3.8 wt.% and the loss on ignition (LOI) is approximately 3.8 wt.%.

[0510] Table I below is based on Figure 3 The layering strength [kPa] EN 1607 is shown.

[0511]

[0512] Table I

[0513] Table I shows a comparison of the absolute delamination strength (C2) of the insulating element 4 according to the present invention with the absolute delamination strength (A2) of the insulating element containing phenol-formaldehyde adhesive and the absolute delamination strength (B2) of the insulating element containing no formaldehyde adhesive. The corresponding curves are illustrated in... Figure 3 middle.

[0514] Table II below is based on Figure 4 The relative stratification intensity is shown as a percentage of the initial stratification intensity according to Table I.

[0515]

[0516] Table II

[0517] Table II shows a comparison of the relative delamination strength (C3) of the insulating element 4 according to the present invention with the relative delamination strength (A3) of the insulating element containing phenol-formaldehyde adhesive and the relative delamination strength (B3) of the insulating element containing no formaldehyde adhesive. The corresponding curves are illustrated in... Figure 4 middle.

[0518] As can be seen in Tables I and II, the delamination strength of the insulating element 4 according to the present invention is very close to the delamination strength of the insulating element containing phenol-cresol adhesive. Furthermore, it can be seen that the loss of delamination strength of the insulating element containing no formaldehyde adhesive is much greater than the increase in delamination strength of the insulating element 4 according to the present invention. Moreover, the delamination strength of the insulating element 4 according to the present invention is very close to the delamination strength of the insulating element containing phenol-formaldehyde adhesive. From... Figure 3 and Figure 4 It can be seen that curves C2 / C3 and A2 / A3 are approximately parallel to each other.

[0519] According to Table II and Figure 4 The relative delamination strength of the insulating element 4 according to the present invention (graph C3) was compared with the relative delamination strength of an insulating element containing phenol-formaldehyde adhesive (graph A3) or an insulating element containing no formaldehyde adhesive (graph B3). All insulating elements 4 to be compared underwent aging treatment as described above.

[0520] In addition, from Table II and Figure 4 It can be seen that the delamination value of the insulating element 4 according to the present invention is approximately equal to the delamination value A3 of the insulating element containing phenol-formaldehyde adhesive.

[0521] Table III below is based on Figure 5 The absolute compressive strength [kPa] is shown in EN 826.

[0522]

[0523] Table III

[0524] Table III shows a comparison of the absolute compressive strength (C4) of the insulating element 4 according to the present invention with the absolute compressive strength (A4) of the insulating element containing phenol-formaldehyde adhesive and the absolute compressive strength (B4) of the insulating element containing no formaldehyde adhesive. The corresponding curves are illustrated in... Figure 5 middle.

[0525] Figure 5The diagram shows a comparison of the compressive strength of the insulating element 4 according to the present invention (curve C4) with the compressive strength of the insulating element containing mineral fibers and no formaldehyde adhesive shown in curve B4, and the compressive strength of the insulating element containing mineral fibers and phenol-formaldehyde adhesive shown in curve A4.

[0526] The compressive strength was measured in accordance with EN 826. It can be seen that the compressive strength was measured immediately after the production of insulating element 4, as well as 7 days, 14 days and 28 days after the production of insulating element 4.

[0527] The compressive strength of the insulating element 4 according to the present invention is very close to the compressive strength (A4) of the insulating element containing phenol-formaldehyde adhesive. However, it can be seen that the loss in compressive strength (B4) of the insulating element containing no formaldehyde adhesive is much greater than the increase in compressive strength of the insulating element 4 according to the present invention. Furthermore, the compressive strength of the insulating element 4 according to the present invention is very close to the compressive strength (A4) of the insulating element containing phenol-formaldehyde adhesive. It can be seen that curves C2 and A2 are approximately parallel to each other.

[0528] Table IV below is in accordance with Figure 6 The relative compressive strength according to Table III is shown as a percentage of the initial compressive strength.

[0529]

[0530] Table IV

[0531] Table IV shows a comparison of the relative compressive strength (C5) of the insulating element 4 according to the present invention with the relative compressive strength (A5) of the insulating element containing phenol-formaldehyde adhesive and the relative compressive strength (B5) of the insulating element containing no formaldehyde adhesive. The corresponding curves are illustrated in... Figure 6 middle.

