EA045325B1 - ROOFING SYSTEM AND INSULATING ELEMENT FOR FLAT ROOF OR FLAT SLANTED ROOF - Google Patents

Description

Field of technology to which the present invention relates

The present invention relates to a roofing system for a flat roof or flat sloping roof of a thermally and/or acoustically insulated building, which consists of a support structure, a roof deck, an optional vapor barrier layer, a waterproof membrane and at least one insulation element that is a product of sized mineral fibers, which is made of mineral fibers, preferably stone wool fibers, and a binder. Furthermore, the present invention relates to an insulating element for such a roofing system made of mineral fibers, preferably rock wool fibers, and a binder.

BACKGROUND OF THE INVENTION

Flat roofs and flat sloped roofs, such as membrane roofing systems, are well known in the prior art, which are generally divided into the following types depending on the location of the main thermal insulation: warm roofs, reverse warm roofs, roof gardens or green roofs and non-insulated roofs.

Nowadays, membrane roofing systems are often created as single-ply roofing systems that are used to protect flat roofs or flat sloped roofs from exposure to any weather conditions that are likely to occur during their service life.

A typical single-ply roofing system contains: a support structure; roof decking providing permanent support; vapor barrier layer (if necessary); thermal insulation; waterproof membrane; and finishes that are wear-resistant or stress-resistant (if required for functional and/or aesthetic reasons).

Most flat roofs or flat sloping roofs are now designed as so-called warm roofs. In such warm roofs, the main thermal insulation is located directly under the roof covering, namely under the waterproof membrane. This keeps the roof deck warm in cold weather and controls moisture condensation without the need for ventilation. Optionally, a vapor barrier layer is installed on top of the roof deck to control the penetration of water vapor into the insulation. This is a very reliable and economical way to insulate a membrane roof to the highest requirements.

There are three main options for attaching single ply roofing systems, namely mechanical fastening, bonding/cold bonding and ballasting, and the insulation and membrane can be attached in the same or different ways.

For roofing systems on flat or flat sloping roofs of buildings, as well as for the use of insulating elements consisting of bonded mineral fiber products, various systems known from the prior art are suitable.

In certain cases, layers of mineral fibers (eg, glass fiber) can also be used as a non-woven fabric with a dense pile or fabric covering the entire area of the insulating elements, said fabric being sandwiched between the insulating elements and the waterproof membrane. A panel formed from several insulating elements located adjacent to each other may be characterized by the presence of a layer of densely brushed non-woven fabric or fabric covering its entire area. This sheet or fabric can be glued to the insulating elements using an adhesive that is applied between the contacting surfaces. This web or fabric provides support for the component elements of the panel, and it can increase its mechanical strength by transferring the force applied to one element to an adjacent element. This web or fabric is characterized by the presence of small pores, for example with pore sizes or distances between adjacent fibers being less than 0.5 mm, for example only 0.1 mm.

Modern roofing systems use fabric or canvas lined or bitumen coated roofing panels to provide the appropriate insulation layer surface required to bond/bond the waterproof membrane. However, despite the possibility of using these systems, they have one drawback, which is that the adhesives can be applied to the layer of the insulating element by spraying. Such a dispersed adhesive significantly impairs the insulating and/or damping characteristics of said insulating layer. Moreover, the use of dispersed adhesive leads to increased adhesive consumption and unregulated adhesive strength, which leads to a higher cost of such a system.

Finally, such adhesives, which are usually organic adhesives, reduce the fire resistance of the insulating elements, particularly in the case of the bitumen-coated roofing panels mentioned above.

For example, WO 98/31895 discloses a roofing system comprising: a mineral fiber core; a fabric covering the core and bonded to the core with resin to form a panel; and a moisture/waterproof fabric covering fabric that is bonded to the panel with an adhesive extending into the mineral fiber core. Although this composite roofing system is widely used on flat and flat sloped roofs, it has several disadvantages described above.

Another example implementation of a roofing system is disclosed in WO 2013/034376. This roofing system includes insulating elements providing thermal and/or sound insulation, consisting of two layers, of which at least one layer is made of mineral fibers, in particular stone wool fibers, and the second layer is made of at least one fabric and attached to the main surface of the first layer with an adhesive, the second layer being provided with a filler which imparts a certain permeability to the second layer.

Since any loads placed on a warm roof are transferred to the entire structure through the insulation, it requires a rigid material to construct it. Its choice is important as different products provide different support strengths and require more or less thickness to achieve the selected insulating capacity. This must be taken into account when designing and planning a roofing system for a flat or sloped flat roof building.

Basically, there are two main types of insulation products:

cellular materials such as, for example, polyisocyanurate (PIR), expanded polystyrene (EPS) or extruded polystyrene (XPS); and fibrous materials such as, for example, mineral wool (MW) and in particular stone wool.

The latest mineral wool products are well known for their excellent thermal and sound insulation properties, as well as their mechanical strength and excellent fire resistance. These products are also referred to as mineral sized fiber products, which consist of mineral fibers and a binder, and the relevant requirements for such products are specified in the European standard EN 13162:2015-04 entitled Thermal insulation products for buildings - factory-made mineral wool (MW) products.

Mineral fiber or rock wool products typically contain glass wool (MMVF). Glass wool (MMVF) can be characterized by any suitable oxide composition. Said fibers may be glass fiber, ceramic fiber, basalt fiber, slag fiber, stone or mineral fiber. Preferably, the fibers are of these types, commonly known as mineral, rock or slag fibers, and more preferably as rock fibers bonded together using a cured thermoset polymer binder.

A preferred binder is a phenol-formaldehyde resin, which can be produced in a cost-effective manner and which can be supplemented with urea before being used as a binder. However, current legislation and proposed legislation aimed at reducing or eliminating formaldehyde emissions have led to the development of formaldehyde-free binders, such as, for example, binder compositions based on polycarboxypolymers or polyols or polyamines.

Another group of binders that do not contain phenol-formaldehyde includes the products of the addition/elimination reaction of aliphatic and/or aromatic anhydrides with alkanolamines. These binder compositions are water soluble and exhibit excellent binding properties in terms of cure speed and cure density.

Since some of the starting materials used in the production of these binders are quite expensive chemicals, there is a pressing need to provide formaldehyde-free binders, sometimes also referred to as no added formaldehyde (NAF) binders, produced in a cost-effective manner.

An additional effect associated with previously known water-based mineral fiber binder compositions is that at least the majority of the starting materials used to produce these binders are derived from fossil hydrocarbons. Today there is a trend in which consumers prefer products that are made entirely or at least partially from renewable raw materials; and therefore there is a need for mineral wool binders that can be at least partially derived from renewable raw materials.

Another additional effect associated with previously known water-based mineral fiber binder compositions is that they contain components that are corrosive and/or toxic. This requires measures to be taken to protect machinery involved in the production of mineral wool products to prevent corrosion, and also requires measures to be taken to ensure the safety of personnel operating that machinery. This leads to increased costs and growing problems associated with protecting health; Consequently, there is a need for mineral fiber products that use binder compositions with reduced levels of corrosive and/or toxic materials.

This includes a range of mineral fiber binders that are largely based on renewable raw materials. In many cases, these binders, based largely on renewable resources, are also free of formaldehyde.

However, many of these binders remain relatively expensive because they are made from relatively expensive raw materials. Moreover, to date they have not provided sufficient strength properties for end-products made from mineral fibers over an extended period of time.

Roofing systems for flat or flat pitched roofs should be designed to last 30 years or more; and thus they require durable materials for their manufacture. Since the loads imposed on such roofs are transferred to the entire structure through the insulation, bonded mineral fiber products must be designed to withstand most loads, especially pressure loads such as, for example, occasional small loads from people walking on the roof during construction. and also, in particular, when carrying out appropriate checks during subsequent maintenance; and, in addition, to withstand any weather conditions, in particular wind loads, that may occur over time. Consequently, mineral fiber products used for insulation of roofing systems require a certain stiffness, which is determined by the density, and therefore the density of such products usually lies in the range from 70 to about 250 kg/m ³ , which determines the corresponding strength characteristics, also over long periods of time. period of time.

Insulation elements, including sized mineral fiber products using these phenol-formaldehyde resins and urea-filled phenol-formaldehyde resins, are known for their superior properties when they lose strength over time, for example due to wear, and are therefore used in for decades. Prior art formaldehyde-free or no added formaldehyde (NAF) binders have proven suitable for use in lightweight products with a bulk density of less than about 60 kg/m ³ , i.e. in products that are placed, for example, in cavities or spaces that are subsequently closed, and when there is no need for these products to carry any loads or have any special mechanical strength. However, these formaldehyde-free binders can be considered as essential elements if such insulating elements are to withstand loads and mechanical stress, since they are generally subject to wear and tear, causing them to lose their strength over time.

Brief Disclosure of the Present Invention

Therefore, the object of the present invention is to provide a roofing system with mineral fiber elements that would be suitable for use in such roofing systems, and which would not use expensive and/or toxic binder materials and/or toxic binders such as such.

Another object of the present invention is to provide mineral fiber elements useful for roofing systems without the use of expensive and/or toxic binder materials and/or without the use of costly and/or toxic binders per se.

According to the present invention, a roofing system comprises a mineral fiber insulating element including a binder which contains a component in the form of one or more oxidized lignins, a component in the form of one or more cross-linking agents and a component in the form of one or more plasticizers, wherein the insulating element is characterized by volume density ranging from 70-250 kg/ ^m3 .

Moreover, according to the present invention, the roof insulation element is made of mineral fibers, preferably rock wool fibers, and a binder, wherein the binder contains a component in the form of one or more oxidized lignins, a component in the form of one or more cross-linking agents and a component in the form of one or more several plasticizers, and the insulating element is characterized by a bulk density ranging from 70-250 kg/m ³ .

It has been found that it is possible to obtain an insulating element made of mineral fibers and a binder as described above, which would provide the necessary mechanical strength for use in a roofing system for a flat or flat sloped roof, and on the one hand this insulating element does not contain a toxic binder , as well as formaldehyde, and on the other hand, the binder has high resistance to aging and very little loss of strength throughout the entire service life of the roofing system. Moreover, it is possible to reduce the volume of the binder compared to formaldehyde-containing binders used in the prior art, such as, for example, the existing NAF type binders.

In one embodiment of the present invention, the insulating element may have any of the preferred features described in connection with a roofing system.

In a preferred embodiment, the insulating element is characterized by a loss on ignition (LOI) in the range of 2-8 wt.%. The binder content is taken as LOI and is determined in accordance with the requirements of the European standard EN 13820:2003. The binder includes oil and other binder additives.

According to one of the preferred embodiments of the present invention, a roofing system is provided with insulating elements having a compressive strength in the range of 50-130 kPa, measured in accordance with the requirements of the European standard EN 826:2013.

According to another embodiment of the present invention, a roofing system is provided with insulating elements having a delamination strength in the range of 20-50 kPa, measured in accordance with the requirements of the European standard EN 1607:2013.

Such insulating elements, which include bonded mineral fiber products, are known for their excellent fire resistance and are generally classified as Euro Class A1 according to the European Standard EN 13501-1:2018, unless they are further treated or provided with either coatings or cladding.

In one embodiment of the present invention, the binder used in the insulating elements of the present invention, which are used in the roofing systems of the present invention, does not contain formaldehyde.

The term formaldehyde-free or formaldehyde-free describes an insulating element made of mineral fibers and a binder, where the release of formaldehyde from the insulating element is less than 5 mg/m ² /hour, and preferably less than 3 mg/m ² /hour. Preferably, a test in accordance with the requirements of ISO 16000 is carried out to determine aldehyde release.

Component (i).

As one of the components (i) the binder contains one or more oxidized lignins.

Lignin, cellulose and hemicellulose are the three main organic compounds that are present in the plant cell wall. Lignin can be thought of as the glue that holds cellulose fibers together. Lignin contains both hydrophilic and hydrophobic groups. It is the world's second most abundant natural polymer, second only to cellulose, and is estimated to account for up to 20-30% of all carbon contained in biomass, amounting to more than one billion tons globally.

In fig. Figure 7 shows a segment of a possible lignin structure.

There are at least four groups of technical lignins available on the market. These four groups are shown in Fig. 9. A possible fifth group, called biorefining lignin, is somewhat different from these groups, since it is not described by an extraction process, but by an initial process, such as biorefining; and thus it may be similar to or different from any of the other groups mentioned. Each group is different and each is suitable for different applications. Lignin is a heterogeneous material with a complex structure, consisting of up to three different phenylpropane monomers, which depends on the source material. Coniferous lignins are composed primarily of coniferyl alcohol units (see FIG. 8) and as a result are more uniform than hardwood lignins, which have a higher lilac alcohol content (see FIG. 8). The appearance and consistency of lignin can be very different, and these parameters largely depend on the technological process.

The properties of these technical lignins are summarized in FIG. 10. Lignosulfonate produced from sulfite pulping remains the largest source of lignin available on the market, with a production volume of 1.4 million tons. But if we put this option aside, at present the most common method of pulp cooking is the kraft process (or kraft cooking), which is gradually replacing sulfite pulping. According to preliminary estimates, the kraft pulping process produces 78 million tons of lignin annually worldwide, but most of it is burned to produce steam and energy. Current kraft production is estimated at 160,000 tons, but some sources claim the volume is only around 75,000 tons. Kraft lignin is produced from black liquor, i.e. from liquor waste from the kraft pulping or kraft process. There are currently three well-known processes used to produce kraft lignin: LignoBoost, LignoForce and SLRP. The three methods are similar in that they involve the addition of _CO2 to reduce the pH to 9-10, followed by acidification to further reduce the pH to about 2. The final step involves some combination of washing, leaching and filtration to remove ash and other pollutants. These three methods are at different stages of commercialization on a global scale.

