EA045582B1 - WATER DRAINAGE METHOD - Google Patents

Description

Field of technology to which the invention relates

The present invention relates to a water drainage method, a water drainage device, and a group of two or more water drainage devices.

State of the art

Precipitation such as rain, snow, sleet, hail, etc. leads to the accumulation of water, which must be securely collected and/or discharged somewhere. Typically, roof gutters and main drainage systems are used to collect excess water and carry it to a collection point. However, surface water often remains on the ground, which can cause the ground to become waterlogged or flooded.

It is known that there are devices incorporating artificial glassy fibers that can absorb and hold excess surface water, and gradually disperse it back into the surrounding soil. It is also known that there are devices that absorb excess surface water and divert the water somewhere else.

Patent document WO 2013/113410 discloses a drainage element formed from a hydrophilic bonded man-made vitreous fiber substrate (MMVF), wherein the man-made vitreous fiber (MMVF) substrate includes artificial vitreous fibers bonded by a cured binder composition, wherein the MMVF substrate has opposing first and second ends and a channel extending from a first opening at a first end to a second opening at a second end.

Patent document WO 2013/072082 discloses a water drainage reservoir including a bonded man-made vitreous fiber substrate and a conduit having two open ends, the MMVF substrate including man-made vitreous fibers bonded by a cured binder composition, the first open end of the conduit being in fluid communication. environment with MMVF substrate.

Patent document WO 2014/029873 discloses a surface water drainage structure including a bonded load distribution layer and a drainage layer, wherein the drainage layer is formed from a group of bonded man-made vitreous fiber (MMVF) drainage elements, each of the drainage elements including bonded man-made vitreous fibers (MMVFs). cured binder composition, the drainage layer being under the load-distributing layer.

Patent document WO 2014/029872 discloses a device including a bonded man-made vitreous fiber substrate, and at least one first conduit and at least one second conduit, each conduit having first and second open ends, wherein the MMVF substrate includes man-made vitreous fibers bonded by a cured binder composition, wherein the first open end of the first conduit and the first open end of the second conduit are, in each case independently, in fluid communication with the MMVF substrate, the first conduit being at a greater height than the second conduit, wherein at least a portion The MMVF substrate is placed between the first and second pipelines.

Such devices typically include phenol-formaldehyde resins and urea-phenol-formaldehyde resins as binders. These binders are economical to produce and provide excellent mechanical handling properties. This is very important since the devices are located deep in the ground and must be able to withstand installation conditions and then pressure from above the ground during operation (eg from vehicles).

However, existing and proposed legislation aimed at reducing or eliminating formaldehyde emissions during manufacturing from the manufacturing plant, but also into the work environment, has led to the development of formaldehyde-free binders. There is also a continuing trend for consumers to prefer products that are formed wholly or at least in part from renewable materials, and therefore there is a need to provide binders for water absorption devices that are formed at least in part from renewable materials. In addition, known formaldehyde-based binders often include corrosive and/or harmful components. This requires protective measures to be taken for the equipment and measures to ensure the safety of personnel operating the equipment.

Previously, formaldehyde-free binders for water-absorbing devices have been proposed. However, there are still some disadvantages associated with MMVF products formed with these binder materials in terms of poor mechanical properties when compared with MMVF products formed from phenol-formaldehyde resins. In addition, such binders are often made from expensive raw materials.

In addition, there is a continuing need to improve the water retention characteristics of drainage devices, such as storage, infiltration and drainage.

In addition, known MMVF drainage devices typically contain wetting agents to improve hydrophilicity. However, certain wetting agents may leach out of the MMVF-1045582 product over time. This is particularly problematic since the drainage devices are located in the soil and thus the wetting agent can be sucked out and contaminate the surrounding soil. In addition, when the wetting agent is washed out, the drainage characteristics of the device would change significantly. Finally, there is a continuing need to reduce the number of components required to produce MMVF drainage devices, both for environmental reasons and in terms of cost-effectiveness.

Therefore, it would be desirable to provide a water drainage device including a binder material that does not contain formaldehyde but has equivalent or superior mechanical handling properties (eg, compressive strength) to phenol-formaldehyde binders. It would be desirable for such a binder to have improved water retention properties (eg, improved accumulation, percolation and drainage characteristics). In addition, it would be desirable for such a binder material to be economical to manufacture and based primarily on renewable sources. Finally, it would be desirable that such a bonding material would not require additional addition of a wetting agent and thereby prevent the leaching of wetting agents into the surrounding soil.

The essence of the invention

The water drainage device used in the present invention solves the above problems.

In a first aspect, a method for water drainage is provided, comprising the steps of providing a water drainage device, wherein the water drainage device includes man-made vitreous fibers (MMVF) bonded with a cured aqueous binder composition; and placing a water drainage device in contact with the ground, the water drainage device absorbing water and releasing water into a receptacle;

wherein the aqueous binder composition, before curing, includes 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.

In a second aspect of the invention, there is provided a water drainage device comprising man-made vitreous fibers (MMVF) bonded by a cured aqueous binder composition, wherein the aqueous binder composition, before curing, comprises 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.

In a third aspect of the invention, a group of two or more water drainage devices is provided, the water drainage devices comprising man-made vitreous fibers (MMVF) bonded by a cured aqueous binder composition, wherein the aqueous binder composition, before curing, comprises 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.

In a fourth aspect of the invention, there is provided a method for producing a water drainage device, comprising the steps of (i) providing artificial vitreous fibers;

(ii) spraying the artificial vitreous fibers with an aqueous binder composition; and (iii) collecting and compacting the artificial vitreous fibers and curing the aqueous binder composition to form a water drainage device;

wherein the aqueous binder composition, before curing, includes 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.

The present inventors have discovered that it is possible to produce a formaldehyde-free binder material that results in a device with mechanical handling properties (e.g., compressive strength as initial strength, but also as strength after aging) equivalent to devices bonded with phenol-formaldehyde binders . The inventors of the present invention have also obtained such a binder material that results in devices that have improved water retention characteristics (eg, accumulation, percolation, drainage), which is very useful for water drainage. The inventors of the present invention have obtained such a binder material which is economical and based mainly on renewable sources. Finally, this binder material means that adding a wetting agent to the device is not required, preventing the wetting agent from leaching into the surrounding soil and providing both environmental and cost benefits.

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Description of the figures

Fig. 1A-1E show the results of compressive strength tests.

Fig. 2 shows the results of average water accumulation.

Fig. 3 shows the results of average water drainage.

Fig. 4 shows the results of average water infiltration.

Fig. 5 schematically shows a water drainage device completely buried in the ground and connected to the roof gutters of the building.

Fig. 6 shows a water drainage device including a channel.

Fig. 7 shows a fragment of a possible lignin structure.

Fig. 8 shows possible lignin precursors and common interblock bonds.

Fig. 9 shows four groups of technical lignins available on the market.

Fig. 10 shows a summary of the properties of technical lignins.

Detailed Description of Embodiments of the Invention

The invention relates to a method of water drainage, comprising the steps of providing a water drainage device, wherein the water drainage device includes man-made vitreous fibers (MMVF) bound by a cured aqueous binder composition; and placing a water drainage device in contact with the ground, the water drainage device absorbing water and releasing water into a receptacle;

wherein the aqueous binder composition, before curing, includes 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.

The invention relates to drained water, preferably to drained surface water. It can be diverted to drain surface water from play areas such as playgrounds and sports fields. Sports grounds include football pitches, rugby pitches, cricket pitches, bowling greens, grass tennis courts, golf courses, playgrounds, athletic fields and equestrian centers. It can also be diverted to drain water from gardens, parks or fields. It can also be diverted to drain water from roof gutters and building or street drainage systems.

The water drainage device has its usual meaning in technology. It is a device that is capable of draining water. Drainage refers to the removal of surface water or subsurface water from an area of excess water. It can do this by absorbing water and holding it in its structure, or transferring water to a receiver, for example, to a water collection point. The water drainage device according to the invention can also be called a water retention device, or a water storage device, or a water storage device. This is due to the fact that it slows down the flow of water to collection points by absorbing it and retaining it within its structure.

The water drainage device is hydrophilic, i.e. it attracts water. The term hydrophilic has its usual meaning in technology.

The hydrophilicity of a water drainage device can be defined in terms of the contact angle with water. The MMVF material of the device preferably has a contact angle with water of less than 90°. The contact angle is measured using the stationary drop measurement method. Any sessile drop method can be applied, for example using a goniometer to measure the contact angle. In practice, a drop is placed on a solid surface and an image of the drop is recorded over time. The static contact angle is then determined according to the Young-Laplace equation around the droplet. The contact angle is taken to be the angle between the calculated drop shape function and the surface of the sample, the projection of which in the drop image is considered the base line. Equilibrium contact angles are used to further estimate and calculate surface free energy using the Owens-Wendt-Rabel-Kjellble method. The method for calculating the contact angle between a material and water is generally known to a qualified specialist.

The hydrophilicity of a drainage device can be determined by hydraulic conductivity. The drainage device preferably has a hydraulic conductivity of 5 to 300 m/day, preferably 50 to 200 m/day. Hydraulic conductivity is measured in accordance with ISO 17312:2005. The advantage of this hydraulic conductivity is that the drainage device can absorb excess water and discharge it at a sufficient rate to prevent flooding.