[0532] according to Figure 6 The relative compressive strength of the insulating element 4 according to the present invention (curve C5) was compared with the relative compressive strength of an insulating element containing phenol-formaldehyde adhesive (curve A5) or an insulating element containing no formaldehyde adhesive (curve B5). All insulating elements to be compared underwent an aging treatment including the steps described above.

[0533] In addition, from Figure 6 It can be seen that the compressive strength value of the insulating element 4 according to the present invention is approximately equal to the compressive strength value of the insulating element containing phenol-formaldehyde adhesive.

Claims

1. A roofing system for a flat or pitched roof of a building with thermal insulation and / or sound insulation properties, the roofing system comprising structural supports, support plates, a waterproof membrane, and at least one insulating element, said at least one insulating element being a bonded mineral fiber product made of mineral fibers and a cured aqueous adhesive composition, wherein the aqueous adhesive composition before curing comprises one or more components in the form of oxidized lignin (i) and one or more components in the form of modifiers (iia), and wherein said insulating element has a strength of 70 kg / m². 3 Up to 250 kg / m 3 The packing density between them.

2. The roof system of claim 1, wherein the roof system includes a steam control layer.

3. The roofing system according to claim 1, wherein the mineral fiber is rock wool fiber.

4. The roof system of claim 1, wherein the insulating element has a loss on ignition (LOI) in the range of 2 to 8 wt%.

5. The roof system of claim 4, wherein the insulating element has a loss on ignition (LOI) in the range of 2 to 5 wt%.

6. The roof system according to claim 1, having an insulating element with a compressive strength between 50 and 130 kPa, said compressive strength being measured according to European standard EN 826:2013.

7. The roof system according to claim 1, having insulating elements with a layer strength between 20 and 50 kPa, said layer strength being measured in accordance with European standard EN 1607:2013.

8. The roofing system according to claim 1, wherein the component (i) is in the form of one or more ammonia-oxidized lignin (AOL).

9. The roofing system of claim 1, wherein the component (iia) comprises one or more modifiers selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

10. The roofing system of claim 1, wherein the component (iia) comprises - One or more modifiers selected from polyethyleneimine, polyethyleneamine, and aliphatic amines; and / or - One or more modifiers in the form of fatty amides; and / or - One or more modifiers selected from dimethoxyacetaldehyde, glycolaldehyde, and glyoxylic acid; and / or - One or more crosslinking agents selected from polyester polyols; and / or - One or more modifiers selected from starch, modified starch, and CMC; and / or - One or more modifiers in the form of aliphatic multifunctional carbodiimides; and / or One or more modifiers selected from melamine-based crosslinking agents.

11. The roof system of claim 10, wherein: - The polyester polyol includes polycaprolactone; and / or - The melamine-based crosslinking agent includes a crosslinking agent based on hexa(methoxymethyl)melamine (HMMM).

12. The roof system according to claim 1, comprising component (iia) in an amount of 1 to 40 wt% based on the dry weight of component (i).

13. The roofing system according to claim 1, comprising component (iia) in an amount of 4 to 20 wt% based on the dry weight of component (i).

14. The roofing system according to claim 1, comprising a component (iia) in an amount of 6 to 12 wt% based on the dry weight of component (i).

15. The roof system of claim 1, further comprising: - Components in the form of one or more crosslinking agents (ii); and / or - One or more components in the form of plasticizers (iii).

16. The roofing system of claim 15, wherein component (ii) comprises: - One or more crosslinking agents selected from β-hydroxyalkylamides and oxazolines; and / or - One or more crosslinking agents selected from polyethyleneimine, polyethyleneamine, and aliphatic amines; and / or - One or more crosslinking agents in the form of fatty amides; and / or - One or more crosslinking agents selected from dimethoxyacetaldehyde, glycolaldehyde, and glyoxylic acid; and / or - One or more crosslinking agents selected from polyester polyols; and / or - One or more crosslinking agents selected from starch, modified starch, and CMC; and / or - One or more crosslinking agents in the form of aliphatic multifunctional carbodiimides; and / or - One or more crosslinking agents selected from melamine-based crosslinking agents.