The crafting process involves the introduction of thiol groups, the so-called stilbene, while maintaining

- 4 045325 of a certain carbohydrate. Soda sulfate is also present as an impurity, due to the precipitation of lignin from the sulfuric acid liquor, but this can be avoided by changing the method of lignin isolation. The kraft process ultimately provides a large volume of phenolic hydroxyl groups, and upon ionization of these groups (pH greater than ~10), this lignin can dissolve in water.

Industrial kraft lignin is generally of higher purity than lignosulfonates. Its molecular weight is 1000-3000 g/mol.

Soda lignin can be produced by soda pulping (cooking with a caustic soda solution), which is used primarily on wheat straw, sugarcane pomace and flax. The properties of soda lignin are similar to those of kraft lignin in terms of solubility and _Tg . This process does not use sulfur and there is no covalently bound sulfur. Ash level is very low. Soda lignin is characterized by low solubility in neutral and acidic environments, but it is completely dissolved at a pH of 12 and above.

The lignosulfonate process involves the introduction of a large number of sulfonate groups, which makes lignin soluble not only in water, but also in acidic water solutions. Lignosulfonates contain up to 8% sulfur as sulfonate, while kraft lignin contains only 1-2% sulfur, mostly bound to the lignin. The molecular weight of lignosulfonate is 15000-50000 g/mol. This lignin contains more residual carbohydrates compared to other types of lignin and also has a higher average molecular weight. The typical hydrophobic core of lignin, together with the large number of ionized sulfonate groups, makes this lignin attractive for use as a surfactant, and it often finds use as a dispersant for cement, etc.

Another group of available lignins are lignins obtained through the biorefining process, in which carbohydrates are separated from lignin through chemical and biochemical processes to obtain a carbohydrate-rich fraction. This residual lignin is called biorefined lignin. Biorefining focuses on the production of energy and substitute products from fossil hydrocarbons and petrochemicals, as well as lignin. The lignin produced by this process is generally considered a low-value product or even a by-product that is used primarily for thermal combustion or as low-grade feed or otherwise disposed waste.

The production of organosolv lignins is still at the pilot production stage. This process involves the extraction of lignin by using water along with various organic solvents (most commonly ethanol) and some organic acids. The advantage of this process is the high degree of purity of the resulting lignin, but at a much higher cost compared to other technical lignins, as well as the ability to dissolve it in organic solvents rather than in water.

Previous attempts to use lignin as a base compound for mineral fiber binder compositions have failed because it has proven difficult to find suitable cross-linking agents that can provide the required mechanical properties to the cured mineral wool product while preventing the use of toxic and/or corrosive components. Currently, lignin is used as a replacement for chemicals derived from crude oil, such as phenol or phenolic resins in binders or bitumen. It is also used as cement and concrete additives and in some aspects as dispersants.

Cross-linking of a polymer should generally improve its properties, such as mechanical strength, chemical resistance, heat resistance, and the like. Lignin is found in large quantities in phenolic and aliphatic hydroxyl groups, which react to form a cross-linked lignin structure. Different lignins will also have other active functional groups that could potentially be used. The presence of these other groups depends largely on the manner in which lignin is isolated from cellulose and hemicellulose (thiols in kraft lignin, sulfonates in hemicellulose, etc.) depending on the source.

It has been found that by using oxidized lignins, a binder composition for mineral fibers can be prepared, which provides excellent properties to the resulting mineral fiber product.

In one embodiment of the present invention, component (i) is in the form of one or more oxidized kraft lignins.

In one embodiment of the present invention, component (i) is in the form of one or more oxidized soda lignins.

In one embodiment of the present invention, component (i) in the form of one or more oxidized lignins is presented in the form of one or more ammonia oxidized lignins. For the purposes of the present invention, the term ammonia-oxidized lignin refers to lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term ammonia-oxidized lignin is given the abbreviation AOL.

- 5 045325

In one alternative embodiment of the present invention, the ammonia is partially or completely replaced by an alkali metal hydroxide, in particular sodium hydroxide and/or potassium hydroxide.

A typical oxidizing agent used to prepare oxidized lignins is hydrogen peroxide.

In one embodiment of the present invention, the ammonia-oxidized lignin contains one or more compounds selected from the group consisting of ammonia, amines, hydroxides, or any salts thereof.

In one embodiment of the present invention, component (i) in the form of one or more oxidized lignins contains a carboxylic acid group in a volume of 0.05-10 mmol/g, for example 0.1-5 mmol/g, for example 0.20-1 .5 mmol/g, for example 0.40-1.2 mmol/g, for example 0.45-1.0 mmol/g, based on the dry weight of the component in the form of one or more oxidized lignins.

In one embodiment of the present invention, component (i) in the form of one or more oxidized lignins has an average content of carboxylic acid groups of more than 1.5 groups per macromolecule of component (i) in the form of one or more oxidized lignins, for example , more than two groups, for example, more than two and a half groups.

It is believed that the content of carboxylic acid groups in the oxidized lignins plays a critical role in providing the striking benefits of the water-based binder compositions used for the mineral fiber elements of the present invention. In particular, it is generally accepted that the carboxylic acid group in oxidized lignins improves cross-linking properties and therefore provides better mechanical properties to cured mineral fiber products.

Component (ii).

Binder component (ii) is in the form of one or more cross-linking agents.

In one embodiment of the present invention, component (ii) contains in one embodiment one or more cross-linking agents selected from β-hydroxyalkylamide cross-linking agents and/or oxazoline cross-linking agents.

Such β-hydroxyalkylamide cross-linkers provide a curing agent for acid-functional macromolecules that provides a strong and stable corrosion-resistant and solvent-resistant cross-linked polymer network. It is generally accepted that β-hydroxyalkylamide cross-linkers cure through an esterification reaction to form multiple ester linkages. To obtain optimal curing response, the hydroxy functionality of β-hydroxyalkylamide cross-linkers should average at least 2; in the preferred embodiment, more than 2; and in a more preferable embodiment - in the range of 2-4.

Oxazoline group-containing cross-linkers are polymers containing one or more oxazoline groups in each molecule, and generally, oxazoline containing cross-linkers can be readily prepared by polymerizing an oxazoline derivative. Such a process is disclosed in US Pat. No. 6,818,699 B2.

In one embodiment of the present invention, component (ii) is an epoxidized triglyceride fatty acid oil.

It should be noted that epoxidized triglyceride fatty acid oils are not considered to be hazardous to health; and, therefore, the use of these compounds in the binder compositions of the present invention does not render these compositions hazardous to handle.

In one embodiment of the present invention, component (ii) is a molecule having three or more epoxy groups.

In one embodiment of the present invention, component (ii) is one or more flexible chain oligomers or polymers, such as an acrylic-based polymer with a low glass transition temperature (Tg), for example, a vinyl-based polymer with a low glass transition temperature, for example, a polyester with low glass transition temperature, which contains reactive functional groups such as carbodiimide groups, for example anhydride groups, for example oxazoline groups, for example amino groups, for example epoxy groups.

In one embodiment of the present invention, component (ii) is selected from the group consisting of curing reaction cross-linking agents such as hydroxyalkyl amide, alkanolamine, alkanolamine reaction product and polycarboxylic acid. A description of the reaction product of an alkanolamine and a polycarboxylic acid can be found in US 6,706,853 B1.

Without being bound by any particular theory, it is generally believed that the highly advantageous properties of the water-based binder composition used in the present invention are due to the interaction of the oxidized lignins used as a component

- 6 045325 (i), and the cross-linking agents mentioned above. There is reason to believe that the presence of carboxylic acid groups in oxidized lignins provides highly efficient cross-linking of oxidized lignins.

In one embodiment of the present invention, component (ii) is one or more cross-linking agents selected from the group consisting of multifunctional organic amines such as alkanolamine, diamines such as hexamethyldiamine, and triamines.

In one embodiment of the present invention, component (ii) is one or more cross-linking agents selected from the group consisting of polyethylenimine, polyvinylamine and fatty amines.

In one embodiment of the present invention, component (ii) is one or more fatty amides.

In one embodiment of the present invention, component (ii) is one or more cross-linking agents selected from the group consisting of dimethoxyethanol, glycolaldehyde and glycine-oxalic acid.

In one embodiment of the present invention, component (ii) is one or more cross-linking agents selected from polyester polyols such as polycaprolactone.

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

In one embodiment of the present invention, component (ii) is one or more aliphatic multifunctional carbodiimides cross-linking agents.

In one embodiment of the present invention, component (ii) is one or more cross-linkers selected from melamine-based cross-linkers, such as hexamethoxymethylmelamine (HMMM) cross-linkers.

Examples of such compounds include Picassian XL 701, 702, 725 (from Stahl Polymers), such as ZOLDINE® XL-29SE (from Angus Chemical Company), such as CX300 (from DSM), and such as Carbodilite V-02-L2 (manufactured by Nisshinbo Chemical Inc.).

Component (ii) may also be a mixture of the above components.

In one embodiment of the present invention, the binder composition used in the present invention includes component (ii), the content of which is 1-40 wt.%, for example 4-20 wt.%, for example 6-12 wt.%, based on the dry weight of the first component.

Component (iii).

Component (iii) is presented in the form of one or more plasticizers.

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

In one embodiment of the present invention, component (iii) is in the form of one or more plasticizers selected from the group consisting of carbonates such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with a structure similar to the structure of lignin-like vanillin, acetosyringone, solvents used as coalescing agents such as alcohol ethers, polyvinyl alcohol.

In one embodiment of the present invention, component (w) is presented in the form of one or more chemically inactive plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and/or other ethers, solvents used in as coalescing agents, such as alcohol ethers, acrylic polymers and polyvinyl alcohol.

In one embodiment of the present invention, component (iii) is one or more plasticizers selected from the group consisting of carbonates such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tricarboxylic acids such as adipic acid, or lactic acid, and/or vanillic acid, and/or ferulic acid, polyurethane dispersions, acrylic polymers with free carboxyl groups, compounds with

- 7 045325 structure similar to the structure of lignin-like vanillin, acetosyringone.

In one embodiment of the present invention, component (iii) is provided in the form of one or more plasticizers selected from the group consisting of fatty alcohols, monohydric alcohols such as pentanol, stearyl alcohol.

In one embodiment of the present invention, component (iii) contains one or more plasticizers selected from the group consisting of polyethylene glycols and polyethylene glycol ethers.

Another striking effect of the present invention is that the use of plasticizers with a boiling point above 100°C, in particular 140-250°C, significantly improves the mechanical properties of the mineral fiber products according to the present invention, although taking into account their boiling point these plasticizers , are likely to at least partially evaporate during the curing of water-based binders in contact with mineral fibers.

In one embodiment of the present invention, component (iii) contains one or more plasticizers with a boiling point greater than 100°C, for example in the range of 110-280°C, more preferably in the range of 120-260°C, and even more preferably within the range of 140-250°C.

It is believed that the effectiveness of these plasticizers in the water-based binder composition of the present invention is related to the effect of increasing the mobility of the oxidized lignins during the curing process. It can be assumed that the increased mobility of lignins or oxidized lignins during the curing process facilitates effective cross-linking.

In one embodiment of the present invention, component (iii) contains one or more polyethylene glycols, the average molecular weight of which lies in the range of 150-50,000 g/mol, in particular in the range of 150-4000 g/mol, in particular in the range of 150 -1000 g/mol, preferably in the range of 150-500 g/mol, and more preferably in the range of 200-400 g/mol.

In one embodiment of the present invention, component (iii) contains one or more polyethylene glycols, the average molecular weight of which lies in the range 4000-25000 g/mol, in particular in the range 4000-15000 g/mol, in particular in the range 8000- 12000 g/mol.

In one embodiment of the present invention, component (iii) is configured to form covalent bonds with component (i) and/or component (ii) during the curing process. Such a component will not evaporate and will remain part of the composition, but will be effectively modified so as not to introduce undesirable side effects, such as absorption of water by the curing product. Non-limiting examples of such a component include caprolactones and acrylic polymers with free carboxyl groups.

In one embodiment of the present invention, component (iii) is selected from the group consisting of fatty alcohols such as pentanol, stearyl alcohol.

In one embodiment of the present invention, component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxylates, such as ethoxylates, such as butanol ethoxylates, such as butoxytriglycol.

In one embodiment of the present invention, component (iii) is selected from one or more propylene glycols.

In one embodiment of the present invention, component (iii) is selected from one or more glycol ethers.

In one embodiment of the present invention, component (iii) is selected from one or more plasticizers selected from the group consisting of adipate, acetate, benzoate, cyclobenzoate, citrate, stearate, sorbate, sebacate, azelainate, butyrate and valerianate.

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

In one embodiment of the present invention, component (iii) is selected from one or more plasticizers selected from the group consisting of silanols and silokeanes.

In one embodiment of the present invention, component (iii) is selected from one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkylaryl sulfonates such as alkyl sulfonates, phosphates such as tripolyphosphates such as tributyl phosphates.

In one embodiment of the present invention, component (iii) is selected from one or more hydroxy acids.

In one embodiment of the present invention, component (iii) is selected from one or more plasticizers selected from the group consisting of monomeric amides,

- 8 045325 such as acetamides, benzamides, fatty acid amides, such as tall oil amides.

In one embodiment of the present invention, component (iii) is selected from one or more plasticizers selected from the group consisting of quaternary ammonium compounds such as trimethylglycine, distearyl dimethylammonium chloride.