The hydrophilicity of a MMVF substrate sample can also be measured by determining the immersion time of the sample. To determine the immersion time, a sample of MMVF substrate having dimensions of 100x100x100 mm is required. A container with a minimum size of 200x200x200 mm is filled with water. Immersion time is the time from the moment the specimen first comes into contact with water until the test specimen is completely immersed. The sample is placed in contact with

- 3 045582 with water in such a way that it first comes into contact with water in a cross section of 100x100 mm. The sample will then need to be immersed slightly more than 100mm to be fully immersed. The faster the sample sinks, the more hydrophilic the sample is. An MMVF substrate is considered hydrophilic if the immersion time is less than 120 s. The immersion time is preferably less than 60 seconds. In practice, the water drainage device may have a immersion time within a few seconds, such as less than 15 seconds.

The method of the present invention includes a water drainage device comprising man-made vitreous fibers (MMVF). Man-made vitreous fibers (MMVF) can have any suitable oxide composition. The fibers may be glass fibers, ceramic fibers, basalt fibers, slag fibers, or mineral or stone fibers. The fibers are preferably of the types commonly known as mineral, stone or slag fibres, most preferably stone fibres.

Stone fibers typically include the following oxides, as a percentage by weight:

SiCh: from 30 to 51

CaO: from 8 to 30

MgO: 2 to 25

FeO (including RegOz): from 2 to 15

Na2O+K2O: no more than 10

CaO+MgO: from 10 to 30

In preferred embodiments, MMVFs have the following elemental contents, calculated as oxides, in wt.%:

West: at least 30, 32, 35 or 37; no more than 51, 48, 45 or 43

AlO3: at least 12, 16 or 17; no more than 30, 27 or 25

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

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

FeO (including RegOz): at least 4 or 5; no more than 15, 12 or 10

FeO+MgO: at least 10, 12 or 15; no more than 30, 25 or 20

MagO+KgO: zero or at least 1; no more than 10

CaO+MgO: at least 10 or 15; no more than 30 or 25

Tyug: zero or at least 1; no more than 6, 4 or 2

Tiug+Peo: at least 4 or 6; no more than 18 or 12

B2O3: zero or at least 1; no more than 5 or 3

P2O5: zero or at least 1; no more than 8 or 5

Other: zero or at least 1; no more than 8 or 5

The MMVF fibers obtained by the method according to the invention preferably have a composition in wt.%: S1O2 from 35 to 50 AI2O3 from 12 to 30 T1O2 to 2 PerO3 from 3 to 12 CaO from 5 to 30 MgO to 15 PaO from 0 to 15 K2O from 0 up to 15 P2O5 up to 3 MnO up to 3 B2O3 up to 3

Another preferred composition for MMVF is as follows, in wt.%:

S1O2 39-55%, preferably 39-52%

AI2O3 16-27%, preferably 16-26%

CaO 6-20%, preferably 8-18%

MgO 1-5%, preferably 1-4.9%

Na2O 0-15%, preferably 2-12%

K2O 0-15%, preferably 2-12%

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R2O (KarO+KrO) 10-14.7%, preferably 10-13.5%

P2O5 0-3%, preferably 0-2%

RegOz (iron in general) 3-15%, preferably 3.2-8%

B2O3 0-2%, preferably 0-1%

Tyug 0-2%, preferably 0.4-1%

Other 0-2.0%

Glass fibers typically include the following oxides, as a percentage by weight:

S1O2: 50 to 70

AI2O3: 10 to 30

CaO: no more than 27

MgO: no more than 12

Glass fibers may also contain the following oxides, as a percentage by weight:

Να ₂ Ο+Κ ₂ Ο: from 8 to 18, in particular Na ₂ O+K ₂ O is greater than CaO+MgO

В2О3: from 3 to 12

Some glass fiber compositions may contain Al ₂ O ₃ : less than 2%.

The geometrically average diameter of the fibers is preferably in the range from 1.5 to 10 microns (µm), in particular from 2 to 8 microns (µm), more preferably from 2 to 5 microns (mm). The present inventors have found that this range of geometric fiber diameters has a positive effect on capillarity, thereby improving the water absorption of the device.

The water drainage device preferably includes at least 90 wt.% artificial vitreous fibers by weight of the total solids content of the water drainage device. The advantage of having so many fibers present in a water drainage device is that there are sufficient pores formed between the fibers to allow the device to hold large quantities of water. The remaining solids content can be composed mainly of the binder material.

The water drainage device is preferably in the form of a bonded MMVF substrate, i.e. bound mass. Those. The water drainage device is preferably a bonded matrix of artificial vitreous fibers that has been prepared as is, but can also be formed by granulating a mineral wool plate and compacting the granular material. A bonded substrate is a single, unified substrate.

The water drainage device according to the invention may optionally include a wetting agent. The wetting agent has its usual meaning in technology and can be a cationic, anionic or non-ionic surfactant.

The water drainage device may include a non-ionic wetting agent such as Rewopal®.

The water drainage device may include an ionic surfactant, more preferably an alkyl ether sulfate surfactant. The wetting agent may be an alkyl metal ether sulfate salt or an ammonium alkyl ether sulfate salt. The wetting agent is preferably sodium alkyl ether sulfate. A commercially available wetting agent based on an alkyl ether sulfate surfactant is Texapon®.

The wetting agent may also be an anionic linear alkyl benzene sulfonate surfactant.

Some non-ionic wetting agents may be leached from the MMVF water drainage device over time. It is therefore preferred to use an ionic wetting agent, in particular an anionic wetting agent such as linear alkyl benzene sulfonate or Texapon®. They do not wash out of the MMVF device to the same extent.

The water drainage device may include 0.01 to 1 wt% wetting agent, preferably 0.05 to 0.5 wt% wetting agent, more preferably 0.1 to 0.3 wt% wetting agent.

However, the inventors of the present invention have discovered that the wetting agent is not essential for the water drainage device according to the invention. This appears to be due to the nature of the binder composition. Therefore, the water drainage device is free from any wetting agent. This means that the water drainage device is preferably free of wetting agent, i.e. includes 0 wt.% wetting agent.

This provides a number of benefits. Firstly, the number of additives in the device is reduced, which is environmentally friendly and also reduces costs. Wetting agents are often derived from non-renewable sources, so it is preferable to avoid their use. In addition, wetting agents can be flushed out of the water drainage device. This poses a problem because the wetting agent can contaminate the surrounding soil. When the wetting agent is washed out, it also changes the nature of the drainage device, typically changing accumulation, drainage and seepage, making it difficult to predict behavior. By eliminating the use of a wetting agent, these problems are avoided.

The water drainage device including MMVF preferably has a density in the range from 60 to 200 kg/m ³ , in particular from 130 to 150 kg/m ³ . The advantage of this density is that the drainage device has a relatively high compressive strength. This is important because the drainage device may be placed in a position where people or vehicles must pass over the ground in which the device is embedded. Optionally, a load distribution plate is placed on top of the drainage device to distribute the loads acting on the drainage device. Such a load distribution plate is preferably not required due to the density of the water drainage device.

The water drainage device including the MMVF preferably has a volume in the range of 10 to 300 L, preferably 100 to 250 L, more preferably 150 to 200 L. The exact volume is selected according to the volume of water expected to be treated. In addition, numerous devices can be used in this field.

The water drainage device according to the invention includes, before curing, an aqueous binder composition comprising 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.

In a preferred embodiment, the binder materials do not contain formaldehyde.

For the purpose of this application, the term formaldehyde free is defined as characterizing a mineral wool product where the emission from the mineral wool product is less than 5 μg/m ² /h of formaldehyde, preferably below 3 μg/m ² /h. The test is preferably carried out in accordance with the ISO 16000 standard for aldehyde emission testing.

Component (i).

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

Lignin, cellulose and hemicellulose are the three main organic compounds 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 second most abundant natural polymer in the world, second only to cellulose, and is estimated to constitute almost 20-30% of all carbon contained in biomass, which amounts to more than 1 billion tons globally.

Fig. 7 shows a fragment 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, biorefined lignin, is a somewhat different material that is characterized not by the extraction process, but instead by the conditions of origin, such as biorefining, and thus may be similar to or different from any of the other groups mentioned. Each group is different from each other, and each is suitable for different applications. Lignin is a complex heterogeneous material composed of up to three different phenylpropane monomers, depending on the source. Softwood lignins are primarily formed by coniferyl alcohol units (see Figure 8) and as a result are more uniform than hardwood lignins, which have a higher syringyl alcohol content (see Figure 8). . The appearance and consistency of lignin varies greatly and is highly dependent on processing conditions.

A summary of the properties of these technical lignins is shown in FIG. 10.