17. The roofing system of claim 15, wherein the component (iii) comprises one or more plasticizers selected from polyethylene glycol, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or acids, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactide, acrylic-based polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups.

18. The roofing system of claim 17, wherein the acid is selected from bisaccharide, vanillic acid, lactic acid and / or ferulic acid.

19. The roofing system of claim 15, wherein component (iii) comprises - One or more plasticizers selected from fatty alcohols and monohydroxy alcohols; and / or - One or more plasticizers selected from alkoxylates; and / or - One or more plasticizers in the form of propylene glycol; and / or - One or more plasticizers in the form of ethylene glycol esters; and / or - Select one or more plasticizers of its own diester, acetate, benzoate, cyclobenzoate, citrate, stearate, sorbate, sebate, azelaate, butyrate, valerate; and / or - One or more plasticizers selected from phenol derivatives; and / or - One or more plasticizers selected from silanols and siloxanes; and / or - One or more plasticizers selected from sulfates, sulfonates, and / or phosphates; and / or - One or more plasticizers in the form of hydroxy acids; and / or - One or more plasticizers selected from monomeric amides, benzamides, and fatty acid amides; and / or - One or more plasticizers selected from quaternary ammonium compounds; and / or - One or more plasticizers selected from vegetable oils; and / or - One or more plasticizers selected from hydrogenated oils and acetylated oils; and / or - One or more plasticizers selected from methyl esters; and / or - One or more plasticizers selected from alkyl polyglycosides, glucosamides, aminoglucosamides, sucrose esters, and sorbitol esters; and / or One or more plasticizers selected from polyethylene glycol and polyethylene glycol ether.

20. The roof system of claim 19, wherein: - The monohydroxy alcohol includes pentanol and / or stearyl alcohol; and / or - The alkoxylated compounds include ethoxylated compounds, butanol ethoxylated compounds, and / or butoxytriethylene glycol; and / or - The phenol derivatives include alkyl and / or aryl substituted phenols; - The sulfate includes alkyl sulfates; and / or - The sulfonate includes alkyl aryl sulfonates; and / or - The phosphate includes tripolyphosphate; and / or - The monomeric amide includes acetamide; and / or - The fatty acid amide includes talloylamide; and / or - The quaternary ammonium compound includes trimethylglycine and / or distearate dimethylammonium chloride; and / or - The vegetable oils include castor oil, palm oil, flaxseed oil, tall oil and / or soybean oil.

21. The roof system according to claim 16, wherein the content of said component (iii) is 0.5 to 50 wt% based on the dry weight of said component (i).

22. The roof system according to claim 21, wherein the content of said component (iii) is 2.5 to 25 wt% based on the dry weight of said component (i).

23. The roof system according to claim 22, wherein the content of said component (iii) is 3 to 15 wt% based on the dry weight of said component (i).

24. The roofing system of claim 1, comprising other components in the form of one or more coupling agents in the adhesive (iv).

25. The roofing system of claim 24, wherein one or more coupling agents comprise organofunctional silanes.

26. The roofing system of claim 1 further comprises one or more components (v) selected from ammonia, amines or any salts thereof in the form of the adhesive.

27. The roofing system of claim 1, comprising other components in the form of urea in the adhesive.

28. The roofing system of claim 27, wherein the urea content in the adhesive is 5 to 40 wt% based on the dry weight of component (i).

29. The roofing system of claim 28, wherein the urea content in the adhesive is 10 to 30 wt% based on the dry weight of component (i).

30. The roofing system of claim 29, wherein the urea content in the adhesive is 15 to 25 wt% based on the dry weight of component (i).

31. The roofing system of claim 1, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); water.

32. The roofing system of claim 31, wherein one or more coupling agents comprise organofunctional silanes.

33. The roofing system of claim 1, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); - One or more components in the form of compounds selected from ammonia, amines, or any salts thereof; water.

34. The roofing system of claim 1, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); - Components in the form of urea; water.

35. The roofing system of claim 1, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); - Components in the form of more reactive or non-reactive silicones; water.

36. The roofing system of claim 1, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); - Hydrocarbon oil; water.

37. The roofing system of claim 1, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); - One or more surfactants; water.