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

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

In one embodiment of the present invention, component (iii) is selected from one or more fatty acid methyl esters.

In one embodiment of the present invention, component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucosides, gluconamides, aminoglucoseamides, sucrose esters, sorbitan esters.

Surprisingly, it has been found that the inclusion of plasticizers in the water-based binder compositions of the present invention significantly improves the mechanical properties of the mineral fiber products of the present invention.

The term plasticizer refers to a substance that is added to a material to make it softer and more flexible (by lowering the glass transition temperature (Tg)) and easier to process.

Component (iii) may also be a mixture of the compounds described above.

In one embodiment of the present invention, the content of component (iii) is in the range of 0.5-50 wt.%, preferably in the range of 2.5-25 wt.%, and in an even more preferred embodiment in the range of 3- 15% by weight, based on the dry weight of component (i).

According to one additional embodiment of the binder used within the scope of the present invention, a water-based binder composition containing component (i) and an alternative component (iia) is described below.

In one embodiment of the present invention, the aqueous mineral fiber binder composition comprises:

component (i) in the form of one or more oxidized lignins; and component (iia) in the form of one or more modifiers. Excellent binding properties can also be obtained by using a two-component system containing component (i) in the form of one or more oxidized lignins and component (iia) in the form of one or more modifiers, and optionally any other components specified above and below.

In one embodiment of the present invention, component (iia) is a modifier in the form of one or more compounds selected from the group consisting of epoxidized fatty acid triglyceride oils.

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

In one embodiment of the present invention, component (iia) is a modifier in the form of one or more flexible chain oligomers or polymers, such as an acrylic-based polymer with a low glass transition temperature (Tg), for example, a vinyl-based polymer with a low glass transition temperature, for example , a low glass transition temperature polyester which contains reactive functional groups such as carbodiimide groups, eg anhydride groups, eg oxazoline groups, eg amino groups, eg epoxy groups.

In one embodiment of the present invention, component (iia) is one or more modifiers selected from the group consisting of polyethylenimine, polyvinylamine and fatty amines.

In one embodiment of the present invention, component (iia) is one or more modifiers selected from the group of aliphatic multifunctional carbodiimides.

Component (iia) may also be a mixture of the compounds described above.

Without being bound by any particular theory, it should be noted that the excellent binding properties of the mineral fiber binder composition containing component (i) and component (iia), as well as optional additional components, are at least partially due to the fact that the modifiers used in as components (iia), at least partially perform the function of a plasticizer and cross-linking agent.

In one embodiment of the present invention, the aqueous binder composition includes component (iia), the content of which is in the range of 1-40 wt.%, for example 4-9045325 wt.%, for example 6-12 wt.%, in based on the dry weight of component (i).

Additional components.

In some embodiments of the present invention, the aqueous binder composition used in the present invention contains additional components.

In one embodiment of the present invention, the aqueous binder composition used in the present invention contains a catalyst selected from the group consisting of inorganic acids such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid and/ or phosphoric acid and/or any of their salts, such as sodium hypophosphate, and/or ammonium salt, such as ammonium salt of sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid and/or phosphoric acid. The presence of such a catalyst may improve the curability of the water-based binder composition used in the present invention.

In one embodiment of the present invention, the aqueous binder composition used in the present invention contains a catalyst selected from the group consisting of Lewis acids that can accept an electron pair from a donor compound to form a Lewis adduct such as ZnCl ₂ . Mg (ClO ₄ ) ₂ and Sn [N(SO ₂ _ _n -C ₈ F ₁₇ ) ₂ ] ₄ .

In one embodiment of the present invention, the aqueous binder composition used in the present invention contains a catalyst selected from metal chlorides such as KCl, MgCl ₂ , ZnCl ₂ , FeCl ₃ and SnCl ₂ .

In one embodiment of the present invention, the aqueous binder composition used in the present invention contains a catalyst selected from the group consisting of organometallic compounds, for example, a titanate catalyst and a tin catalyst.

In one embodiment of the present invention, the aqueous binder composition used in the present invention contains a catalyst selected from the group consisting of chelating agents such as transition metals such as iron ions, chromium ions, manganese ions and copper ions .

In one embodiment of the present invention, the aqueous binder composition used in the present invention further comprises an additional component (iv) in the form of one or more silanes.

In one embodiment of the present invention, the aqueous binder composition used in the present invention contains an additional component (iv) in the form of one or more coupling agents, such as organofunctional silanes.

In one embodiment of the present invention, component (iv) is selected from the group consisting of organofunctional silanes such as primary or secondary amine 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.

In one embodiment of the present invention, the aqueous binder composition used in the present invention further comprises component (v) in the form of one or more components selected from the group consisting of ammonia, amines or any salts thereof.

It has been found that the inclusion of ammonia, amines or their salts as additional component (v) may be particularly advantageous when component (i) uses oxidized lignins that have not been oxidized in the presence of ammonia.

In one embodiment of the present invention, the aqueous binder composition used within the framework of the present invention further contains an additional component in the form of urea, in particular in a volume of 5-40 wt.%, for example 10-30 wt.%, for example 15- 25% by weight, based on the dry weight of component (i).

In one embodiment of the present invention, the aqueous binder composition used within the present invention further comprises an additional component in the form of one or more carbohydrates selected from the group consisting of sucrose, reducing sugars, in particular dextrose, polycarbohydrates and their mixtures; preferably dextrins and maltodextrins; more preferably, glucose syrups; and in an even more preferred embodiment, glucose syrups with a dextrose equivalent value from DE=30 to less than 100, for example from DE=60 to less than 100, for example from DE=60 to 99, for example from DE=85 to 99, for example from DE= 95 to 99.

In one embodiment of the present invention, the aqueous binder composition used in the present invention further contains an additional component in the form of one or more carbohydrates selected from the group consisting of sucrose and reducing sugars, the content of which is in the range of 5-50 wt.%, for example ranging from 5

- 10 045325 to less than 50 wt.%, for example in the range from 10 to 40 wt.%, for example in the range from 15 to 30 wt.%, based on the dry weight of component (i).

With respect to the binder used herein, a binder composition with a sugar content of 50% by weight or higher based on the total dry weight of the binder components is considered a sugar-based binder. A binder composition with a sugar content of less than 50% by weight, based on the total dry weight of the binder components, is considered a non-sugar based binder.

In one embodiment of the present invention, the aqueous binder composition used in the present invention further contains an additional component in the form of one or more surfactants, which are in the form of ionic and/or nonionic emulsifiers, such as polyoxyethylene (4) lauryl alcohol ether, for example lecithin, for example sodium dodecyl sulfate.

In one embodiment of the present invention, the aqueous binder composition used in the present invention comprises:

component (i) in the form of one or more ammonia-oxidized lignins with a content of carboxylic acid groups in the range of 0.05-10 mmol/g, for example in the range of 0.1-5 mmol/g, for example in the range of 0.20- 1.5 mmol/g, for example in the range of 0.40-1.2 mmol/g, for example in the range of 0.451.0 mmol/g, based on the dry weight of component (i);

component (ii) in the form of one or more cross-linking agents selected from the group consisting of β-hydroxyalkylamide cross-linking agents and/or oxazoline cross-linking agents, and/or in the form of one or more cross-linking agents selected from the group consisting of multifunctional organic amines such such as alkanolamine, diamines, for example hexamethyldiamine, triamines;

component (iii) in the form of one or more polyethylene glycols, the average molecular weight of which lies in the range of 150-50,000 g/mol, in particular in the range of 150-4000 g/mol, in particular in the range of 150-1000 g/mol, in a preferred embodiment, in the range of 150-500 g/mol, and in a more preferred embodiment, in the range of 150-300 g/mol; or in the form of one or more polyethylene glycols, the average molecular weight of which lies in the range 4000-25000 g/mol, in particular in the range 4000-15000 g/mol, in particular in the range 8000-12000 g/mol; wherein in a preferred embodiment, the aqueous-based binder composition contains component (ii) in a volume of 1-40 wt.%, for example 4-20 wt.%, for example 6-12 wt.%, based on the dry weight of component (i), and the content of component (iii) is in the range of 0.5-50 wt.%, preferably in the range of 2.5-25 wt.%, and in a more preferred embodiment in the range of 3-15 wt.%, calculated per dry weight of component (i).

In one embodiment of the present invention, the aqueous binder composition used in the present invention comprises:

component (i) in the form of one or more ammonia-oxidized lignins with a content of carboxylic acid groups in the range of 0.05-10 mmol/g, for example in the range of 0.1-5 mmol/g, for example in the range of 0.20- 1.5 mmol/g, for example in the range of 0.40-1.2 mmol/g, for example in the range of 0.451.0 mmol/g, based on the dry weight of component (i);

component (ii) in the form of one or more modifiers selected from epoxidized oils based on triglycerides of fatty acids.

In one embodiment of the present invention, the aqueous binder composition used in the present invention comprises:

component (i) in the form of one or more ammonia-oxidized lignins with an average content of carboxylic acid groups of more than 1.5 groups per macromolecule of the first component, for example, more than two groups, for example, more than two and a half groups;

component (ii) in the form of one or more cross-linking agents selected from the group consisting of β-hydroxyalkylamide cross-linking agents and/or oxazoline cross-linking agents, and/or in the form of one or more cross-linking agents selected from the group consisting of multifunctional organic amines such such as alkanolamine, diamines, for example hexamethyldiamine, triamines;

component (iii) in the form of one or more polyethylene glycols, the average molecular weight of which lies in the range 150-50000 g/mol, in particular in the range 150-4000 g/mol, in particular in the range 150-1000 g/mol, in preferably in the range of 150-500 g/mol, and in a more preferred embodiment in the range of 150-300 g/mol; or in the form of one or more polyethylene glycols, the average molecular weight of which lies in the range 4000-25000 g/mol, in particular in the range 4000-15000 g/mol, in particular in the range 8000-12000 g/mol; wherein in a preferred embodiment, the aqueous-based binder composition contains component (ii) in a volume of 1-40 wt.%, for example 4-20 wt.%, for example 6-12 wt.%, based on the dry weight of component (i), and the content of component (iii) is in the range of 0.5-50 wt.%, preferably in the range of 2.5-25 wt.%, and in a more preferred embodiment in the range of 3-15 wt.%, calculated per dry weight of component (i).

- 11 045325

In one embodiment of the present invention, the aqueous binder composition used in the present invention comprises:

component (i) in the form of one or more ammonia-oxidized lignins with an average content of carboxylic acid groups of more than 1.5 groups per macromolecule of component (i), for example, more than two groups, for example, more than two and a half groups;

component (iia) in the form of one or more modifiers selected from epoxidized oils based on triglycerides of fatty acids.

In one embodiment of the present invention, the aqueous binder composition used in the present invention substantially includes:

component (i) in the form of one or more oxidized lignins;

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

component (iii) in the form of one or more plasticizers;

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

optionally a component in the form of one or more compounds selected from the group consisting of ammonia, amines or any salts thereof;

optionally a urea component;

optionally a component in the form of one or more reactive or chemically inactive silicone polymers;

optionally hydrocarbon oil;

optionally one or more surfactants, water.

In one embodiment of the present invention, the aqueous binder composition used in the present invention substantially includes:

component (i) in the form of one or more oxidized lignins;

component (iia) in the form of one or more modifiers selected from epoxidized oils based on triglycerides of fatty acids;

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

optionally a component in the form of one or more compounds selected from the group consisting of ammonia, amines or any salts thereof;

optionally a urea component;

optionally a component in the form of one or more reactive or chemically inactive silicone polymers;

optionally hydrocarbon oil;

optionally one or more surfactants, water.

Preparation of ammonia-oxidized lignin (AOL) resin.

3267 kg of water is poured into a reactor with a capacity of 6000 liters, after which 287 kg of aqueous ammonia solution (24.7%) is added there. 1531 kg of UPM BioPiva 100 lignin is then gradually added over 30 or 45 minutes. This mixture is then heated to 40°C and left at this temperature for one hour. After one hour, the lignin converted into insoluble form is checked. This can be done by testing the solution on a glass plate or using a Hegman meter. The insoluble lignin appears as small particles in a brown binder. During the dissolution step, the lignin solution changes color from brown to glossy black.

Once the lignin has completely dissolved, one liter of foam control agent (Skumdaemper 11-10 from NCA-Verodan) is added. The mixing temperature is maintained at 40°C.

After this, the stage of adding 307.5 kg of 35% hydrogen peroxide begins. Hydrogen peroxide is supplied in doses at a rate of 200-300 liters per hour. The first half of hydrogen peroxide is added at a rate of 200 liters per hour, after which the dosing rate increases to 300 liters per hour.

During the addition of hydrogen peroxide, the temperature of the reaction mixture is controlled by heating or cooling it so that the final reaction temperature is set at 65°C.

After 15 minutes of reaction at 65°C, the reaction mixture cools to less than 50°C. This produces a resin having a COOH value with a solids content of 1.2 mmol/g.

Preparation of the final binder.

From this AOL resin, a binder was prepared by adding 270 kg of polyethylene glycol 200 and 433 kg of a 31% solution of Primid XL-552 in water. Primid XL552 has the following structure:

- 12 045325

Analysis of the finally obtained binder showed the following data:

Solids content: 18.9% pH: 9.7

Viscosity: 25.5 mPa-s

Density: 1.066 kg/l

Oxidized lignins that can be used as a component of the aqueous binder composition for mineral fibers according to the present invention, and a method for preparing such oxidized lignins.

The following describes oxidized lignins that can be used as a component of the binder composition and their preparation.