Lignosulfonate from the sulfite pulping process remains the largest source of industrially produced lignin, at a scale of up to 1.4 million tonnes. But despite this, the sulfate cooking process is currently the most widely used cooking method, and is gradually replacing the sulfite method. An estimated 78 million tonnes of lignin per year worldwide are produced by kraft pulping, but the majority is burned to produce steam and power. The current level of kraft pulping production is estimated to be 160,000 tons, but sources indicate that current production is only about 75,000 tons. Kraft lignin is recovered from black liquor, waste liquor from the kraft process, or kraft process. Currently, 3 well-known methods are used to produce kraft lignin: LignoBoost, LignoForce and SLRP. These 3 methods are similar in that they involve the addition of CO2 to reduce the pH value to 9-10, followed by acidification to further reduce the pH to approximately 2. The final stage involves some combination of washing, leaching and filtration to remove ash and other contaminants. The three methods are at different stages of industrialization in the world.

The sulfate process introduces thiol groups, stilbene, while some carbohydrates remain. Sodium sulfate is also present as an impurity due to the precipitation of lignin from the liquor by the action of sulfuric acid, but can potentially be eliminated by changing the order of lignin extraction. The sulfate process results in a large number of phenolic hydroxyl groups, and this lignin is soluble in water when these groups are ionized (above pH~10).

Industrial kraft lignin is generally of higher purity than lignosulfonates.

Molecular masses are 1000-3000 g/mol.

Soda lignin is obtained from sodium hydroxide pulping processes, which are mainly used for wheat straw, sugarcane bagasse and flax. The properties of soda lignin are similar to kraft lignins in terms of solubility and _Tg . This method does not use sulfur and there is no covalently bound sulfur. Ash content is very low. Soda lignin has low solubility in neutral and acidic environments, but is completely dissolved at pH 12 and above.

The lignosulfonate method introduces a large number of sulfonate groups, making lignin soluble in water, but also in acidic aqueous solutions. Lignosulfonates have up to 8% sulfur in the form of sulfonate, while kraft lignin has 1-2% sulfur, mainly associated with lignin. The molecular weight of lignosulfonate is 15000-50000 g/mol. This lignin contains more carbohydrate residues compared to other types and has a higher molecular weight. The typical hydrophobic core of lignin, together with the large number of ionized sulfonate groups, makes this lignin attractive as a surfactant and often finds use in cement dispersing, etc.

Another group of lignins that is becoming available are lignins formed in biorefining processes in which carbohydrates are separated from the lignin by chemical or biochemical processes to form a carbohydrate-rich fraction. This residual lignin is called biorefined lignin. Biorefining focuses on energy production and the production of substitutes for products derived from fossil fuels and petrochemicals, as well as lignin. Lignin from this process is typically considered a low-value product, or even a waste product used primarily for thermal combustion, or used as low-grade feed, or otherwise disposed of.

The availability of organosolv lignin is still considered to be at semi-plant scale. The method involves extracting lignin using water along with various organic solvents (most often ethanol) and some organic acids. The advantage of this method is the high purity of the resulting lignin, but at a much higher cost compared to technical lignins and solubility in organic solvents, but not in water.

Previous attempts to use lignin as the main compound for mineral fiber binder compositions have been unsuccessful because it has proven difficult to find suitable crosslinking agents that provide the desired mechanical properties of the cured mineral wool product while at the same time avoiding harmful and/or corrosive components . Lignin is currently used to replace petroleum-derived chemicals such as phenol in phenolic resins, binder applications or bitumen. It is also used as an additive to cement and concrete and in some aspects as a dispersant.

Cross-linking of a polymer should generally provide improved properties such as mechanical properties, chemical and thermal resistance, etc. Lignin is particularly rich in phenolic and aliphatic hydroxyl groups, which can react leading to a cross-linked lignin structure. Different lignins will also have other available functional groups that could potentially be used. The presence of these other groups is highly dependent on the way in which the lignin was separated from cellulose and hemocellulose (thiols in kraft lignin, sulfonates in lignosulfonate, etc.) depending on the source.

It has been found that by using oxidized lignins, mineral fiber binder compositions can be prepared which provide superior properties to the mineral fiber product.

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

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

In one embodiment, component (i) is in the form of one or more ammonium oxidized lignins. For the purpose of the present invention, the term ammonium oxidized lignins should be understood as lignin that has been oxidized using an oxidizing agent in the presence of ammonia. The term ammonium oxidized lignin is abbreviated as AOL.

In an alternative embodiment, 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 produce oxidized lignins is hydrogen peroxide.

In one embodiment, the ammonium oxidized lignin includes one or more compounds selected from the group of ammonia, amines, hydroxides, or any salts thereof.

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In one embodiment, component (i) has a carboxylic acid group content of

0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as from 0.45 to 1.0 mmol/g, based on the dry weight of component (i).

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

It appears that the content of carboxylic acid groups in the oxidized lignins plays an important role in the unexpected benefits of the aqueous mineral fiber binder compositions of the present invention. In particular, carboxylic acid groups in oxidized lignins appear to improve cross-linking characteristics and therefore provide better mechanical properties to cured mineral fiber products.

Component (ii).

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

In one embodiment, component (ii) includes, in one embodiment, one or more crosslinkers selected from β-hydroxyalkylamide crosslinkers and/or oxazoline crosslinkers.

β-Hydroxyalkylamide crosslinkers are hardeners for acid-functional macromolecules. It creates a hard, durable, corrosion-resistant and solvent-resistant cross-linked polymer network structure. It appears that β-hydroxyalkylamide crosslinkers are cured by an esterification reaction to form multiple ester linkages. The hydroxyl functional group of β-hydroxyalkylamide cross-linkers should be on average at least 2, preferably more than 2, and more preferably 2-4, in order to obtain an optimal curing result.

Oxazoline group-containing cross-linkers are polymers containing one or more oxazoline groups in each molecule, and, in general, oxazoline-containing cross-linkers can be easily prepared by polymerizing oxazoline derivatives. US Patent 6,818,699 B2 presents an invention for such a method.

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

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

In one embodiment, component (ii) is a molecule having 3 or more epoxy groups.

In one embodiment, component (ii) is one or more flexible oligomers or polymers, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as a low Tg polyester, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

In one embodiment, component (ii) is selected from the group consisting of curing reaction crosslinkers such as hydroxyalkyl amide, alkanolamine, alkanolamine reaction product and polycarboxylic acid. The reaction product of an alkanolamine and a polycarboxylic acid can be found in US Pat. No. 6,706,853 B1.

Without intending to go into any particular theory, it is believed by the present inventors that the very favorable properties of the aqueous binder compositions are due to the interaction of the oxidized lignins used as component (i) and the above-mentioned cross-linking agents. It appears that the presence of carboxylic acid groups in oxidized lignins allows for very efficient cross-linking of oxidized lignins.

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

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

In one embodiment, component (ii) is one or more fatty amides/fatty acid amides.

In one embodiment, component (ii) is one or more cross-linking agents selected from the group consisting of dimethoxyethanal, glycolaldehyde, glyoxalic acid.

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

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

In one embodiment, component (ii) is one or more cross-linking agents in the form of aliphatic polyfunctional carbodiimides.

In one embodiment, component (ii) is one or more crosslinkers selected from melamine crosslinkers, such as hexakis(methylmethoxy)melamine (HMMM) crosslinkers.

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

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

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

Component (iii).

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

In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of polyols such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene 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-based 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, 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 lignin-like structure such as vanillin, acetosyringone, solvents , used as coagulants, such as alcohol ethers, polyvinyl alcohol.

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

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

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

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

Another specific unexpected aspect of the present invention is that the use of plasticizers having a boiling point greater than 100°C, in particular from 140 to 250°C, significantly improves the mechanical properties of the mineral wool products according to the present invention, although, due to their boiling point It is possible that these plasticizers will, at least partially, evaporate during the curing of the aqueous binder materials in contact with the mineral fibers.

In one embodiment, component (iii) includes one or more plasticizers having a boiling point greater than 100°C, such as 110 to 280°C, more preferably 120 to 260°C, more preferably 140 to 250°C.

It appears that the effectiveness of these plasticizers in aqueous binder compositions is due to the effect of increasing the mobility of oxidized lignins during the curing process. It appears that increased mobility of lignins or oxidized lignins during the curing process facilitates efficient cross-linking.

In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of from 150 to 50,000 g/mol, in particular from 150 to 4000 g/mol, more

- 9 045582 specifically from 150 to 1000 g/mol, preferably from 150 to 500 g/mol, more preferably from

200 to 400 g/mol.

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

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

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

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

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

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

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

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

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

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

In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of monomer amides such as acetamides, benzamide, fatty acid amides such as tall oil amides.

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

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

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

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

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

Surprisingly, it has been found that the inclusion of plasticizers in aqueous binder compositions very significantly improves the mechanical properties of the water drainage device according to the invention.

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

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

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

An aqueous binder composition for mineral fibers, comprising components (i) and (iia).

In one embodiment, the present invention is directed to an aqueous mineral fiber binder composition comprising component (i) in the form of one or more oxidized lignins; and component (iia) in the form of one or more modifiers.

The present inventors have found that excellent binding properties can also be achieved by a two-component system which includes component (i) in the form of one or more

- 10 045582 oxidized lignins and component (iia) in the form of one or more modifiers, and optionally any of the other components mentioned above and below.

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

In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from molecules having 3 or more epoxy groups.

In one embodiment, component (iia) is a modifier in the form of one or more flexible oligomers or polymers, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as a low Tg polyester, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

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

In one embodiment, component (iia) is one or more modifiers selected from aliphatic polyfunctional carbodiimides.