38. An insulating element for a roofing system according to claim 1, said insulating element being made of mineral fibers and a cured aqueous adhesive composition, wherein the aqueous adhesive composition before curing comprises one or more components in the form of oxidized lignin (i), one or more components in the form of a modifier (iia), and wherein said insulating element has a strength of 70 kg / m³. 3 Up to 250 kg / m 3 The packing density between them.

39. The insulating element according to claim 38, wherein the mineral fiber is rock wool fiber.

40. The insulating element according to claim 38, having a loss on burn (LOI) in the range of 2 to 8 wt%.

41. The insulating element according to claim 38, having a loss on burn (LOI) in the range of 2 to 5 wt%.

42. The insulating element according to claim 38 has a compressive strength between 50 and 130 kPa as measured according to European standard EN 826:2013.

43. The insulating element according to claim 38 has a delamination strength between 20 and 50 kPa as measured in accordance with European standard EN 1607:2013.

44. The insulating element according to claim 38, wherein the component (i) is in the form of one or more ammoniacal lignin (AOL).

45. The insulating element according to claim 38, wherein the component (iia) comprises one or more modifiers selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

46. ​​The insulating element according to claim 38, wherein the component (iia) comprises: - One or more modifiers selected from polyethyleneimine, polyethyleneamine, and fatty amines; and / or - One or more modifiers in the form of fatty amides; and / or - One or more modifiers selected from dimethoxyacetaldehyde, glycolaldehyde, and glyoxylic acid; and / or - One or more modifiers selected from polyester polyols; and / or - One or more modifiers selected from starch, modified starch, and CMC; and / or - One or more modifiers in the form of aliphatic multifunctional carbodiimides; and / or - One or more modifiers selected from melamine-based crosslinking agents.

47. The insulating element according to claim 46, wherein: - The polyester polyol includes polycaprolactone; and / or - The melamine-based crosslinking agent includes a crosslinking agent based on hexa(methoxymethyl)melamine (HMMM).

48. The insulating element according to claim 38, comprising component (iia) having a dry weight of 1 to 40 wt% based on component (i).

49. The insulating element according to claim 48, comprising component (iia) having a dry weight of 4 to 20 wt% based on component (i).

50. The insulating element according to claim 48, comprising component (iia) having a dry weight of 6 to 12 wt% based on component (i).

51. The insulating element according to claim 38, further comprising: - Components in the form of one or more crosslinking agents (ii); and / or - One or more components in the form of plasticizers (iii).

52. The insulating element according to claim 51, wherein the component (ii) comprises: - One or more crosslinking agents selected from β-hydroxyalkylamides and oxazolines; and / or - One or more crosslinking agents selected from polyethyleneimine, polyethyleneamine, and aliphatic amines; and / or - One or more crosslinking agents in the form of fatty amides; and / or - One or more crosslinking agents selected from dimethoxyacetaldehyde, glycolaldehyde, and glyoxylic acid; and / or - One or more crosslinking agents selected from polyester polyols; and / or - One or more crosslinking agents selected from starch, modified starch, and CMC; and / or - One or more crosslinking agents in the form of aliphatic multifunctional carbodiimides; and / or - One or more crosslinking agents selected from melamine-based crosslinking agents.

53. The insulating element according to claim 51, wherein the component (iii) comprises one or more plasticizers selected from polyethylene glycol, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or acids, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactide, acrylic-based polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups.

54. The insulating element according to claim 53, wherein the acid is selected from adipic acid, vanillic acid, lactic acid and / or ferulic acid.

55. The insulating element according to claim 51, wherein the component (iii) comprises: - One or more plasticizers selected from fatty alcohols and monohydroxy alcohols; and / or - One or more plasticizers selected from alkoxylates; and / or - One or more plasticizers in the form of propylene glycol; and / or - One or more plasticizers in the form of ethylene glycol esters; and / or - Select one or more plasticizers of its own diester, acetate, benzoate, cyclobenzoate, citrate, stearate, sorbate, sebate, azelaate, butyrate, valerate; and / or - One or more plasticizers selected from phenol derivatives; and / or - One or more plasticizers selected from silanols and siloxanes; and / or - One or more plasticizers selected from sulfates, sulfonates, and / or phosphates; and / or - One or more plasticizers in the form of hydroxy acids; and / or - One or more plasticizers selected from monomeric amides, benzamides, and fatty acid amides; and / or - One or more plasticizers selected from quaternary ammonium compounds; and / or - One or more plasticizers selected from vegetable oils; and / or - One or more plasticizers selected from hydrogenated oils and acetylated oils; and / or - One or more plasticizers selected from methyl esters; and / or - One or more plasticizers selected from alkyl polyglycosides, glucosamides, aminoglucosamides, sucrose esters, and sorbitol esters; and / or - One or more plasticizers selected from polyethylene glycol and polyethylene glycol ether.