Method I for the preparation of oxidized lignins.

Oxidized lignins, which can be used as a component of the binders according to the present invention, can be prepared using a method involving contacting:

component (a) containing one or more lignins;

component (b) containing ammonia, one or more amino components and/or any salts thereof; and component (c) containing one or more oxidizing agents.

Component(s).

Component (a) contains one or more lignins.

In one embodiment of the method according to the present invention, component (a) contains one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins obtained by biorefining of lignocellulosic raw materials, or any mixtures thereof.

In one embodiment of the present invention, component (a) contains one or more kraft lignins.

Component (b).

In one embodiment of the present invention, component (b) contains ammonia, one or more amino components and/or any salts thereof. Without intending to be bound by any particular theory, it is noted that according to the present invention, the replacement of caustic alkalis used in well-known prior art lignin oxidation processes with ammonia, one or more amino components and/or any salts thereof plays a large role in improving the properties oxidized lignins prepared using the method according to the present invention.

The inventors of the present invention were surprised to find that lignins oxidized with an oxidizing agent in the presence of ammonia or amines are characterized by a high content of nitrogen, which is part of the structure of the oxidized lignins. Without intending to be bound by any particular theory, the present invention provides improved flame retardancy properties of oxidized lignins used in products where they form part of binder compositions and which are prepared using the process of the present invention, at least in part are caused by the nitrogen content in the structure of oxidized lignins.

In one embodiment of the present invention, component (b) contains ammonia and/or any of its salts.

Without intending to be bound by any particular theory, the present inventors believe that the improved stability characteristics of the derivatized lignins prepared in accordance with the present invention are at least partially due to the fact that ammonia is a volatile compound and therefore evaporates from the final product. product, or the fact that it can be easily removed and reused. In contrast, difficulties have been found in removing residual amounts of caustic used in the well known prior art oxidation process.

However, the method according to the present invention may provide the advantage that component (b), in addition to ammonia, one or more amino components and/or any salts thereof, also contains a relatively small volume of caustic alkali and/or alkaline earth hydroxide metals, such as sodium hydroxide and/or potassium hydroxide.

- 13 045325

In one embodiment of the present invention, in which component (b) contains caustic alkali and/or hydroxides of alkaline earth metals, for example, caustic soda and/or caustic potassium as a component complementing ammonia, one or more amino components and/or any their salts, the volume of caustic alkali and/or hydroxides of alkaline earth metals is usually small, amounting to, for example, 5-7 parts by weight, for example 10-20 parts by weight, based on the weight of ammonia.

Component (c).

In the context of the method according to the present invention, component (c) contains one or more oxidizing agents.

In one embodiment of the present invention, component (c) contains one or more oxidizing agents in the form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogenated oxidizing agents, or mixtures thereof.

At the initial stage of oxidation, active oxidizing radicals usually remove a proton from the phenolic group, since this bond has the lowest dissociation energy in lignin. The potential of lignin to stabilize radicals through the mesomeric effect opens up many possibilities for the continuation (but also termination) of the reaction and the production of various intermediates and end products. Due to this complexity (and the conditions chosen), the average molecular weight can either increase or decrease, but in our experiments, the present inventors have typically observed a modest increase in average molecular weight of about 30%.

In one embodiment of the present invention, component (c) contains hydrogen peroxide.

Hydrogen peroxide is probably the most commonly used oxidizing agent due to a combination of factors such as its low cost, high efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of a catalyst, alkaline conditions and temperature become important, since subsequent reactions lead to the formation of radicals:

HiOj + OH ’ g± HOO- + HiO

HjOj + UN sr OH + HjO μ '07

The present inventors have found that derivatized lignins prepared using the process of the present invention are characterized by an increased content of carboxylic acid groups as a result of the oxidation process. Without intending to be bound by any particular theory, the present inventors believe that the content of carboxylic acid groups in the oxidized lignins prepared by the process of the present invention plays a large role in providing the desired reactivity of the derivatized lignins prepared using the method according to the present invention.

Another advantage of the oxidation process is that the oxidized lignin is characterized by higher hydrophilicity. Increased hydrophilicity makes it soluble in water and facilitates adhesion to polar substrates such as mineral fibers.

Additional components.

In one embodiment, the method according to the present invention involves the use of additional components, in particular component (d) in the form of an oxidation catalyst, such as one or more transition metal catalysts such as ferrous sulfate, for example, in the form of a catalyst containing manganese, palladium, selenium and tungsten.

Such oxidation catalysts can increase the reaction rate, which improves the properties of the oxidized lignins prepared using the process of the present invention.

Component mass ratio.

One skilled in the art will use components (a), (b) and (c) in relative amounts so as to provide the desired degree of oxidation of the lignins. In one embodiment:

component (a) contains one or more lignins;

component (b) contains ammonia; and component (c) contains one or more oxidizing agents in the form of hydrogen peroxide;

wherein the mass ratio of lignin, ammonia and hydrogen peroxide is such that the volume of ammonia is 0.01-0.5 mass fractions, for example 0.1-0.3 mass fractions or, for example 0.15-0.25 mass fractions in calculation on dry weight of lignin; and the volume of hydrogen peroxide is 0.025-1.0 parts by weight, for example 0.05-0.2 parts by weight or, for example, 0.075-0.125 parts by weight based on the dry weight of the lignin.

Technological process.

- 14 045325

There is more than one possibility of bringing components (a), (b) and (c) into contact to achieve the desired oxidation reaction.

In one of its embodiments, the method according to the present invention includes the following steps:

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

a step of adjusting the pH by adding component (b) containing an aqueous solution of ammonia, one or more amino components and/or any salt thereof; and an oxidation step by adding component (c) containing an oxidizing agent.

In one embodiment of the present invention, the pH adjustment step is performed such that the resulting aqueous solution and/or dispersion has a pH of >9, eg >10, eg >10.5.

In one embodiment of the present invention, the pH adjustment step is performed so that the resulting aqueous solution and/or dispersion has a pH in the range of 10.5-12.

In one embodiment of the present invention, the pH adjustment step is performed such that the temperature can be raised to a level >25°C, after which it is adjusted in the range of 25-50°C, for example 30-45°C, for example 35-40°C WITH.

In one embodiment of the present invention, during the oxidation step, the temperature may be raised to >35°C, after which it is controlled in the range of 35-150°C, for example 4090°C, for example 45-80°C.

In one embodiment of the present invention, the oxidation steps are carried out for a period of from 1 second to 48 hours, for example for a period of time from 10 seconds to 36 hours, for example for a period of time from 1 minute to 24 hours, for example for a period of 2-5 hours.

Method II for the preparation of oxidized lignins.

Oxidized lignins, which can be used as a component of the binders according to the present invention, can be prepared using a method involving contacting:

component (a) containing one or more lignins;

component (b) containing ammonia, and/or one or more amino components, and/or any salts thereof, and/or caustic alkali and/or alkaline earth metal hydroxide, for example, caustic soda and/or caustic potassium;

component (c) containing one or more oxidizing agents; and component (d) in the form of one or more plasticizers.

Component(s).

Component (a) contains one or more lignins.

In one embodiment of the method according to the present invention, component (a) contains one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins obtained by biorefining of lignocellulosic raw materials, or any mixtures thereof.

In one embodiment of the present invention, component (a) contains one or more kraft lignins.

Component (b).

In one embodiment of the present invention, component (b) contains ammonia, one or more amino components and/or any salts thereof, and/or caustic alkali and/or an alkaline earth metal hydroxide, for example caustic soda and/or caustic potassium.

The term ammonia-oxidized lignin refers to lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term ammonia-oxidized lignin is given the abbreviation AOL.

In one embodiment of the present invention, component (b) contains ammonia and/or any salt thereof.

Without intending to be bound by any particular theory, the present inventors believe that the improved stability characteristics of derivatized lignins prepared according to the present invention using component (b) of ammonia and/or any salt thereof is at least in part due to the fact that ammonia is a volatile compound and therefore evaporates from the final product, or the fact that it can be easily removed and reused.

However, the method according to this embodiment may provide the advantage that component (b), in addition to ammonia, one or more amino components

- 15 045325 and/or any of their salts, also contains a relatively small amount of caustic alkali and/or hydroxide of alkaline earth metals, for example, caustic soda and/or caustic potassium.

In embodiments of the present invention in which component (b) contains caustic alkali and/or hydroxides of alkaline earth metals, for example, caustic soda and/or caustic potassium as a component complementing ammonia, one or more amino components and/or any of them salts, the volume of caustic alkali and/or hydroxides of alkaline earth metals is usually small, amounting to, for example, 5-7 parts by weight, for example 10-20 parts by weight, based on the weight of ammonia.

Component (c).

In the context of the method according to the present invention, component (c) contains one or more oxidizing agents.

In one embodiment of the present invention, component (c) contains one or more oxidizing agents in the form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogenated oxidizing agents, or any mixture thereof.

In the initial stages of oxidation, active oxidizing radicals usually remove a proton from the phenolic group, since this bond has the lowest dissociation energy in lignin. The potential of lignin to stabilize radicals through the mesomeric effect opens up many possibilities for the continuation (but also termination) of the reaction and the production of various intermediates and end products. Due to this complexity (and the conditions chosen), the average molecular weight can either increase or decrease, but in our experiments, the present inventors have typically observed a modest increase in average molecular weight of about 30%.

In one embodiment of the present invention, component (c) contains hydrogen peroxide.

Hydrogen peroxide is probably the most commonly used oxidizing agent due to a combination of factors such as its low cost, high efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of a catalyst, alkaline conditions and temperature become important, since subsequent reactions lead to the formation of radicals:

H^ + OH’ rfHOO +nu

H2O2 + UN- lON + HtO h Ό,

The present inventors have found that derivatized lignins prepared using the process of the present invention are characterized by an increased content of carboxylic acid groups as a result of the oxidation process. Without intending to be bound by any particular theory, the present inventors believe that the content of carboxylic acid groups in the oxidized lignins prepared by the process of the present invention plays a large role in providing the desired reactivity of the derivatized lignins prepared using the process of the present invention.

Another advantage of the oxidation process is that the oxidized lignin is characterized by higher hydrophilicity. Increased hydrophilicity makes it soluble in water and facilitates adhesion to polar substrates such as mineral fibers.

Component (d).

Component (d) contains one or more plasticizers.

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

The present inventors have found that the inclusion of component (d) in the form of one or more plasticizers reduces the viscosity of the reaction mixture, allowing the production of oxidized lignins in a highly efficient manner.

In one embodiment of the present invention, component (d) contains one or more plasticizers selected from the group consisting of polyols such as carbohydrates, hydrogenated sugars such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyvinyl alcohol, acrylic polymers with free carboxyl groups and/or dispersions

- 16 045325 polyurethane with free carboxyl groups, polyamides, amides such as urea/urea, or any mixtures thereof.

In one embodiment of the present invention, component (d) contains one or more plasticizers selected from the group consisting of propylene glycols, polyvinyl alcohol, urea, or any of a mixture.

Additional components.

In one of its embodiments, the method according to the present invention further provides for the use of additional components, in particular component (v) in the form of an oxidation catalyst, such as one or more transition metal catalysts such as ferrous sulfate, for example, in the form of a catalyst containing manganese, palladium, selenium and tungsten.

Such oxidative catalysts can increase the reaction rate, which improves the properties of oxidized lignins prepared using the proposed method.

Component mass ratio.

One skilled in the art will use components (a), (b), (c) and (d) in relative amounts so as to provide the desired degree of oxidation of the lignins.

In one of its embodiments, the method according to the present invention is implemented in such a way that the method involves the use of the following components:

component (a) containing one or more lignins;

component (b) containing ammonia;

component (c) containing one or more oxidizing agents in the form of hydrogen peroxide; and component (d) containing one or more plasticizers selected from the group of polyethylene glycols;

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

For the purposes of the present invention, the dry weight of lignin is defined as the weight of lignin in the state in which it was supplied.

Technological process.

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

In one embodiment of the present invention, the method comprises the following steps:

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 in the aqueous solution is in the range of 5-90 wt.%, for example, in the range of 10-85 wt.%, or, for example , in the range of 15-70 wt.%, based on the total weight of the aqueous solution;

a step of adjusting the pH by adding component (b);

a step of adding component (d); and an oxidation step by adding component (c) containing an oxidizing agent.

In one embodiment of the present invention, the pH adjustment step is performed such that the resulting aqueous solution and/or dispersion has a pH of >9, for example >10, for example >10.5 or for example >10.5 .

In one embodiment of the present invention, the pH adjustment step is performed so that the resulting aqueous solution and/or dispersion has a pH value in the range of 9.5-12.

In one embodiment of the present invention, the pH adjustment step is performed such that the temperature can be raised to a level >25°C, after which it is adjusted in the range of 25-50°C, for example 30-45°C, for example 35-40°C WITH.

In one embodiment of the present invention, during the oxidation step, the temperature may be raised to >35°C, after which it is controlled in the range of 35-150°C, for example 4090°C, for example 45-80°C.

In one embodiment of the present invention, the oxidation steps are carried out for a period of from 1 s to 24 hours, for example for a time from 1 minute to 12 hours, for example for a time from 10 minutes to 8 hours, for example for a time from 5 minutes to 1 hour

The authors of the present invention have found that the technological process according to the present invention makes it possible to obtain a reaction mixture with a high dry matter content

- 17 045325 substances; and, therefore, the process according to the present invention provides high productivity, which allows the use of the reaction product in the form of oxidized lignins as a component in mass-produced products, for example, in mineral fiber products.