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

Without intending to go into any particular theory, it is believed by the present inventors that the excellent binding properties achieved by a mineral fiber binder composition comprising components (i) and (iia), and optionally additional components, are at least in part due to the effect that the modifiers, used as components (iia), at least in part, serve as a plasticizer and cross-linking agent.

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

Additional components.

In some embodiments, the aqueous binder composition includes additional components.

In one embodiment, the aqueous binder composition includes a catalyst selected from inorganic acids such as sulfuric acid, sulfamic acid, nitric acid, boric acid, phosphoric acid, and/or phosphoric acid, and/or any salts thereof, such as sodium hypophosphite, and/or ammonium salts, such as ammonium salts of sulfuric acid, sulfamic acid, nitric acid, boric acid, phosphoric acid and/or phosphoric acid. The presence of such a catalyst can improve the curing characteristics of aqueous binder compositions.

In one embodiment, the aqueous binder composition includes a catalyst selected from 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 , Sn[N(SO ₂ -HC ₈ F ₁₇ ) ₂ ] ₄ .

In one embodiment, the aqueous binder composition includes a catalyst selected from metal chlorides such as KCl, MgCl ₂ , ZnCl ₂ , FeCl ₃ and SnCl ₂ .

In one embodiment, the aqueous binder composition includes a catalyst selected from organometallic compounds such as titanate catalysts and tin catalysts.

In one embodiment, the aqueous binder composition includes a catalyst selected from chelating agents such as transition metals such as iron ions, chromium ions, magnesium ions, copper ions.

In one embodiment, the aqueous vehicle composition includes an additional component (iv) in the form of one or more silanes.

In one embodiment, the aqueous binder composition includes an additional component (iv) in the form of one or more binders, such as organofunctional silanes.

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

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

The present inventors have found that the addition of ammonia, amines or any salts thereof as an additional component may be particularly beneficial when oxidized lignins are used in component (i) where the oxidized lignin has not been oxidized in the presence of ammonia.

- 11 045582

In one embodiment, the aqueous binder composition further includes an additional component in the form of urea, in particular in an amount of from 5 to 40 wt.%, such as from 10 to 30 wt.%, from 15 to 25 wt.%, based on dry matter. weight of component (i).

In one embodiment, the aqueous binder composition further includes an additional component in the form of one or more carbohydrates selected from the group consisting of sucrose, reducing sugars, in particular dextrose, polysaccharides, and mixtures thereof, preferably dextrins and maltodextrins, more preferably starch syrup and more preferably starch syrup with a dextrose equivalent number DE=ot 30 to less than 100, such as DE=ot 60 to less than 100, such as DE=60-99, such as DE=85-99, such as DE=95-99.

In one embodiment, the aqueous binder composition further includes an additional component in the form of one or more carbohydrates selected from the group consisting of sucrose and reducing sugars, in an amount of from 5 to 50 wt.%, such as from 5 to less than 50 wt.%, such as 10 to 40 wt.%, such as 15 to 30 wt.%, based on the dry weight of component (i).

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

In one embodiment, the aqueous adhesive further includes an additional component in the form of one or more surfactants, which are in the form of nonionic and/or ionic emulsifiers, such as polyoxyethylene lauryl ether (4), such as soy lecithin, such as sodium dodecyl sulfate .

In one embodiment, the aqueous binder composition includes component (i) in the form of one or more ammonium oxidized lignins having a carboxylic acid group content of from 0.05 to 10 mmol/g, such as from 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (i);

component (ii) in the form of one or more crosslinkers selected from β-hydroxyalkylamide crosslinkers and/or oxazoline crosslinkers, and/or one or more crosslinkers selected from the group consisting of polyfunctional organic amines such as alkanolamine, diamines , such as hexamethyldiamine, triamines;

component (iii) in the form of one or more polyethylene glycols having an average molecular weight of from 150 to 50,000 g/mol, in particular from 150 to 4000 g/mol, more particularly from 150 to 1000 g/mol, preferably from 150 to 500 g/ mol, more preferably from 150 to 300 g/mol, or one or more polyethylene glycols having an average molecular weight of from 4000 to 25000 g/mol, in particular from 4000 to 15000 g/mol, more particularly from 8000 to 12000 g/mol; wherein the aqueous binder composition preferably includes component (ii) in an amount of from 1 to 40 wt.%, such as from 4 to 20 wt.%, from 6 to 12 wt.%, based on the dry weight of component (i), and ( iii) is present in an amount of 0.5 to 50% by weight, preferably 2.5 to 25% by weight, more preferably 3 to 15% by weight, based on the dry weight of component (i).

In one embodiment, the aqueous binder composition includes component (i) in the form of one or more ammonium oxidized lignins having a carboxylic acid group content of from 0.05 to 10 mmol/g, such as from 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (i);

component (iia) in the form of one or more modifiers selected from epoxidized fatty acid triglyceride oils.

In one embodiment, the aqueous binder composition includes component (i) in the form of one or more ammonium oxidized lignins having an average content of carboxylic acid groups of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups;

component (ii) in the form of one or more crosslinkers selected from β-hydroxyalkylamide crosslinkers and/or oxazoline crosslinkers, and/or is one or more crosslinkers selected from the group consisting of polyfunctional organic amines such as alkanolamine , diamines such as hexamethyldiamine, triamines;

component (iii) in the form of one or more polyethylene glycols having an average molecular weight of from 150 to 50,000 g/mol, in particular from 150 to 4000 g/mol, more particularly from 150 to 1000 g/mol, preferably from 150 to 500 g/ mol, more preferably from 150 to 300 g/mol, or one or more polyethylene glycols having an average molecular weight of from 4000 to 25000 g/mol, in particular from 4000 to 15000 g/mol, more particularly from 8000 to 12000 g/mol; wherein the aqueous binder composition preferably includes component (ii) in an amount of from 1 to 40 wt.%, such as from 4 to 20 wt.%,

- 12 045582 from 6 to 12% by weight, based on the dry weight of component (i), and (iii) is present in an amount of from 0.5 to 50% by weight, preferably from 2.5 to 25% by weight, more preferably from 3 to 15% by weight, based on the dry weight of component (i).

In one embodiment, the aqueous binder composition includes component (i) in the form of one or more ammonium oxidized lignins having an average content of carboxylic acid groups of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups;

component (iia) in the form of one or more modifiers selected from epoxidized fatty acid triglyceride oils.

In one embodiment, the aqueous binder composition consists essentially of 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 binders such as organofunctional silanes;

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

optionally a urea component;

optionally a component in the form of more reactive or non-reactive silicones;

optionally hydrocarbon oil;

optionally one or more surfactants;

water.

In one embodiment, the aqueous binder composition consists essentially of component (i) in the form of one or more oxidized lignins;

component (iia) in the form of one or more modifiers selected from epoxidized fatty acid triglyceride oils;

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

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

optionally a urea component;

optionally a component in the form of more reactive or non-reactive silicones;

optionally hydrocarbon oil;

optionally one or more surfactants;

water.

The water drainage device preferably includes from 1.0 to 6.0 wt.% of the cured adhesive composition, preferably from 2.5 to 4.5 wt.%, most preferably from 3.0 to 3.8 wt.%, based on weight water drainage device. Determination of binder content is carried out according to standard DS/EN13820:2003. The content of the binder material is taken as waste loss. Binder content includes any binder additives.

The above-described oxidized lignins in an aqueous binder composition can be prepared as follows.

Method I for obtaining oxidized lignins.

Oxidized lignins, which can be used as a component for the binder materials used in the present invention, can be obtained by a method comprising contacting component (a) comprising one or more lignins;

component (b) comprising ammonia, one or more amine components, and/or any salt thereof;

component (c) comprising one or more oxidizing agents.

Component(s).

Component (a) includes one or more lignins.

In one embodiment, component (a) includes one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from biorefining processes of lignocellulosic feedstocks, or any mixtures thereof.

In one embodiment, component (a) includes one or more kraft lignins.

Component (b).

In one embodiment, component (b) includes ammonia, one or more amine components and/or any salts thereof. Without intending to go into any specific theory, the authors of this

- 13 045582 of the invention, it appears that replacing the alkali metal hydroxides used in previously known lignin oxidation processes with ammonia, one or more amine components, and/or any salts thereof plays an important role in improving the properties of the oxidized lignins obtained by the process of the present invention.

The inventors of the present invention have surprisingly found that lignins oxidized by an oxidizing agent in the presence of ammonia or amines contain significant amounts of nitrogen as part of the structure of the oxidized lignins. Without intending to be bound by any particular theory, it is believed by the present inventors that the improved stability characteristics of oxidized lignins when used in products where they are included in a binder composition with said oxidized lignins produced by the process described herein are at least in part due to nitrogen content in the structure of oxidized lignins.

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

Without intending to go into any particular theory, it is believed by the present inventors that the improved stability characteristics of the derivatized lignins produced according to the present invention are at least partially due to the fact that ammonia is a volatile compound and therefore evaporates from the final product, or can be easily removed and reused. In contrast, it has proven difficult to remove residual amounts of alkali metal hydroxides used in the previously known oxidation process.