56. The insulating element according to claim 55, wherein: - The monohydroxy alcohol includes pentanol and / or stearyl alcohol; and / or - The alkoxylated compounds include ethoxylated compounds, butanol ethoxylated compounds, and / or butoxytriethylene glycol; and / or - The phenol derivatives include alkyl and / or aryl substituted phenols; - The sulfate includes alkyl sulfates; and / or - The sulfonate includes alkyl aryl sulfonates; and / or - The phosphate includes tripolyphosphate; and / or - The monomeric amide includes acetamide; and / or - The fatty acid amide includes talloylamide; and / or - The quaternary ammonium compound includes trimethylglycine and / or distearate dimethylammonium chloride; and / or - The vegetable oils include castor oil, palm oil, flaxseed oil, tall oil and / or soybean oil.

57. The insulating element according to claim 51, wherein the content of said component (iii) is 0.5 to 50 wt% based on the dry weight of said component (i).

58. The insulating element according to claim 57, wherein the content of said component (iii) is 2.5 to 25 wt% based on the dry weight of said component (i).

59. The insulating element according to claim 57, wherein the content of said component (iii) is 3 to 15 wt% based on the dry weight of said component (i).

60. The insulating element of claim 38, comprising other components in the form of one or more coupling agents in the adhesive (iv).

61. The insulating element according to claim 60, wherein the one or more coupling agents comprise organofunctional silanes.

62. The insulating element of claim 38 further comprises a component (v) selected from ammonia, amine or any salt thereof in the adhesive.

63. The insulating element of claim 38, comprising other components in the form of urea in the adhesive.

64. The insulating element according to claim 63, wherein the urea content in the adhesive is 5 to 40 wt% based on the dry weight of component (i).

65. The insulating element according to claim 64, wherein the urea content in the adhesive is 10 to 30 wt% based on the dry weight of component (i).

66. The insulating element according to claim 64, wherein the urea content in the adhesive is 15 to 25 wt% based on the dry weight of component (i).

67. The insulating element of claim 38, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); water.

68. The insulating element according to claim 67, wherein the one or more coupling agents comprise organofunctional silanes.

69. The insulating element of claim 38, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); - One or more components in the form of compounds selected from ammonia, amines, or any salts thereof; water.

70. The insulating element of claim 38, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); - Components in the form of urea; water.

71. The insulating element according to claim 38, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); - Components in the form of more reactive or non-reactive silicones; water.

72. The insulating element of claim 38, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); - Hydrocarbon oil; water.

73. The insulating element of claim 38, wherein the adhesive comprises: - One or more components in the form of oxidized lignin (i); - Components in the form of one or more modifiers (iia); - Components in the form of one or more coupling agents (iv); - One or more surfactants; water.

74. The insulating element of claim 38, comprising a first layer and a second layer, the first layer comprising rock wool fibers and an adhesive, the second layer being made of glass wool, wherein the second layer is fixed to the main surface of the first layer by an adhesive, wherein the first layer is made of at least one thin layer having a fiber orientation substantially perpendicular to the main surface of the second layer, and wherein the first layer contains a cured adhesive. Its features are, The adhesive is partially disposed in the region between the fibers of the first layer facing the main surface of the second layer, and partially disposed in the region of the second layer facing the main surface of the first layer, such that the adhesive connects the first layer and the second layer in such a way that forces perpendicular to the second layer can be compensated by the tensile strength of the second layer combined with the flexural strength of the adhesive and / or the fibers of the first layer, thereby producing a maximum deformation of the insulating element of less than or equal to 5% of its thickness.

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