In one of its embodiments, the method according to the present invention is implemented in such a way that the dry matter content in the reaction mixture is in the range of 20-80 wt.%, for example in the range of 40-70 wt.%

In one of its embodiments, the method according to the present invention is implemented in such a way that the viscosity of the oxidized lignins is characterized by a value in the range of 100100000 cP, for example in the range of 500-50000 cP, for example in the range of 1000-25000 cP.

For the purposes of the present invention, viscosity is dynamic viscosity, which is defined as the resistance to change in shape of a liquid/paste or displacement of adjacent particles relative to each other. Viscosity is measured in centipoise (cP), which is equivalent to 1 mPa-s (millipascals per second). Viscosity is measured at 20°C using a viscometer. For the purposes of the present invention, dynamic viscosity can be measured at a temperature of 20°C using a Wells-Brookfield viscometer with a cone/plate geometry.

In one of its embodiments, the method according to the present invention is implemented in such a way that the method involves the use of a rotor-stator device.

In one of its embodiments, the method according to the present invention is implemented in such a way that the method is carried out in a continuous or semi-continuous mode.

Device for implementing the method.

The present invention also relates to a device for implementing the method described above.

In one embodiment of the present invention, a device for implementing the method contains:

rotor-stator device;

a device for pre-mixing components (a), (b) and (d);

one or more inlets for water and components (a), (b), (c) and (d); and one or more outlets for oxidized lignin.

In one of the embodiments of the present invention, the proposed device is designed in such a way that inlets for pre-mixing components (a), (b) and (d) are connected to the rotor-stator device, and the device itself additionally contains a chamber, wherein said chamber is equipped with an inlet for supplying component (c), and wherein said chamber is provided with an outlet for oxidized lignin.

A rotor-stator device is a material handling device comprising a stator that is configured as an internal cone equipped with gears. The stator interacts with a rotor containing rods extending from the hub. Each of these rods carries teeth that mesh with the teeth of the stator gears. With each revolution of the rotor, the material to be processed is transferred further one more stage, while it is subjected to intense shearing, mixing and redistribution. The rotor bar and the lower container chamber of the vertically mounted device provide the ability to constantly redistribute material from inside to outside and multiple processing of dry and/or highly viscous material, due to which this device has excellent efficiency in intensive mixing, kneading, fibrillation, decomposition and similar processes of great importance in industrial production. The vertical position of the housing makes it easier to tilt the material from the periphery to the center of the device.

In one embodiment of the present invention, a rotor-stator device used in the method of the present invention comprises a stator with gears and a rotor with teeth meshing with the teeth of the stator. In this embodiment of the present invention, the rotor-stator device is characterized by the following features: a guide bell protrudes between the rotor rods, in which the flow of material entering from above into the central region of the container is concentrated. The outer surface of the guide bell sets the annular gap, throttling the flow of material. The rotor is equipped with a feed auger, which is fed towards the working area of the device. The guide bell holds the product in the active area of the device, and the feed auger creates increased pressure of the material in the center.

More detailed information about the rotor-stator device, which is used in the implementation of one embodiment of the method according to the present invention, is presented in the document US 2003/0042344 A1, the contents of which are incorporated herein by reference.

In one embodiment of the present invention, the method is implemented in such a way that it involves the use of a rotor-stator device. In this embodiment, mixing the components and carrying out the reaction of the components are performed in the same rotor-stator device.

- 18 045325

In one embodiment of the present invention, the method is carried out in such a way that it involves the use of two or more rotor-stator devices, wherein at least one rotor-stator device is used for mixing components and at least one rotor-stator device is used for implementation of the reaction of the components.

This process can be broken down into two stages:

1. Preparation of lignin mass (a)+(b)+(d); And

2. Oxidation of lignin mass.

Two different types of rotor/stator devices are commonly used.

1. An open rotor/stator device suitable for mixing lignin powder with water in ultra-high concentration (30-50 wt.%). It provides less intensive mixing, but contains special auxiliary means (inlet bell, auger, etc.) that allow handling highly viscous materials. It is characterized by a reduced peripheral speed (up to 15 m/s). This device can be used as a batch or continuous loading system.

2. Flow rotor/stator device, which is characterized by much higher shear forces (with peripheral speeds up to 55 m/s), and which creates favorable conditions for ultra-fast chemical reactions. This device must operate continuously.

In an open rotor/stator system, a highly concentrated mass (45-50 wt%) of lignin is prepared. Powdered lignin is gradually added to warm water (3060°C), to which the required amount of aqueous ammonia and/or alkali has been added. This may be batch loading, or materials may be added periodically/continuously, creating a continuous flow of mass for the next stage.

The temperature of the created mass must be maintained at approximately 60°C to keep the viscosity at the lowest possible level and, accordingly, to ensure the ability to pump the material. The hot lignin/water mass with a pH of 9-12 is then transferred to the oxidation stage using a suitable pump, such as a screw pump or other positive displacement pump.

In one embodiment of the present invention, the oxidation is carried out in a closed rotor/stator system in a continuous flow reactor. An aqueous solution of ammonia and/or alkali is dosed into the rotor/stator chamber at the point of maximum swirl/shear using a metering pump. This ensures a fast oxidation reaction. The oxidized material (AOL) leaves the flow reactor and is collected in appropriate tanks.

Reaction product.

The present inventors were surprised to find that the prepared oxidized lignins had the full required reactivity and, at the same time, improved fire resistance characteristics when used in products where they are part of the binder composition, as well as more long-term stability in comparison with well-known oxidized lignins. ny lignins of the prior art.

Oxidized lignin also exhibits increased hydrophilicity.

An important parameter of the reactivity of prepared oxidized lignins is the content of carboxylic acid groups in the oxidized lignins.

In one embodiment of the present invention, the prepared oxidized lignin is characterized by a content of carboxylic acid groups in the range of 0.05-10 mmol/g, for example in the range of 0.1-5 mmol/g, for example in the range of 0.20-2.0 mmol /g, for example in the range of 0.40-1.5 mmol/g, for example in the range of 0.45-1.0 mmol/g based on the dry weight of component (a).

Another way to describe the content of carboxylic acid groups is to use the average content of carboxylic acid groups in oxidized lignins per lignin macromolecule, determined by the following formula:

Average functionality COOH total mole fractions COOH total mole fractions lignin

In one embodiment of the present invention, the prepared oxidized lignin has a carboxylic acid group content of more than 1.5 groups per macromolecule of component (a), for example, more than two groups, for example, more than two and a half groups.

Method III of preparation of oxidized lignins.

Oxidized lignins, which can be used as a component of the binder used in the present invention, can be prepared using a method involving contacting the following components:

component (a) containing one or more lignins;

component (b) containing ammonia and/or one or more amino components and/or any salt thereof, and/or caustic alkali and/or hydroxide of alkaline earth metals, for example caustic soda and/or caustic potassium;

- 19 045325 component (c) containing one or more oxidizing agents; and optionally component (d) in the form of one or more plasticizers;

and allowing a mixing/oxidation step that produces an oxidized mixture to be performed, followed by an oxidation step that can continue to react the oxidized mixture for a dwell time with a dwell time ranging from 1 second to 10 hours, for example ranging from 10 seconds up to 6 hours, for example in the range from 30 s to 2 hours.

Components (a), (b), (c) and (d) correspond to the components described above within the framework of the implementation of method II for the preparation of oxidized lignins.

In one embodiment of the present invention, the process includes a premixing step in which the components are brought into contact with each other.

At the pre-mixing stage, the following components can be brought into mutual contact:

component (a) and component (b); or component (a), and component (b), and component (c); or component (a), and component (b), and component (d); or component (a), and component (b), and component (c), and component (d).

In one embodiment of the present invention, it is possible to perform the premixing step as a separate step, with the mixing/oxidation step occurring after the premixing step. In such an embodiment of the present invention, it is particularly advantageous that component (a) and component (b), and optionally component (d), are brought into mutual contact during the premixing step. In the subsequent mixing/oxidation step, component (c) is added to the premix obtained in the premixing step.

In another embodiment of the present invention, the premixing step may correspond to a mixing/oxidation step. In this embodiment of the present invention, mixing of components, for example, component (a), component (b) and component (c), occurs simultaneously with the start of the oxidation process. In this case, it is possible to implement the subsequent holding time in the same device as the device used to perform the mixing/oxidation step. This implementation of the present invention is particularly advantageous if component (c) is air.

The inventors of the present invention have found that by allowing a mixing/oxidation step to be performed followed by an oxidation step in which the reaction mixture preferably does not continue to mix, the rate of oxidation can be controlled in a highly efficient manner. At the same time, the cost of implementing the method is reduced, since the oxidation stage following the mixing/oxidation stage requires less complex equipment.

Another advantage is that the resulting oxidized lignin is substantially stable. Another striking advantage is that the resulting oxidized lignin is extremely adjustable with respect to its viscosity. Another striking advantage is the ability to provide high concentrations of oxidized lignin.

In one embodiment of the present invention, the residence time is selected such that the oxidation reaction is brought to the desired degree of completion, preferably complete completion.

System I for implementing method III.

In one embodiment of the present invention, a system for implementing this method comprises:

at least one rotor-stator device;

one or more inlets for water and components (a) and (b);

one or more outlets of the rotor-stator device;

at least one reaction device, in particular at least one reaction tube, which is located downstream of at least one or more outlets in the direction of the process flow.

In one embodiment of the present invention, the proposed system includes one or more inlets for component (c) and/or component (d).

In one embodiment of the present invention, the proposed system includes a premixing device.

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).

In one embodiment of the present invention, the premixing device includes water inlets for both component (a) and component (b).

It is possible that during the pre-mixing step, component (c) is also mixed with the three specified ingredients (water, component (a) and component (b)). Accordingly, it is not

- 20 045325 states that the premixing device may contain an additional inlet for component (c). If component (c) is air, the premixing device can be designed as an open mixing vessel, whereby component (c) is already brought into contact with the other components (water, component (a) and component (b) ) through the opening of the vessel. Moreover, in this embodiment of the present invention, it is not excluded that the premixing device may optionally include an inlet for component (d).

In one embodiment of the present invention, the system is designed such that the inlets for components (a), (b) and (d) are inlets of a premixing device, in particular an open rotor-stator device, whereby the system also includes an additional rotor-stator device, wherein said additional rotor-stator device comprises an inlet for component (c), and said additional rotor-stator device comprises an outlet for oxidized lignin.

The premixing step and the mixing/oxidation step can be performed simultaneously. In this case, the premixing device and the mixing/oxidizing device are one device, i.e. rotor-stator device.

In one embodiment of the present invention, one rotor-stator device used in implementing the method according to the present invention includes a stator with gears and a rotor with teeth meshing with the teeth of the stator. In this embodiment of the present invention, the rotor-stator device is characterized by the following features: a guide bell protrudes between the rotor rods, in which the flow of material entering from above into the central region of the container is concentrated. The outer surface of the guide bell sets the annular gap, throttling the flow of material. The rotor is equipped with a feed auger, which is fed towards the working area of the device. The guide bell holds the product in the active area of the device, and the feed auger creates increased pressure of the material in the center.

System II for implementing method III.

In one embodiment of the present invention, a system for implementing this method comprises:

one or more inlets for water and components (a) and (b);

at least one mixing and oxidation device with one or more outlets; and at least one mixer/heat exchanger that is located downstream of the at least one or more outlets in the direction of the process flow, wherein the mixer/heat exchanger includes a temperature controller.

In one embodiment of the present invention, the proposed system includes one or more additional inlets for component (c) and/or component (d).

In one embodiment of the present invention, the proposed system includes a premixing device.

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).

In one embodiment of the present invention, the premixing device includes water inlets for both component (a) and component (b).

It is possible that during the pre-mixing step, component (c) is also mixed with the three specified ingredients (water, component (a) and component (b)). Accordingly, it is possible that the premixing device may include an additional inlet for component (c).

If component (c) is air, the premixing device can be designed as an open mixing vessel, whereby component (c) is already brought into contact with the other components (water, component (a) and component (b) ) through the opening of the vessel. Moreover, in this embodiment of the present invention, it is not excluded that the premixing device may optionally include an inlet for component (d).

In one embodiment of the present invention, the system is designed such that the inlets for components (a), (b) and (d) are inlets of an open rotor-stator device, which system also includes an additional mixer/heat exchanger containing an inlet for component (c) ) and release for oxidized lignin.

The premixing step and the mixing/oxidation step can be performed simultaneously. In this case, the premixing device and the mixing/oxidizing device are one device.

In one embodiment of the present invention, one rotor-stator device used in implementing the method according to the present invention comprises a stator with geared

- 21 045325 wheels and a rotor with teeth that engage with the stator teeth. In this embodiment of the present invention, the rotor-stator device is characterized by the following features: a guide bell protrudes between the rotor rods, in which the flow of material entering from above into the central region of the container is concentrated. The outer surface of the guide bell sets the annular gap, throttling the flow of material. The rotor is equipped with a feed auger, which is fed towards the working area of the device. The guide bell holds the product in the active area of the device, and the feed auger creates increased pressure of the material in the center.

Of course, other devices can also be used as premixing devices. In addition, the possibility of performing a pre-mixing step in the mixing and oxidation device is not excluded.

In one embodiment of the present invention, the mixing and oxidation device is a static mixer. A static mixer is a device for continuously mixing flowable materials without any moving parts. In one design, the static mixer is a plate type mixer, while another commonly used type of such mixer consists of elements enclosed in a cylindrical (tube) or square body.