However, it may be advantageous in the process that component (b), in addition to ammonia, one or more amine components and/or any salts thereof, also includes a relatively small amount of an alkali and/or alkaline earth metal hydroxide, such as sodium hydroxide and/or or potassium hydroxide.

In embodiments in which component (b) includes alkali and/or alkaline earth metal hydroxides, such as sodium hydroxide and/or potassium hydroxide, as a component in addition to ammonia, one or more amine components, and/or any salts thereof, the amount of alkali and/or alkaline earth metal hydroxides is usually small, such as 5 to 70 parts by weight, such as 10 to 20 parts by weight of alkali and/or alkaline earth metal hydroxide, based on ammonia.

Component (c).

In the method described herein, component (c) includes one or more oxidizing agents.

In one embodiment, component (c) includes 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, reactive radicals from the oxidant will usually capture a proton from the phenolic group, since this bond has the lowest dissociation energy in lignin. Due to the ability of lignin to stabilize radicals through mesomerism, multiple pathways for the continuation (but also termination) of the reaction are opened up, and various intermediates and end products are formed. The average molecular weight can either increase or decrease due to this complexity (and the conditions chosen), and in their experiments the present inventors have typically seen a modest increase in average molecular weight of about 30%.

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

Hydrogen peroxide may be the most widely used oxidizing agent due to its combination of low cost, good efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of catalysts, alkaline conditions and temperature are important due to the following reactions leading to the formation of radicals:

Η ₂ Ο ₂ +ΟΗ ϊ+ΗΟΟ + H ₂ O

H ₂ O ₂ + UN-on + H ₂ O + o ₂

The present inventors have found that derivatized lignins produced by the process described herein contain increased amounts of carboxylic acid groups as a result of the oxidation process. Without intending to go into any particular theory, it is believed by the present inventors that the content of carboxylic acid groups in the oxidized lignins produced by the process plays an important role in achieving the desired reactivity characteristics of the derivatized lignins produced by the process described herein.

Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. High hydrophilicity can enhance water solubility and facilitate adhesion on polar substrates such as mineral fibers.

Additional components.

In one embodiment, the process for producing oxidized lignins preferably includes additional components, in particular component (d) in the form of an oxidation catalyst, such as a catalyst of one or more transition metals, such as ferrous sulfate, such as manganese containing catalysts , palladium, selenium, tungsten.

Such oxidation catalysts can increase the reaction rate, thereby improving the properties of the oxidized lignins.

Mass ratios of components.

One skilled in the art will employ components (a), (b) and (c) in relative amounts that achieve the desired degree of lignin oxidation.

In one embodiment, component (a) includes one or more lignins;

component (b) includes ammonia; and component (c) includes one or more oxidizing agents in the form of hydrogen peroxide, wherein the weight ratios of lignin, ammonia and hydrogen peroxide are such that the amount of ammonia is from 0.01 to 0.5 parts by weight, such as from 0.1 to 0 .3 parts by weight, such as 0.15 to 0.25 parts by weight of ammonia, based on the dry weight of lignin, and wherein the amount of hydrogen peroxide is from 0.025 to 1.0 parts by weight, such as 0.05 to 0. 2 parts by weight, such as 0.075 to 0.125 parts by weight hydrogen peroxide, based on the dry weight of lignin.

Way.

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

In one embodiment, the method includes the following steps:

the step of obtaining 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 from 1 to 50 wt.%, such as from 5 to 25 wt.%, such from 15 to 22 wt.%, such as from 18 to 20 wt.%, based on the total weight of the aqueous solution;

a step of adjusting the pH value by adding component (b) comprising an aqueous solution of ammonia, one or more amine components, and/or any salt thereof;

an oxidation step by adding component (c) comprising an oxidizing agent.

In one embodiment, the pH adjustment step is carried out such that the resulting aqueous solution and/or dispersion has a pH value >9, such as >10, such as >10.5.

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

In one embodiment, the pH adjustment step is carried out such that the temperature is raised to >25°C and then adjusted to a range of 25-50°C, such as 30-45°C, such as 35-40°C.

In one embodiment, during the oxidation step, the temperature is raised to >35°C and then controlled in the range of 35-150°C, such as 40-90°C, such as 45-80°C.

In one embodiment, the oxidation step is carried out for a time of 1 second to 48 hours, such as 10 seconds to 36 hours, such as 1 minute to 24 hours, such as 2 to 5 hours.

Method II for obtaining oxidized lignins.

Oxidized lignins, which are used as a component for the binder materials used in the present invention, can be obtained by a method comprising contacting component (a) comprising one or more lignins;

component (b) comprising ammonia, and/or one or more amine components, and/or any salt thereof, and/or an alkali and/or alkaline earth metal hydroxide, such as sodium hydroxide and/or potassium hydroxide;

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

Component(s).

Component (a) includes one or more lignins.

In one embodiment of the method for producing oxidized lignins, component (a) includes one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from biorefining processes of lignocellulosic raw materials, or any a mixture of them.

In one embodiment, component (a) includes one or more kraft lignins.

Component (b).

In one embodiment of the production of oxidized lignins, component (b) includes ammonia, one or more amine components, and/or any salts thereof, and/or an alkali and/or alkaline earth metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.

Ammonium oxidized lignin should be understood as lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term ammonium oxidized lignin is abbreviated as AOL.

- 15 045582

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

Without intending to go into any particular theory, it is believed by the present inventors that the improved stability characteristics of the derivatized lignins prepared according to the present invention with component (b), which is ammonia and/or any salt thereof, are at least partially due to the fact that Ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused.

However, in this embodiment of the process for producing oxidized lignins, it may be advantageous that component (b), in addition to ammonia, one or more amine components, and/or any salts thereof, also includes a relatively small amount of alkali and/or alkaline earth metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.

In embodiments in which component (b) includes alkali and/or alkaline earth metal hydroxides, such as sodium hydroxide and/or potassium hydroxide, as a component in addition to ammonia, one or more amine components, and/or any salts thereof, the amount of alkali and/or alkaline earth metal hydroxides is usually small, such as 5 to 70 parts by weight, such as 10 to 20 parts by weight of alkali and/or alkaline earth metal hydroxide, based on ammonia.

Component (c).

In the method for producing oxidized lignins, component (c) includes one or more oxidizing agents.

In one embodiment, component (c) includes 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, reactive radicals from the oxidant will usually capture a proton from the phenolic group, since this bond has the lowest dissociation energy in lignin. Due to the ability of lignin to stabilize radicals through mesomerism, multiple pathways are opened for the continuation (but also termination) of the reaction and the formation of various intermediates and end products. The average molecular weight can either increase or decrease due to this complexity (and the conditions chosen), and in their experiments the present inventors have typically seen a modest increase in average molecular weight of about 30%.

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

Hydrogen peroxide may be the most widely used oxidizing agent due to its combination of low cost, good efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of catalysts, alkaline conditions and temperature are important due to the following reactions leading to the formation of radicals:

The present inventors have found that derivatized lignins produced by the process described herein contain increased amounts of carboxylic acid groups as a result of the oxidation process. Without intending to go into any particular theory, it is believed by the inventors that the content of carboxylic acid groups in the oxidized lignins produced by the process of the present invention plays an important role in achieving the desired reactivity characteristics of the derivatized lignins produced by the process described herein.

Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. High hydrophilicity can enhance water solubility and facilitate adhesion on polar substrates such as mineral fibers.

Component (d).

Component (d) includes one or more plasticizers.

In one embodiment, component (d) includes one or more plasticizers in the form of polyols such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerin, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers, polyethers, phthalates and/or acids such 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-based 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 introduction of component (d) in the form of one or more plasticizers provides a reduction in the viscosity of the reaction mixture, which allows for a very effective process for the production of oxidized lignins.

In one embodiment according to the present invention, component (d) includes one

- 16 045582 or more plasticizers in the form of polyols such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerin, monoethylene glycol, polyethylene glycols, polyvinyl alcohol, acrylic-based 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 according to the present invention, component (d) includes one or more plasticizers selected from the group of polyethylene glycols, polyvinyl alcohol, urea, or any mixtures thereof.

Additional components.

In one embodiment, the method for producing oxidized lignins preferably includes additional components, in particular component (v) in the form of an oxidation catalyst, such as a catalyst of one or more transition metals, such as ferrous sulfate, such as catalysts containing manganese, palladium, selenium, tungsten.

Such oxidation catalysts can increase the reaction rate, thereby improving the properties of the oxidized lignins obtained by this method.

Mass ratios of components.

One skilled in the art will employ components (a), (b), (c) and (d) in such relative amounts that the desired degree of oxidation of the lignins is achieved.

In one embodiment, the method is carried out such that the method includes component (a) includes one or more lignins;

component (b) includes ammonia;

component (c) includes one or more oxidizing agents in the form of hydrogen peroxide;

component (d) includes one or more plasticizers selected from the group of polyethylene glycol, wherein the weight ratios of lignin, ammonia, hydrogen peroxide and polyethylene glycol are such that the amount of ammonia is from 0.01 to 0.5 parts by weight, such as from 0.1 up to 0.3 parts by weight, such as 0.15 to 0.25 parts by weight of ammonia (25% by weight solution in water), based on the dry weight of lignin, and wherein an amount of hydrogen peroxide (30% by weight solution in water) is 0.025 to 1.0 parts by weight, such as 0.07 to 0.50 parts by weight, such as 0.15 to 0.30 parts by weight, based on the dry weight of lignin, and wherein the amount of polyethylene glycol is 0.03 to 0.60 parts by weight, such as 0.07 to 0.50 parts by weight, such as 0.10 to 0.40 parts by weight of polyethylene glycol, based on the dry weight of lignin.

For the purpose of the present invention, the term dry weight of lignin preferably refers to the weight of lignin in delivery form.

Way.

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, the method includes the following steps:

the step of obtaining 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 from 5 to 90 wt.%, such as from 10 to 85 wt.%, such from 15 to 70 wt.%, based on the total weight of the aqueous solution;

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

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

In one embodiment, the pH adjustment step is carried out such that the resulting aqueous solution and/or dispersion has a pH value >9, such as >10, such as >10.5.

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

In one embodiment, the pH adjustment step is carried out such that the temperature is raised to >25°C and then adjusted to a range of 25-50°C, such as 30-45°C, such as 35-40°C.

In one embodiment, during the oxidation step, the temperature is raised to >35°C, and then controlled in the range of 35-150°C, such as 40-90°C, such as 45-80°C.

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

The present inventors have found that the process as described herein produces a high dry matter content in the reaction mixture and therefore high yields are possible in the process of the present invention, thereby providing a reaction product in the form of oxidized lignins useful as a component in industrial products. mass production, such as mineral fiber products.

In one embodiment, the method is carried out such that the dry material content of the reaction mixture is from 20 to 80 wt.%, such as from 40 to 70 wt.%.

- 17 045582

In one embodiment, the method is carried out such that the viscosity of the oxidized lignin has a value from 100 to 100,000 cP, such as a value from 500 to 50,000 cP, such as a value from 1000 to 25,000 cP.

For the purpose of the present invention, viscosity is dynamic viscosity and is defined as the resistance of a liquid/paste to change in shape or movement of adjacent parts relative to each other. Viscosity is measured in centipoise (cP), which is equivalent to 1 mPas (millipascals per second). Viscosity is measured at 20°C using a viscometer. For the purpose of the present invention, dynamic viscosity can be measured at 20°C using a Brookfield cone-plate viscometer.

In one embodiment, the method is carried out such that the method includes a rotor-stator device.

In one embodiment, the method is carried out such that the method is carried out as a continuous or semi-continuous process.

Device for executing the method.

The present invention is also directed to an apparatus for performing the method described herein.

In one embodiment, the device for executing the method includes a rotor-stator device;

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

one or more inlet channels for water, components (a), (b), (c) and (d); and one or more outlet channels for oxidized lignin.

In one embodiment, the device is designed such that inlets for premixing components (a), (b) and (d) are located on the rotor-stator device, and the device further includes a chamber, said chamber having an inlet for component (c) and wherein said chamber has an outlet for oxidized lignin.

A rotor-stator device is a material handling device including a stator configured as an internal cone provided with ring gears. The stator interacts with a rotor that has spokes protruding from the hub. Each of these spokes contains a tooth in mesh with a tooth on the stator ring gears. With each rotation of the rotor, the material being processed is transferred further outward in one stage, while being subjected to intense shearing, mixing and redistribution. The rotor spoke and the underlying container chamber of the vertical device provide the possibility of constant regrouping of the material from the inside out and creates a multi-faceted processing of dry and/or highly viscous material so that the device is highly effective for intensive mixing, plasticizing, fibrillation, crushing, and similar processes important in industrial production. The vertical placement of the housing facilitates the movement of material from the periphery towards the center of the device.

In one embodiment, the rotor-stator device used in the method according to the present invention includes a stator with ring gears, and a rotor with a tooth in mesh with a stator tooth. In this embodiment, the rotor-stator device has the following features: a guide funnel protrudes between the rotor spokes, which concentrates the flow of material entering from above into the central part of the container. The outer surface of the guide funnel defines an annular gap that throttles the flow of material. The rotor is equipped with a feed auger, which delivers the material towards the working part of the device. The guide funnel holds the product in the active zone of the device, and the feed auger creates increased pressure of the material in the center.

For a more detailed description of the rotor-stator device used in one embodiment of the method, reference is made to patent document US 2003/0042344 A1, which is incorporated by reference.

In one embodiment, the method is performed such that a single rotor-stator device is used in the method. In this embodiment, the mixing of the components and the reaction of the components are carried out in the same rotor-stator device.

In one embodiment, the method is carried out such that two or more rotor-stator devices are used in the method, wherein at least one rotor-stator device is used to mix the components and at least one rotor-stator device is used to react the components.

This method can be divided into two stages:

1) obtaining lignin mass (a)+(b)+(d); And

2) oxidation of the lignin mass.

Typically, two different types of rotor/stator machines are used.

1. An open rotor/stator machine suitable for mixing lignin powder with water to a very high concentration (30 to 50 wt.%). Less intensive mixing, but special auxiliary elements (inlet funnel, auger, etc.) are used for processing highly viscous materials. Lower peripheral speed (up to 15 m/s). The machine can be used as

- 18 045582 system of periodic or continuous action.

2. Rotor/stator machine in the process line, which creates much higher shear loads - peripheral speeds up to 55 m/s - and provides favorable conditions for a very fast chemical reaction. The machine must be used continuously.

In an open rotor/stator system, a high concentration of lignin/water mass (45 to 50 wt%) is obtained. Powdered lignin is slowly introduced into warm water (30 to 60° C.) to which appropriate amounts of aqueous ammonia and/or alkaline base have been added. This can be done in batch mode, or the materials are fed alternately/continuously, creating a continuous flow of mass into the next stage.

The created mass must be maintained at a temperature of approximately 60° to keep the viscosity as low as possible, and thus the ability to pump the material. The hot lignin/water slurry, pH 9 to 12, is then transferred using a suitable pump, such as a cavitation screw pump or other positive displacement pump, to the oxidation step.

In one embodiment, the oxidation is carried out in a closed rotor/stator system under continuous reaction conditions in the process line. An aqueous solution of ammonia and/or alkaline base is dosed via a metering pump into the rotor/stator chamber at the location of greatest turbulence/shear. This ensures a fast oxidation reaction. The oxidized material (AOL) is removed from the process line reactor and collected in appropriate tanks.

Reactive product.

The inventors of the present invention have surprisingly found that the resulting oxidized lignins have highly desirable reactivity characteristics, while at the same time exhibiting improved flame retardant properties when used in products where they are included in the binder composition, and improved long-term stability superior to those of known oxidized lignins. .

In addition, oxidized lignin exhibits improved hydrophilicity.

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

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

Another option for describing the content of carboxylic acid groups is to use the average content of carboxylic acid groups per lignin macromolecule according to the following formula:

Average COOH functionality = (moles of total COOH)/(moles of total lignin)

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

Method III for obtaining oxidized lignins.

Oxidized lignins, which are used as a component for the binder material used in the present invention, can be obtained by a method comprising contacting component (a) comprising one or more lignins;

component (b) comprising ammonia, and/or one or more amine components, and/or any salt thereof, and/or an alkali and/or alkaline earth metal hydroxide, such as sodium hydroxide and/or potassium hydroxide;

component (c) comprising one or more oxidizing agents; and optionally component (d) in the form of one or more plasticizers, and performing a mixing/oxidation step, wherein an oxidized mixture is obtained followed by an oxidation step, wherein the oxidized mixture is allowed to continue reacting for a holding time of from 1 second to 10 hours, such as from 10s to 6h, such as 30s to 2h.

Components (a), (b), (c) and (d) are as defined above in section Method II for producing oxidized lignins.

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

During the pre-mixing stage, the following components can be brought into contact with each other:

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, it is possible that the premixing step is carried out as a separate step and after the premixing step, a mixing/oxidation step is carried out. IN

- 19 045582 In this embodiment of the invention it is particularly preferred to bring component (a) and component (b), and optionally component (d) into contact with each other in a pre-mixing step. Then, in a subsequent mixing/oxidation step, component (c) is added to the premix formed in the premixing step.

In one embodiment, it is possible that the premixing stage corresponds to the mixing/oxidation stage. In this embodiment of the invention, components such as component (a), component (b) and component (c) are mixed and the oxidation process is started at the same time. It is possible that subsequent holding times are carried out in the same apparatus as was used to perform the mixing/oxidation step. This embodiment of the invention is particularly advantageous if component (c) is air.

The inventors of the present invention have found that by carrying out a mixing/oxidation step followed by an oxidation step in which preferably the reaction mixture is not further stirred, the rate of oxidation can be controlled in a very efficient manner. At the same time, the cost of running the process is reduced since the oxidation step carried out after the mixing/oxidation step requires less complex equipment.

Another advantage is that the oxidized lignin that is obtained is particularly stable. Another unexpected advantage is that the resulting lignin is very controllable in terms of viscosity. Another unexpected advantage is that the concentration of oxidized lignin can be very high.

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

System I for execution of method III.