In one embodiment of the present invention, the mixer/heat exchanger is designed as a multi-tube heat exchanger with mixing elements. The mixing elements are preferably fixed devices through which the mixture must flow, resulting in mixing. The mixer/heat exchanger can be designed as a pulsating flow reactor.

Examples I.

Example IA - oxidation of lignin in an aqueous ammonia solution with hydrogen peroxide.

The amount of ingredients used according to Example IA is presented in Tables IA 1.1 and IA 1.2.

Although kraft lignin is soluble in water with a relatively high pH, it is known that at a certain concentration by weight, the viscosity of the solution will increase dramatically. It is generally accepted that the reason for this dramatic increase in viscosity lies in the combination of strong hydrogen bonding and the interaction of π electrons from the numerous aromatic nuclei present in lignin. For kraft lignin, a sharp increase in viscosity was observed at its concentration in the range of about 21-22 wt.%, and in the given example the proportion of kraft lignin was 19 wt.%.

At the pH correction stage, an ammonia aqueous solution was used as a basis. Its volume was fixed at 4 wt.%, based on the total weight of the reaction. The pH value after the stage of its correction and at the beginning of oxidation was 10.7.

In table IA2 shows the results of CHNS elemental analysis (determination of the main elemental composition - carbon, hydrogen, nitrogen, sulfur) before and after oxidation of kraft lignin. Before analysis, samples were heat treated at 160°C to remove adsorbed ammonia. The result of the analysis showed that during the oxidation process, a certain amount of nitrogen became part of the structure of the oxidized lignin.

Through parallel testing, it was found that for oxidation it is beneficial to add the entire volume of hydrogen peroxide over a short period of time, as opposed to adding small amounts of peroxide over an extended period of time. In the example given, the proportion of H ₂ O ₂ was 2.0 wt.%, based on the total weight of the reaction.

Oxidation is an exothermic reaction and an increase in temperature is noted after the addition of peroxide. In this example, the temperature was maintained at 60°C for three hours of reaction.

After oxidation, the volume of lignin functional groups per gram of sample increased, as determined by ^31P NMR (phosphorus-31 nuclear magnetic resonance) and aqueous titration methods. Sample preparation for ^31P NMR was carried out using 2-chloro-4,4,5,5-tetramethyl-1,3,2dioxophospholane (TMDP) as the phosphitylation reagent and cholesterol as the internal standard. NMR spectra of kraft lignin before and after oxidation were generated, and the results were summarized in Table. IA3.

The change in COOH groups was determined by aqueous titration and using the following formula:

I _ (K^d/l ^{- -} (^id/l ^- %.yl/l) * ^acid/ol/l

CCOOH, mmol/g) ^- ~ ^m s^ where the values of V _2s and V _1s indicate the preset final sample volume, while the values of V _1b and V _1b indicate the volume of the blind sample. The value of _Skislot in this case is equal to 0.1 M HCl, and the value of ms denotes the weight of the sample. The values obtained from the results of aqueous titration before and after oxidation are presented in table. IA4.

The average COOH functionality can also be quantified as the saponification coefficient, which represents the number of milligrams of potassium hydroxide (KOH) required to saponify one gram of lignin. This method can be found in the AOCS (American Society of Fat Chemists) Official Method Cd 325.

The average molecular weight was also determined before and after oxidation using a PSS PolarSil column (0.05 M LiBr in a 9:1 (v/v) dimethyl sulfoxide in water solvent) and a UV wavelength detector 280 nm. The combination of COOH concentration and average molecular weight also made it possible to calculate the average content of carboxylic acid groups per lignin macromolecule, and these results are presented in Table. IA5.

Example IB - scaling up lignin oxidation in ammonia using hydrogen peroxide to pilot scale.

Lignin oxidation is an exothermic process, and significant temperature increases have been observed after addition of peroxide, even on a laboratory scale. Increasing the scale of chemical processes is a natural concern because the amount of heat produced relative to size increases cubed (volume), while cooling relative to size typically increases squared (area). Additionally, due to the high viscosity of adhesive intermediates, care must be taken in the selection or design of processing equipment. Accordingly, the scale-up was carefully designed and carried out in several stages.

The first upscaling was carried out from the 1 liter level (lab scale) to the 9 liter level using a professional stainless steel mixer providing highly efficient mechanical mixing. Scaling up resulted in only a slight increase in the final temperature compared to the value obtained at laboratory scale, which was due to the efficient air cooling of the reactor and the slow addition of hydrogen peroxide.

The next upscaling step was carried out in a 200 liter closed reactor with a high efficiency water jacket and a high efficiency propeller stirrer. The scale this time was 180 liters and hydrogen peroxide was added in two stages approximately 30 minutes apart. This upscaling was relatively successful, although a noticeable amount of foam was observed due to the high reactor fill level. To control foaming, a small amount of food grade antifoam agent was sprayed onto the foam. Most importantly, by using external water cooling, temperature control was possible and the final temperatures were less than 70°C.

Pilot-scale reactions were carried out in an 800-liter reactor with a water-cooling jacket and a two-bladed propeller mixer. During and after the addition of hydrogen peroxide, the 158 kg lignin level was carefully monitored and cooling water was supplied to the water jacket to maintain acceptable foam levels and temperature rises of no more than 4°C per minute, and to ensure that the final temperature was less than 70°C.

After the temperature rise was completed, the refrigeration was switched off and the product mixture was stirred for a further two hours before being transferred for transport (BioPiva 100 from UPM LignoBoost™) with a dry mass of 67 wt.% ground and suspended in 224 kg of water, followed by mixing to obtaining a homogeneous suspension. With continued stirring, 103 kg of 25 percent aqueous ammonia was pumped into the reactor and stirred for another two hours to produce a viscous, dark-colored lignin solution.

140 kg of 7.5% by weight hydrogen peroxide was added to the mixed lignin solution over 15 minutes at a temperature of 20-25°C.

Temperature and foam container.

Based on the results of scale-up trials, it can be concluded that even though the reactions are exothermic in nature, a significant portion of the heat generated during the reaction is actually neutralized by the heat capacity of water entering at room temperature and heated to about 60 °C, and only the last part should be neutralized by cooling. It should be noted that this, coupled with the short reaction time, would make the process ideal for scale-up and process intensification using continuous reactors such as in-line mixers, tube reactors or CSTRs. environment). This would provide efficient temperature control and a more clearly defined reaction process.

A series of scale-up tests showed that the resulting oxidized lignin had properties consistent with those obtained in the laboratory.

- 23 045325

Table IA 1.1

Volumes of materials used as supplied Material____________________________________ wt.%_____________

BioPiva 100 from UPM, kraft lignin28

H2O2, 30% by weight solution in water6.6

NH _3j 25% by weight aqueous solution16

Water_________________________________________________49.4___________________________

Table IA 1.2

Volumes of active materials used

Material__________________________________________% wt.__________________

Kraft lignin19

H2O22

NH ₃ 4

Water 75

Table IA 2

Analysis of kraft lignin before and after oxidation

Try N (wt.%) s (wt.%) N (wt.%) S (wt.%) Kraft lignin OD 64.9 5.8 1.7 Oxidized with ammonia 1.6 65.5 5.7 1.6 kraft lignin

Table IA 3

Distribution of functional groups of kraft lignin before and after oxidation obtained by ³¹ P NMR method ______________Concentration (mmol/g)______________

Sample Aliphatic Phenolic Acid _________________________OH-group______OH-group______OH-group

Kraft lignin 1.60 3.20 0.46

Oxidized with ammonia. " _O "

2.11 3.00 U,oU kraft lignin ’

Table IA 4

Content of COOH groups in mmol/g, determined by aqueous titration

Sample______________________________COOH group (mmol/g)_________

Kraft lignin 0.5

Ammonia-oxidized θ $ kraft lignin’

Table IA 5

Number-average (Mn) and weight-average (Mw) molecular weights, determined by size exclusion chromatography and expressed in g/mol, together with the average content of carboxylic acid groups per lignin macromolecule before and after oxidation

Average

Sample Mn, g/mol Mw, g/mol functionality __________________________________________ coon

Kraft lignin 1968 21105 0.9

Kraft lignin oxidized by ammonia 7 η___________________________ _________________________________

Example II.

In the examples described below, several oxidized lignins were prepared. The following properties have been determined for oxidized lignins.

Solid content.

The content of each component in a given solution of oxidized lignin depends on the anhydrous mass of the components, or it is determined as described below.

Kraft lignin was provided by UPM in the form of BioPiva100™ dry powder. The NH ₄ OH ingredient at 25% concentration was provided by Sigma-Aldrich and used as supplied. Hydrogen peroxide (H ₂ O ₂ ) at 30% concentration (CAS No. 7722-841) was provided by Sigma-Aldrich and used as supplied or as an aqueous solution. The plasticizer PEG200 was provided by Sigma-Aldrich and, for simplicity, was considered anhydrous and used as such. The ingredients PVA (Mw 89.000-98.000, Mw 85.000-124.000, Mw 130.000, Mw 146.000186.000) (CAS No. 9002-89-5) were supplied by Sigma-Aldrich and for simplicity they were considered anhydrous and used as such . Urea (CAS No. 57-13-6) was

- 24 045325 was provided by Sigma-Aldrich and was used as supplied or as an aqueous solution, and for the sake of simplicity it was considered anhydrous and used as such.

Oxidized lignin solids.

The content of oxidized lignin after heating to a temperature of 200°C for one hour is determined by the term Dry mass and is expressed as a percentage of the mass remaining after heating.

Disc-shaped rock wool samples (diameter: 5 cm; height: 1 cm) were cut from rock wool and heat treated at 580°C for at least 30 min to remove all organic matter. Solids in the binder mixture were measured by distributing a sample of the binder mixture (approximately 2 g) onto a heat-treated rock wool disk in a tin foil container. A tin foil container containing a disc of rock wool was weighed before and immediately after the addition of the binder mixture. Two such rock wool discs were prepared in a tin foil container, loaded with a binder mixture, after which they were calcined at 200° C. for one hour. After cooling and holding at room temperature for 10 min, the samples were weighed and the dry weight was calculated from the two average values obtained.

Content of COOH groups.

The change in the content of COOH groups was also determined by aqueous titration using the following formula:

I _ (i$ _ml - K _{ls ml} ) - (V2£, _/MJI - _ml ) * C _{acid mol} / _l ^(COOH, mmol/g) ^- “ ™s,r where the values V _2s and V _1s are preliminarily designated specified final sample volumes, while the values V _2b and V _1b indicate the volume of the blind sample. The value of C _acid in this case is equal to 0.1 M HCl, and the value of m _s , _r indicates the weight of the sample.

Method for producing oxidized lignin.

1) Mixing water and lignin in a three-neck glass-bottom flask connected to a condenser and a logging thermometer in a water bath at room temperature (20-25°C) with stirring. Stirring for one hour.

2) Add ammonia during stirring in a single dose.

3) Raising the temperature to 35°C by heating, if the temperature itself does not increase due to a slight exothermic reaction.

4) pH measurement.

5) Add PEG200 plasticizer and stir for 10 minutes.

6) After the lignin has completely dissolved, after about one hour, slowly add 30 percent hydrogen peroxide (H2O2) in a single dose.

7) The exothermic reaction caused by the addition of H ₂ O ₂ increases the temperature in the glass bottom flask - if the reaction temperature is below 60°C, then the temperature should be increased to 60°C and the sample should be left at 60°C for another hour .

8) Remove the round bottom flask from the water bath and cool it to room temperature.

9) Extraction of samples to determine dry weight, COOH, viscosity, density and pH. Variants of the composition of oxidized lignin.

In the examples below, the input numbers of oxidized lignin correspond to the input numbers indicated in the table. II.

Example IIA.

Biopiva 100 lignin from UPM weighing 71.0 g was dissolved in 149.0 grams of water at a temperature of 20°C, followed by the addition of 13.3 g of 25% NH ₄ OH solution and stirring for one hour using a magnetic stirrer, after to which 16.8 g of 30% H ₂ O ₂ was slowly added with stirring. The temperature in the water bath was increased to 60°C. After one hour of oxidation, the water bath was cooled, after which the reaction was accordingly terminated. The resulting material was analyzed for COOH, dry weight, pH, viscosity and density.

Example IIE.

UPM Biopiva 100 lignin weighing 71.0 grams was dissolved in 88.8 grams of water at 20°C, followed by the addition of 13.3 grams of 25% NH4OH solution and stirring for one hour using a magnetic stirrer. 22.8 g of PEG200 plasticizer was then added and mixed for 10 minutes, after which 16.7 g of 30% H ₂ O ₂ was slowly added with stirring. The temperature in the water bath was increased to 60°C. After one hour of oxidation, the water bath was cooled, after which the reaction was accordingly terminated. The resulting material was analyzed for COOH, dry weight, pH, viscosity and density.

- 25 045325

Example IIC.

Biopiva UPM 100 lignin weighing 71.0 grams was dissolved in 57.1 grams of water at 20°C, followed by the addition of 13.3 g of 25% NH4OH solution and stirring for one hour using a mechanical stirrer, after which it was 16.6 g of 30% H ₂ O ₂ was slowly added with stirring. The temperature in the water bath was increased to 60°C. After one hour of oxidation, the water bath was cooled, after which the reaction was accordingly terminated. The resulting material was analyzed for COOH, dry weight, pH, viscosity and density.

Example IIF.