In one embodiment, a system for executing the method includes at least one rotor-stator device;

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

one or more outlet channels in the rotor-stator device;

at least one reaction device, in particular at least one reaction pipe, which is located downstream in the direction of the process flow to one or more outlet channels.

In one embodiment, the system includes one or more inlet ports for component (c) and/or component (d).

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

It is possible that in the pre-mixing step, component (c) is also mixed with the three mentioned ingredients (water, component (a) and component (b)). It is then possible that the premixing device has an additional inlet for component (c). If component (c) is air, it is possible that the premixing device is formed by an open mixing tank so that in this case component (c) is already brought into contact with other components (water, component (a) and component (b)) through a hole in the tank. Moreover, in this embodiment of the invention, it is possible that the premixing device optionally includes an inlet port for component (d).

In one embodiment, the system is configured such that the inlet ports for components (a), (b) and (d) are inlet ports of a premixing device, in particular an open rotor-stator device, whereby the system further includes an additional rotor-stator device, wherein said additional rotor-stator device has an inlet port for component (c) and said additional rotor-stator device has an outlet port for oxidized lignin.

It is possible that the premixing step and the mixing/oxidation step are carried out simultaneously. In this case, the premixing device and the mixing/oxidizing device are a single device, i.e. rotor-stator device.

In one embodiment, a single rotor-stator device used in the method of the present invention includes a stator with ring gears, and a rotor with a tooth in mesh with the stator tooth. In this embodiment, the rotor-stator device has the following features: a guide funnel protrudes between the rotor spokes, which concentrates the flow of material entering from above into the central part of the container. The outer surface of the guide funnel defines an annular gap that throttles the flow of material. The rotor is equipped with a feed auger, which delivers the material towards the working part of the device. The guide funnel holds the product in the active zone of the device, and the feed auger creates increased pressure of the material in the center.

System II for execution of method III

- 20 045582

In one embodiment, a system for executing the method includes one or more inlet channels for water and components (a) and (b);

at least one mixing and oxidation device with one or more outlet channels; and at least one mixer/heat exchanger that is positioned downstream of the process stream of at least one or more outlet passages, wherein the mixer/heat exchanger includes a temperature control device.

In one embodiment, the system includes an additional one or more inlet ports for component (c) and/or component (d).

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

It is possible that in the pre-mixing step, component (c) is also mixed with the three mentioned ingredients (water, component (a) and component (b)). It is then possible that the premixing device has an additional inlet for component (c). If component (c) is air, it is possible that the premixing device is formed by an open mixing tank so that in this case component (c) is already brought into contact with other components (water, component (a) and component (b)) through a hole in the tank. Moreover, in this embodiment of the invention, it is possible that the premixing device optionally includes an inlet port for component (d).

In one embodiment, the system is configured such that the inlet ports for components (a), (b) and (d) are inlet ports of an open rotor-stator device, whereby the system further includes a mixer/heat exchanger having an inlet port for component (c) and an outlet for oxidized lignin.

It is possible that the premixing step and the mixing/oxidation step are carried out simultaneously. In this case, the premixing device and the mixing/oxidizing device are a single device.

In one embodiment, a single rotor-stator device used in the method of the present invention includes a stator with ring gears, and a rotor with a tooth in mesh with the stator tooth. In this embodiment, the rotor-stator device has the following features: a guide funnel protrudes between the rotor spokes, which concentrates the flow of material entering from above into the central part of the container. The outer surface of the guide funnel defines an annular gap that throttles the flow of material. The rotor is equipped with a feed auger, which delivers the material towards the working part of the device. The guide funnel holds the product in the active zone 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. It is further possible that the premixing step is carried out in a mixing and oxidation apparatus.

In one embodiment, the mixing and oxidation device is a static mixer. A static mixer is a device for continuously mixing fluid materials without moving parts. One design of a static mixer is a plate type mixer, and another device of a commonly known type consists of mixing elements contained in a cylindrical (tubular) or square body.

In one embodiment, the mixer/heat exchanger is formed as a multi-tube heat exchanger with mixing elements. The mixing elements are preferably fixed structures through which the mixture must flow, thereby causing mixing to occur as a result of flowing through them. The mixer/heat exchanger can be configured as a reactor in slug flow mode.

In the method according to the invention, the water drainage device is placed in contact with the ground and, at least partially, buried within the ground. The water drainage device is preferably located completely buried in the ground, for example completely covered with earth. Earth includes sediment, sand, clay, soil, gravel, etc. For example, the drainage device may be buried to a depth of at least 20 cm of soil, preferably at least 40 cm of soil, most preferably at least 50 cm of soil.

In the method according to the invention, the water drainage device absorbs water and releases the water into a receptacle. The device may absorb water directly from the surrounding soil, or it may be transferred to the device through some means, such as a pipe. The device can hold water and then release it into a receptacle. The receiver may be the surrounding ground, i.e. Water from the device disperses back into the ground as soon as the ground becomes dry. The receptacle may also be a water collection point, reservoir, tank, drain, drainage pipe or sewer.

The water drainage device preferably includes a first pipeline. The first conduit preferably passes water into the water drainage device. This ensures that water can flow along the first pipeline and directly into the water drainage device. The first conduit preferably has a first open end and a second open end, the first open end being in fluid communication with the MMVF of the water drainage device. Of course, it is envisaged that the water drainage device may be adjacent to the first pipeline, preferably a pipe through which rainwater will flow, in order to reach this fluid communication. However, for the effectiveness of the first pipeline, it is preferable that it is at least partially integrated into the drainage device. The built-in portion of the first conduit may have an opening in its outer wall, preferably more than one opening. The presence of the hole provides the advantage of having a larger area through which water can flow into the drainage device.

The first conduit may be an open channel, and water may flow along this channel into a drainage device, such as from a main drainage system or roof gutters. The conduit is preferably a pipe. The advantage of the pipe is that it is hollow and therefore can freely transfer water underground to the drainage device. In addition, the pipe wall prevents rock debris from entering the pipe.

The first conduit, preferably a pipe, is preferably placed in fluid communication with the lower section of the water drainage device. This means that during installation the first pipeline is positioned in fluid communication with the lower half of the water drainage device by volume. This is done in order to fill the entire device quickly enough so that the air that is present in the device before the rain begins to be displaced. This happens fastest in the above configuration.

The piping, preferably a pipe, is in fluid communication with the drainage device, and may be in fluid communication with a piping system, preferably pipes, and one or more downpipes such that water that flows from the roof into the gutter and then into drainpipe, could be held inside the drainage device during wet weather. This is in addition to the water that the device can absorb from the surrounding soil (i.e. reducing surface water). When the surrounding soil dries out, water gradually dissipates from the drainage device into the soil. The drainage device thereby creates an efficient path for eliminating rainwater that does not require any pressurized injection from existing main drainage systems. There is no need to drain the water anywhere, although this is possible; water can be retained within the soil. For example, a structure may have one or more water drainage devices connected to its roof gutters, thereby being able to remove this surface water within its own property.

The water drainage device may have a channel that extends from the first end of the water drainage device towards the second end of the water drainage device, wherein the first and second ends are located oppositely and wherein the first end of the channel is preferably in fluid communication with water from a pipeline, preferably a pipe.

The channel may extend from 10 to 100% of the way through the drainage device, preferably from 20 to 99% of the way through the drainage device, preferably from 50 to 99% of the way through the drainage device, more preferably from 80 to 95% of the way through the substrate. The advantage of the channel is that there is an increased area through which water can flow into the drainage device. The channel can have any cross-section, preferably circular, triangular or square.

The channel can be formed by embedding a conduit, preferably a pipe, into a water drainage device as described above. The conduit preferably has an opening in its outer wall, preferably more than one opening. The presence of the hole provides the advantage of a larger area through which water can flow into the drainage device.

The channel may be formed as a separate pipe that has at least one opening. The pipe is preferably a perforated plastic pipe such as polyvinyl chloride (PVC) pipe. The pipe gives strength to the drainage device and prevents the channel from becoming blocked. The pipe is perforated to allow water to flow into the channel. The built-in pipe provides support to the channel, making it more resilient or pressure resistant. In the absence of a pipe, the channel could become blocked by pressure on the drainage device, such as from a vehicle passing over the drainage device.

The channel can be formed by removing a section of the drainage device, such as drilling. The resulting channel will be porous and thereby allow the water drainage device to absorb water from the channel.

The water drainage device may include a first portion in contact with a second portion, with a channel disposed between the first portion and the second portion. This means that the first part can be pre-

- 22 045582 is strictly formed with a groove along at least part of the length of the water drainage device, and when the first part and the second part are connected to each other, the channel becomes formed by the groove and the second part. Alternatively, both the first and second portions may have a groove, and the grooves may be aligned to form a channel when the first portion and the second portion are coupled together. The groove or grooves may have any shape that is required to form the channel. Therefore, the groove or grooves may have a cross-section that is semicircular, triangular, rectangular, or the like.

The first and second parts of the water drainage device can be connected by placing the two parts together or using an adhesive.

The channel can be formed by a combination of the approaches described above.

The cross-sectional areas of the first and second ends of the channel are preferably in the range from 2 to 200 cm ² , preferably from 5 to 100 cm ² .