UPM Biopiva 100 lignin weighing 71.0 grams was dissolved in 57.1 grams of water at 20°C, followed by the addition of 13.3 grams of 25% NH ₄ OH solution and stirring for one hour using a mechanical stirrer. 19.0 g of PEG200 plasticizer was then added and mixed for 10 minutes, after which 16.6 g of 30% H ₂ O ₂ was slowly added with stirring. The temperature in the water bath was increased to 60°C. After one hour of oxidation, the water bath was cooled, after which the reaction was accordingly terminated. The resulting material was analyzed for COOH, dry weight, pH, viscosity and density.

Table IIA

Example Etc PA Pr pv Etc PS Etc IID Etc NOT Etc IIF Etc IIG Pr Mon Pr III Pr Sh Etc PC Pr IIL Etc THEM Etc IIN Etc BY PR PR Etc HQ Pr IIR PR IIS Materials, weight in grams Lignin 71.0 71.0 71.0 71.0 71.0 71.0 71.0 71.0 71.0 71.0 71.0 71.0 71.0 71.0 71.0 71.0 93 5 112.3 149.5 Water 149.0 88.8 57.1 17.7 88.8 57.1 17.7 88.8 57.1 17.7 88.8 57.1 17.7 88.8 57.1 17.7 117 90.3 37.3 ΝΉ4ΟΗ (25% by weight solution in water) 13.3 13.3 13.3 13.4 13.3 13.3 13.4 13.3 13.3 13.4 13.3 13.3 13.4 13.3 13.3 13.4 17.5 21 28.3 H2O2 (30% by weight solution in water) 16.8 16.7 16.6 17.2 16.7 16.6 17.2 16.7 16.6 17.2 16.7 16.6 17.2 16.7 16.6 17.2 22 26.3 36.3 PEG200 θ,θ 0.0 0.0 0.0 22.8 19.0 14.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 PVA 0 0 0 0 0 0 0 5 10 15 0 0 0 0 0 0 0 0 0 Urea (25% by weight solution in water) 0 0 0 0 0 0 0 0 0 0 3.2 3.8 5.0 0 0 0 0 0 0 G licerin 0 0 0 0 0 0 0 0 0 0 0 0 0 16.0 21.0 30.0 0 0 0 Sorbitol 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 16.0 21.0 30.0 Dry weight in %, at 200 °C, 1 hour 18.2 27.1 30.5 40.1 26.5 33 40.3 28.2 34.4 46.3 25.1 30.2 40.2 25.3 29.3 40.3 25.3 30.5 38.8 pH 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9.5 9 5 Viscosity, cP at 20 °C 450.5 25000 above 10000 0 above 10000 0 15000 25000 50000 15000 25000 50000 15000 25000 50000 15000 25000 50000 15000 25000 50000 Appearance ** *** * * *** *** *** *** *** *** *** *** *** *** *** *** *** *** *** COOH, mmol/g 1.1 0.9 0.9 0.8 0.8 1.9 - Initial lignin concentration Mass fraction of aqueous solution 0.32 0.44 0.55 0.80 0.44 0.55 0.80 0.44 0.55 0.80 0.44 0.55 0.80 0.44 0.55 0.80 0.44 0.55 0.80

[*] heterogeneous solution of thick black color, [**] solution of black color, [***] homogeneous solution of thick black color

Example III.

8.5 L of hot water (50°C) and 1.9 L of NH4OH (24.7%) were mixed, followed by the slow addition of 9.0 g of lignin (Biopiva 100 from UPM) over 10 min with vigorous stirring. (660 rpm, 44 Hz).

Due to high shear forces, the temperature increased. After 30 minutes, 4 L of hot water was added and the material was mixed for a further 15 minutes before adding the remainder of the hot water (5 L). The samples were then removed for undissolved lignin analysis using a Hegman meter and pH measurements.

This pre-mixture was then transferred to the rotor-stator and reaction apparatus where oxidation was carried out using H ₂ O ₂ (17.5 vol.%). The reaction apparatus used herein was at least partly a reaction tube and a reaction vessel. The dosage of the pre-mixture was 150 l/h, and the dosage of H2O2 was 18 l/h.

In this case, a Cavitron CD1000 rotor-stator unit was used to perform the mixing/oxidation step. This rotor-stator device operated at a frequency of 250 Hz (with a peripheral speed of 55 m/s) and a back pressure of 2 bar. The residence time in the reaction tube was 3.2 minutes, and in the reaction vessel - two hours.

The premix temperature was 62°C, and the oxidation step increased this temperature to 70°C.

The final product was analyzed for COOH content, _dry weight, pH, viscosity and remaining _H2O2 .

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Table III

Example Dry weight, 200 °C, 1 hour, % coone, mmol/g solids pH Viscosity III 22.3 1.13 9.6 average

Example IV.

484.1 L of hot water (70°C) and 47.0 L of NH ₄ OH (24.7%) were mixed, after which 224.0 kg of lignin (Biopiva 100 from UPM) was slowly added over 15 min. intensive mixing. The samples were then removed for undissolved lignin analysis using a Hegman meter and pH measurements.

This pre-mixture was then transferred to a static mixer and mixer/heat exchanger where oxidation was carried out using H ₂ O ₂ (35% vol). The dosed supply of the preliminary mixture was 600 l/h, and the dosed supply of H ₂ O ₂ was 17.2 l/h. The holding time in the mixer/heat exchanger was 20 minutes.

The temperature of the mixture increased during the oxidation stage to 95 °C.

The final product was analyzed for COOH content, dry weight, pH, viscosity and remaining H2O2.

From this AOL a binder was formed: 49.3 g AOL (19.0% solids); 0.8 g Primid XL552 (100% solids); and 2.4 g PEG200 (100% solids) were mixed with 0.8 g water to give 19% solids; after which the resulting mixture was used to test the mechanical properties during tests on specimen bars.

Tests on samples bars.

The mechanical strength of the binders was tested during testing on sample bars. To study each binder, 16 bars were prepared from a mixture of binder and pieces of stone wool obtained by spinning stone wool fibers.

A sample of this binder solution containing 15% solids (16.0 g) was thoroughly mixed with the indicated portions (80.0 g). The resulting mixture was then poured into four slots in a heat-resistant silicone mold to obtain small bars (4x5 slots per mold; slot dimensions at the top: length = 5.6 cm, width = 2.5 cm; slot dimensions at the bottom parts: length=5.3 cm, width=2.2 cm; slot height=1.1 cm). After this, the mixtures placed in the slots were pressed using a metal plate of appropriate size to obtain smooth surfaces of the bars. In this way, 16 bars were made for each binder. The resulting bars were then cured at 200°C. The curing time was one hour. After cooling to room temperature, these bars were carefully removed from their nests. Five bars were aged in a water bath at 80°C for three hours.

After drying for 1-2 days, the aged bars, as well as five unaged bars, were broken in a three-point bending test (test speed: 10.0 mm/min; breaking rate: 50%; nominal strength: 30 N/mm ² ; support base: 40 mm; maximum deflection: 20 mm; nominal modulus of elasticity: 10,000 N/mm ² ) using the Bent Tram testing facility to study their mechanical strength. The bars were placed in the specified setup with their face up (ie, the side with dimensions: length = 5.6 cm, width = 2.5 cm).

AOL Features Bar tests Sample name Solids, 200 °C, 1 hour, % COOH (mmol/g solids) Viscosity Initial strength (kN) Strength after aging (kN) Pr IV 17.7 1.69 low 0.28 0.11

Brief description of the figures

The present invention is further described below in connection with the accompanying drawings, wherein the figures show the following:

in fig. 1 shows a portion of a first embodiment of a roofing system for a flat roof in cross section;

in fig. 2 shows a portion of a second embodiment of a roofing system for a flat roof in cross section;

in fig. 3 is a graph illustrating the delamination strength of an insulation member used in a roofing system compared with the delamination strength of a prior art insulation member;

- 27 045325 in Fig. 4 is a graph illustrating the delamination strength of an insulation member used in a roofing system after aging compared with the delamination strength of an insulating member of a prior art insulation member after aging;

in fig. 5 is a graph illustrating the compressive strength of an insulating member used in a roofing system compared with the compressive strength of a prior art insulating member;

in fig. 6 is a graph illustrating the compressive strength of an insulating member used in a roofing system after aging compared with the compressive strength of a prior art insulating member after aging;

in fig. 7 shows a segment of a possible lignin structure;

in fig. Figure 8 shows different lignin precursors and common connections between structural units;

in fig. 9 shows four groups of technical lignins available on the market; and in fig. 10 summarizes the properties of technical lignins.

Detailed Disclosure of the Present Invention

In fig. 1 shows a portion of a first embodiment of a flat roof 1, comprising: a support structure 2, a vapor barrier layer 3, an insulating element 4 and a covering waterproof membrane 20. The insulating element 4 is a product consisting of bonded mineral fibers, made of mineral fibers, and a binder.

The covering waterproof membrane 20 is connected to the insulating element 4 by an adhesive material 9, which may be an integral part of the membrane 20. The adhesive material 9 may be a bituminous adhesive that is activated by a torch commonly used in roofing; those. the membrane 20 is soldered to the insulating element 4. The dotted line passing through the insulating element 4 indicates the area 10 to which molten bitumen adhesive material 9 is applied before curing and bonding the membrane 20 to the insulating element 4.

In fig. 2 shows a portion of a second embodiment of a flat roof 1, comprising: a support structure 2, a vapor barrier layer 3, an insulation element 4, and a waterproof membrane 20 (not shown; but comparable to the membrane shown in FIG. 1). The insulating element 4 includes a first layer 5 containing rock wool fibers and a binder, and a second layer 6 consisting of a glass wool sheet with an elastic modulus of 573 MPa. The tensile strength of glass wool is 71 N.

The first layer 5 is provided in the form of one or more thin composite layers of fibers oriented substantially perpendicular to the main surface 7 of the second layer 6. The thin composite layer and therefore the entire first layer 5 has a density of 110 kg/m ³ and a typical thickness of 150 mm. The mineral fibers are bonded together by means of a binder cured in a curing oven before attaching the second layer 6 to the surface 8 of the first layer 5 using an adhesive material 9. The adhesive material 9 in this particular embodiment of the present invention may be selected from the group consisting of melamine -urea-formaldehyde, preferably in the form of a two-component adhesive; water-based acrylic glue; phenol-formaldehyde powder binder; water-based neoprene foam adhesive, polyamide-based powder adhesive; polyurethane adhesive, preferably in the form of a two-component adhesive; polyurethane moisture-resistant glue; or a sealing modified binder, preferably in the form of a one-component moisture-resistant adhesive. However, in a preferred embodiment, the adhesive material 9 in this particular embodiment of the present invention is similar to the binder composition that is used to bind together the mineral fibers of the insulating element 4.

All of these adhesive materials 9 create a strong bond with the mineral fibers, and all of these adhesive materials 9 are configured to form substantially completely enclosed layers in the thin composite layer region as well as in the web region, which enhances the strength of the insulating element 4 in a direction parallel to the main surfaces 7 thin compound layers.

The adhesive material 9 is located partially in the area 10 closer to the main surface 8 of the first layer 5, facing the second layer 6, and in the area 11 closer to the main surface 7 of the second layer 6, facing the first layer 5, as a result of which the adhesive material 9 connects between the first layer 5 and the second layer 6 in such a way that the forces directed perpendicular to the second layer 6 can be compensated by the tensile strength of the second layer 6 in combination with the adhesive material 9 and/or the deflection of the fibers of the first layer 5. Such a force, for example, 80 kPa, directed perpendicular to the second layer 6, causes limited deformation of the insulating element 4 (first and second layers 5 and 6), amounting to less than 5% of its thickness, i.e. no more than 7.5 cm with a thickness of the first layer of 5 to 150 mm. The thickness of the second layer 6 is approximately no more than 1 mm; and, accordingly, it can be ignored. A sufficient amount of adhesive material 9 is provided between the fibers of the first layer 5 to enclose the fibers and create a layer of adhesive material 9 that penetrates and hardens into the first layer 5.

- 28 045325

Adhesive material 9 in the form of acrylic glue is applied between two layers 5 and 6 at the rate of 80 grams per square meter. A sufficient amount of adhesive material 9 penetrates into the first layer 5 and into the second layer 6. Consequently, the adhesive material 9 forms a layer connecting the first layer 5 and the second layer 6, and is fixed in both of these layers 5 and 6.

The binder used in the insulating element 4 contains a first component in the form of one or more ammonia-oxidized lignins. In the graph shown in FIG. 3 shows the absolute values of the peel strength of the insulating element 4 according to the present invention (curve C2) in comparison with the peel strength of the insulating element with one of the prior art binders that does not contain formaldehyde (curve A ₂ ) and the peel strength of the insulating element , containing the traditionally used binder based on phenol-urea-formaldehyde (curve Br).

Delamination strength is measured in accordance with the requirements of EN 1607:2013, with a first initial measurement carried out on unaged samples immediately or shortly after production of the insulating element 4. This initial test and the corresponding average result from a representative number of samples are displayed at time 0 on the X axis of the graph. The specified time 0 corresponds to day 0, i.e. starting the accelerated aging test as described below.

To determine the aging resistance of mineral fiber products exposed to moisture and heat during the life of the structure, mineral fiber products that emphasize mechanical properties are subjected to accelerated aging. Aging resistance is defined as the ability of a product to retain its original mechanical properties and is calculated as the strength after aging as a percentage of the original strength. The test methodology corresponds to the so-called Nordtest method (NT Build 434: 1995.05), extended over 28 days.

The purpose of this method is to subject insulating materials to accelerated aging through increased temperature and heat. It is applicable to all insulating materials manufactured in the form of insulating boards. This method is not predictive in nature, i.e. it is not intended to evaluate the service life, but serves only as a precondition for obtaining a satisfactory result that aging using this method will not lead to significant changes in the properties of the materials under study. Nordtest's experience with this method over more than two decades has proven its ability to provide reliable data to ensure acceptable mechanical performance, particularly for mineral fiber products used as insulation elements in roofing systems.

In this method, a representative number of test specimens are exposed to heat and moisture for 7, 14 and 28 days at a temperature of 70 ± 2°C and a relative humidity of 95 ± 5% in a climate chamber. The samples are then maintained at a temperature of 23±2°C and a relative humidity of 50±5% for at least 24 hours and, after drying, are prepared for testing of mechanical properties such as, for example, delamination strength, which is measured in accordance with the requirements standard EN 1607:2013, or compressive strength, which is measured in accordance with the requirements of standard EN 826:2013, which will be further described below.

The relative aging resistance is then calculated as a percentage of and based on the original absolute value measured at time 0. Results are documented and demonstrated after 7, 14 and 28 days of accelerated aging.

As shown in FIG. 3-6, and as described in the examples provided herein, the insulation element 4 is a bonded mineral fiber roofing product commercially produced by authorized or affiliated companies, which is manufactured with the various types of binders specified above and tested for mechanical properties. The described product provides the required density of about 145 kg/m ³ and loss on ignition (LOI) of about 3.8 wt.%.

In the next table. I presents the delamination strength [kPa] values according to EN 1607 shown in Fig. 3.

Table I

0 days 7 days 14 days 28 days A ₂ 38.6 28.4 27.9 26.9 AT ₂ 32.1 23.7 21.1 15.3 from ₂ 33.4 25.7 23.5 21.8

In table I shows the absolute values of the delamination strength of the insulating element 4 (C ₂ ) according to the present invention in comparison with the insulating element A ₂ containing a phenol-formaldehyde binder and with the insulating element B2 containing a binder without formaldehyde. The corresponding curves are presented in the graph shown in FIG. 3.

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In the next table. II presents the values of the delamination strength relative to the delamination strength according to table. I as a percentage of the original strength shown in Fig. 4.

Table II

0 days 7 days 14 days 28 days Az 100.0 73.6 72.1 68.7 Vz 100.0 75.2 67.1 48.3 NW 100.0 77.5 71.1 66.2

In table I shows the relative peel strength of the insulating element 4 (C ₃ ) according to the present invention in comparison with the insulating element A ₃ containing a phenol-formaldehyde binder and with the insulating element B ₃ containing a binder without formaldehyde. The corresponding curves are presented in the graph shown in FIG. 4.

From Tables I and II, it can be seen that the peel strength of the insulating element 4 according to the present invention is as close as possible to the peel strength of the insulating element containing phenol-formaldehyde binder. Moreover, it can be seen that the loss of delamination strength of the insulating member containing the formaldehyde-free binder is increased much more than that of the insulating member 4 according to the present invention. Moreover, the peel strength of the insulating element 4 according to the present invention is as close as possible to the peel strength of the insulating element containing phenol-formaldehyde binder. In fig. 3 and 4 it can be seen that the curves C ₂ /C ₃ and A ₂ /A ₃ run essentially parallel to each other.

In table II and in fig. 4 shows the relative peel strength of the insulating element 4 according to the present invention (curve C ₃ ) in comparison with the peel strength of insulating elements containing a phenol-formaldehyde binder (curve A ₃ ) or insulating elements containing a binder without formaldehyde (curve B3). All compared insulating elements were subjected to an aging process as described above.

Moreover, as can be seen in FIG. 4, the delamination values of the insulating element 4 according to the present invention are approximately equal to the delamination values of the insulating element A ₃ containing phenol-formaldehyde binder.

In the next table. III the absolute compressive strength [kPa] values according to EN 826 are shown in Fig. 5.

Table III

0 days 7 days 14 days 28 days a ₄ 82.6 65.5 63.9 61.3 at ₄ 66.3 55.1 51.4 43.9 from ₄ 71.5 58.5 56.1 54.0

In table III shows the absolute compressive strength of the insulating element 4 (C ₄ ) according to the present invention in comparison with the insulating element A ₄ containing a phenol-formaldehyde binder and with the insulating element B4 containing a binder without formaldehyde. The corresponding curves are presented in the graph shown in FIG. 5.

In fig. 5 shows the compressive strength of the insulating element 4 according to the present invention (curve C ₄ ) in comparison with the compressive strength of the insulating element containing mineral fibers and a formaldehyde-free binder (curve B ₄ ), and with the compressive strength of the insulating element containing mineral fibers and phenol-formaldehyde binder (curve A4).

The compressive strength is measured in accordance with the requirements of the EN 826 standard, and it can be seen that the compressive strength was measured immediately after the production of the insulating element 4, and also 4, 7, 14 and 28 days after the production of the insulating element 4.

While the compressive strength of the insulating member 4 according to the present invention is as close as possible to that of the insulating member A ₄ containing a phenol-formaldehyde binder, it can be seen that the loss of compressive strength of the insulating member B ₄ containing a binder without formaldehyde is increased much more than that of insulating element 4 according to the present invention. In addition, the compressive strength of the insulating element 4 according to the present invention is as close as possible to the compressive strength of the insulating element containing phenol-formaldehyde binder (curve A ₄ ). It can be seen that curves C2 and A2 run substantially parallel to each other.

In the next table. IV presents the values of compressive strength relative to the compressive strength according to table. III as a percentage of the original strength shown in FIG. 6.

Table IV

0 days 7 days 14 days 28 days a ₅ 100.0 80.5 78.5 75.2 at ₅ 100.0 83.2 77.8 66.6 from ₅ 100.0 82.5 79.0 76.1

In table IV shows the relative compressive strength of the insulating element 4 (C5) according to the present invention in comparison with the insulating element A ₅ containing a phenol-formaldehyde binder and with the insulating element B ₅ containing a binder without formaldehyde. The corresponding curves are presented in the graph shown in FIG. 6.

In fig. 6, the relative compressive strength of the insulating element 4 according to the present invention (curve C ₅ ) is compared with insulating elements containing a phenol-formaldehyde binder (curve A ₅ ) or with insulating elements containing a binder without formaldehyde (curve B ₅ ). All compared insulating elements were subjected to an aging process involving the steps described above.

In addition, in FIG. 6, it can be seen that the compressive strength values of the insulating element 4 according to the present invention are approximately equal to the compressive strength values of the insulating element containing phenol-formaldehyde binder.

Claims (18)

1. A roofing system for a flat roof or flat sloping roof of a building with thermal and/or sound insulation, consisting of a support structure, a roof deck, an optional vapor barrier layer, a waterproof membrane and at least one insulating element that is a bonded mineral fiber product, which is made of mineral fibers, preferably rock wool fibers, and a cured water-based binder composition, wherein the water-based binder composition, before curing, contains component (i) in the form of one or more oxidized lignins, component (ii) in the form of one or more cross-linking agents and component (iii) in the form of one or more plasticizers; and at the same time the insulating element is characterized by a bulk density in the range of 70-250 kg/m ³ . 2. The roofing system according to claim 1, wherein the insulating element has a loss on ignition (LOI) of 2-8 wt%, preferably 2-5 wt%. 3. Roofing system according to any of the previous paragraphs, characterized by the presence of insulating elements having a compressive strength in the range of 50-130 kPa, measured in accordance with the requirements of the European standard EN 826:2013. 4. Roofing system according to any of the previous paragraphs, characterized by the presence of insulating elements with a delamination strength in the range of 20-50 kPa, measured in accordance with the requirements of the European standard EN 1607:2013. 5. The roofing system according to any of the preceding claims, wherein component (i) is in the form of one or more ammonia-oxidized lignins (AOL). 6. The roofing system according to any of the preceding claims, wherein component (ii) contains one or more cross-linking agents selected from β-hydroxyalkylamide cross-linking agents and/or oxazoline cross-linking agents. 7. The roofing system according to any of the preceding claims, wherein component (ii) contains: one or more cross-linking agents selected from the group consisting of polyethylenimine, polyvinylamine and fatty amines; and/or one or more cross-linking agents in the form of fatty amides; and/or one or more cross-linking agents selected from the group consisting of dimethoxyethanol, glycolaldehyde and glycine-oxalic acid; and/or one or more cross-linking agents selected from polyester polyols such as polycaprolactone; and/or one or more cross-linking agents selected from the group consisting of starch, modified starch and carboxymethylcellulose (CMC); and/or one or more cross-linking agents in the form of aliphatic multifunctional carbodiimides; and/or one or more cross-linking agents selected from melamine-based cross-linking agents, such as hexamethoxymethylmelamine (HMMM) cross-linking agents. 8. The roofing system according to any one of the preceding claims, comprising component (ii), the content of which is 1-40 wt.%, for example 4-20 wt.%, for example 6-12 wt.%, based on the dry weight of the component (i). 9. The roofing system according to any of the preceding claims, wherein component (iii) contains one or more plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyesters, hydrogenated sugars, phthalates and/or acids such as adipic acid, vanillic acid, lactic acid and/or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic polymers with free carboxyl groups and/or polyurethane dispersions with free carboxyl groups. 10. The roofing system according to any of the preceding claims, wherein component (iii) contains: - 31 045325 one or more plasticizers selected from the group consisting of fatty alcohols such as pentanol, stearyl alcohol; and/or one or more plasticizers selected from the group consisting of alkoxylates, such as ethoxylates, such as butanol-ethoxylates, such as butoxytriglycol; and/or one or more plasticizers in the form of propylene glycols; and/or one or more glycol ether plasticizers; and/or one or more plasticizers selected from the group consisting of adipate, acetate, benzoate, cyclobenzoate, citrate, stearate, sorbate, sebacate, azelainate, butyrate and valerianate; and/or one or more plasticizers selected from the group consisting of phenol derivatives such as alkyl- or aryl-substituted phenols; and/or one or more plasticizers selected from the group consisting of silanols and siloxanes; and/or one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkylaryl sulfonates such as alkyl; and/or sulfonates, phosphates such as tripolyphosphates; and/or one or more hydroxy acid plasticizers; and/or one or more plasticizers selected from the group consisting of monomer amides such as acetamides, benzamides, fatty acid amides such as tall oil amides; and/or one or more plasticizers selected from the group consisting of quaternary ammonium compounds such as trimethylglycine, distearyl dimethylammonium chloride; and/or one or more plasticizers selected from the group consisting of vegetable oils such as castor oil, palm oil, linseed oil, tall oil and soybean oil; and/or one or more plasticizers selected from the group consisting of hydrogenated oils and acetylated oils; and/or one or more plasticizers selected from methyl acid esters; and/or one or more plasticizers selected from the group consisting of alkyl polyglucosides, gluconamides, aminoglucoseamides, sucrose esters and sorbitan esters; and/or one or more plasticizers selected from the group consisting of polyethylene glycols and polyethylene glycol ethers. 11. The roofing system according to any of the preceding paragraphs, in which the content of component (iii) is in the range of 0.5-50 wt.%, preferably in the range of 2.5-25 wt.%, more preferably in the range of 3-15 wt. %, based on the dry weight of component (i). 12. The roofing system according to any of the preceding claims, comprising additional component (iv) in the form of one or more coupling agents, such as organofunctional silanes in the binder. 13. The roofing system according to any of the preceding claims, further comprising component (v) in the form of one or more components selected from the group consisting of ammonia, amines or any of their salts in the binder. 14. The roofing system according to any of the preceding claims, comprising an additional component in the form of urea in the binder, the content of which lies in particular in the range of 5-40 wt.%, for example in the range of 10-30 wt.%, for example in the range 15-25% by weight, based on the dry weight of component (i). 15. The roofing system according to any of the preceding claims, wherein the binder essentially contains: component (i) in the form of one or more oxidized lignins; component (ii) in the form of one or more cross-linking agents; component (iii) in the form of one or more plasticizers; component (iv) in the form of one or more coupling agents such as organofunctional silanes; optionally a component in the form of one or more compounds selected from the group consisting of ammonia, amines or any salts thereof; optionally a urea component; optionally a component in the form of one or more reactive or chemically inactive silicone polymers; optionally hydrocarbon oil; optionally one or more surfactants; and water. 16. An insulating element for a roofing system according to any one of the preceding claims 1 to 15, made of mineral fibers, preferably rock wool fibers, and a water-based binder composition, wherein the water-based binder composition, before curing, contains component (i) in the form of one or more oxidized lignins, component (ii) in the form of one or more - 32 045325 how many cross-linking agents and components (iii) in the form of one or more plasticizers; and at the same time the insulating element is characterized by a bulk density lying in the range of 70250 kg/m ³ . 17. The insulating element according to claim 16, additionally characterized by the features according to any of the previous claims 2-15. 18. An insulating element for a roofing system for a flat roof or a flat sloping roof of a building according to any one of the preceding claims 1 to 15, including a first layer comprising rock wool fibers and a binder, and a second layer made of glass wool, the second layer being attached to the main surface of the first layer with an adhesive material, wherein the first layer consists of at least one thin composite layer, the fibers of which are oriented perpendicular to the main surfaces of the second layer, and wherein the first layer contains a cured binder; characterized in that the adhesive material is located partially in the area between the fibers closer to the main surface of the first layer, facing towards the second layer, and in the area closer to the main surface of the second layer, facing towards the first layer, as a result of which the adhesive material connects the first layer together and a second layer such that the forces directed perpendicular to the second layer can be compensated by the tensile strength of the second layer in combination with the adhesive material and/or deflection of the fibers of the first layer, which causes limited deformation of <5% of the thickness of the insulating element.