The cross-sectional area of the first end of the channel is from 0.5 to 15% of the cross-sectional area of the first end of the water drainage device, preferably from 1 to 10%.

The cross-sectional area of the second end of the channel is from 0.5 to 15% of the cross-sectional area of the second end of the water drainage device, preferably from 1 to 10%.

The holes occupy such a small proportion of the cross-sectional area of the ends of the drainage device because the majority of the drainage device is used to store the amount of water that enters the drainage device. The larger the proportion of the water drainage device, the greater the volume of water that can be accumulated by the water drainage device for a given cross-sectional area.

The cross-sectional area of the channel is preferably substantially constant along its length. By substantially constant is meant that the cross-sectional area is within 10% of the average cross-sectional area, preferably within 5%, most preferably within 1%. However, if necessary, the cross-sectional area can be varied according to the requirements for the channel to be reduced or enlarged.

The channel can be straight through the water drainage device, i.e. the channel creates the most direct path towards the second end of the drainage device so that water can have the most direct path along the channel.

The channel may follow an indirect path through the drainage device to increase the surface area of the channel so that water can flow into the drainage device at a higher velocity.

There may be more than one channel through the drainage device to increase the surface area of the channel so that water can flow into the drainage device at a higher rate. Where there is more than one channel, the channels are preferably connected to form a network of channels so that water can flow through the network of channels. Each channel may be in fluid communication with another channel, thereby allowing water to flow from various sources for absorption by the drainage device.

Channels can be in the lower part, as well as in the upper part of the water drainage device. The advantage of having channels at the top and at the bottom is that when water enters through the bottom channel, any air that is present in the device before water begins to fill can be forced out through the top channel in the device.

The channel may have a triangular cross-section. During installation, the base of the triangle is preferably parallel to the base of the water drainage device. Alternatively, the channel may have a semicircular cross-section. Again, the base of the drainage device is preferably parallel to the base of the semicircle. Alternatively, the channel may have a circular or rectangular cross-section. The advantage of these cross sections is that the largest surface area of the channel is at the lowest point, creating the largest surface area for water to flow through it.

The channel is preferably placed at the center of the cross-sectional width of the drainage device. The rationale for this essentially central placement is that the flow of water to be absorbed will be under the center of the drainage device. This has the advantage that the strength of the drainage device is maintained at the sides of the drainage device. However, if the channel is placed closer to one side of the drainage device, this may cause weakening of the structure.

In applications where the channel extends from the first end to the second end of the drainage device, the second end of the channel is preferably closed to prevent soil from entering the channel and reducing the size of the channel. The second end of the channel may be closed by placing a plate over the hole, such as an MMVF plate, a metal plate, a plastic plate, or the like. Alternatively, the second end of the channel may be plugged with a plug, such as a plug made of MMVF, metal, plastic, or the like. The second end may be wrapped in geotextile material to seal the second end of the channel.

The advantage of using the water drainage device according to the invention is that

- 23 045582 it can absorb water from the soil and hold it inside its open-porous structure. The water drainage device may also pass water along an optional channel towards the second opening. This means that the drainage device can hold water when required and also conduct water to a receiver, such as a disposal device, when required.

In this application, a water drainage device will be positioned to drain water-saturated soil, particularly when precipitation such as rain, snow, sleet, hail, etc. results in the accumulation of surface water which causes the soil to become saturated. This can typically occur near buildings, particularly where part of the surrounding ground is covered by buildings, pavement, concrete pads or the like, without proper drainage. If there is no proper drainage, it puts pressure on the soil surrounding the area, distributing the surface water that has accumulated. This causes the surrounding area to become waterlogged and require drainage.

An additional advantage of using the device according to the present invention is that it retains water entering a water collection area such as a tank or reservoir. When a heavy rainstorm occurs, the reservoir or tank may become overfilled with a sudden influx of water. By using the device according to the present invention, the flow of abundant water into the reservoir or tank is delayed and thereby helps prevent flooding.

As discussed above, a water drainage device does not require any piping and can act as a drainage device by absorbing excess water from the surrounding soil during periods of high water input levels and releasing water back into the soil during periods of low water input levels. Thus, the water drainage device according to the present invention can be used for draining water-saturated soil. This can be achieved by absorbing excess water into the open-pore structure of the drainage device and retaining the water until the soil dries out, and then gradually dissipating the water into the soil.

The water drainage device may optionally have a first conduit and a second conduit. The first pipeline conveys water to the water drainage device and is preferably located in the lower half of the device. The second pipeline is preferably located in the upper half of the device. The main purpose of the second pipeline is to displace air from the device. However, it can also act as a drain pipe. This means that when the device becomes saturated with water, a second pipe drains the water to a holding tank, water mains, or drainage collection tank.

Alternatively, the first conduit and the second conduit may be connected by a channel, as discussed above. Water-saturated soil is drained, which is discharged along the channel of the water drainage device towards the second hole and into a disposal system, such as a tank, water supply network or drainage collection tank. If there is a low level of excess water in the soil, a drainage device can hold that excess water until the soil is dry enough to dissipate the water back into the soil. If high levels of excess water occur, it can be directed along the channel to a disposal system.

Water may be forced along the optional channel by gravity, for example by positioning the drainage device at an angle such that the second end of the drainage device is lower than the first end of the drainage device. The tilt angle is preferably from 2 to 10° from the horizontal. The advantage of placing a drainage system on a slope is that there is no need to pump water out of the drainage element.

Alternatively, a pump may be in fluid communication with the second channel opening, the pump directing water toward the second channel opening. The pump may be in fluid communication with a second conduit opening, such as a pipe. Water can be pumped along a channel to a water disposal system such as a tank, mains water supply, or drainage catch basin. The advantage of using a pump is that the drainage element can be placed without tilting and therefore installation does not require digging deeper at one end of the structure.

It is possible to place both a water drainage device with an inclination and a pumping system.

In use, the channel is preferably offset towards the first direction and the drainage device is oriented such that the first direction is a downward direction. It is favorable for the channel to be located at the bottom of the water drainage device.

The water holding capacity of the water drainage device is preferably at least 80% by volume, preferably 80-99%, most preferably 85-95%. The higher the water holding capacity, the more water can be held for a given volume. The water-holding capacity of the water drainage device is high due to its open-pore structure and hydrophilicity.

The amount of water that is retained by the water drainage device when it releases water is less than 20% by volume, preferably less than 10% by volume, most preferably less than 5% by volume. The retained water may be from 2 to 20% by volume, such as from 5 to 10% by volume. The smaller the amount of water retained by the water drainage device, the higher the capacity of the water drainage device

- 24 045582 take more water. Water may exit the drainage device by dispersing into the soil when the surrounding soil is dry and the capillary balance is such that the water dissipates into the soil.

Buffer capacity of the water drainage device, i.e. the difference between the maximum amount of water that can be retained and the amount of water that is retained when the water drainage device releases water is preferably at least 60 vol.%, preferably at least 70 vol.%, preferably at least 80 vol. %. The buffer capacity may be 60 to 90 vol.%, such as 60 to 85 vol.%. The advantage of such a high buffer storage capacity is that the drainage device can hold a large volume of water for a given volume, i.e. A drainage device can hold a large volume of water when it rains and release a large volume of water into the dry surrounding soil. The buffer capacity is so high because the water drainage device requires low suction pressure to remove water from it.

The water holding capacity, amount of water retained and buffer capacity of a drainage device can be measured in accordance with the EN 13041:1999 standard.

Water is retained in the drainage device when the surrounding soil is saturated, i.e. capillary balance means that water is retained within the drainage device. When the surrounding soil dries out, the capillary balance shifts and water dissipates from the drainage device into the surrounding soil. Thus, water is retained inside the drainage device when the surrounding soil is saturated. When the surrounding soil dries out, water dissipates from the drainage device into the soil. The water drainage device is then able to receive more water, for example through a pipe or pipeline.

The structure of the water drainage device is such that when water can disperse from the substrate into the ground, the water drainage device does not pollute the ground. This is ensured by the small pore size inside the water drainage device. Therefore, there is no need to wrap the drainage device in geotextile to prevent contamination. This has the advantage that during assembly the installer does not have to manually wrap the drainage device in geotextile material. The screwing step of other water drainage devices is inconvenient and time-consuming because it is performed during the installation phase. The water drainage device according to this invention does not pose this problem.

The water drainage device may include a load distribution layer.

The load distribution layer is preferably placed on the top surface of the water drainage device when it is used.

The load distribution layer may be a bonded MMVF layer, it preferably has a compressive strength of at least 200 kPa, and the compressive strength may be up to 1 MPa. It is preferably 200 to 500 kPa, more preferably 300 to 400 kPa. Compressive strength is measured according to European Standard EN 826:1996. Load-distributing layers with such compressive strength are particularly suitable for use in the present invention because they ensure that loads applied from the soil surface are not concentrated at one point in the drainage device, but are instead distributed over a large area.

When the load distribution layer is a bonded MMVF layer, it preferably has a density of at least 100 kg/m ³ , such as 100 to 280 kg/m ³ , preferably 150 to 200 kg/m ³ , and the density can be up to 600 kg/ ^m3 . Load-distributing layers of this density are particularly suitable for use in the present invention because they ensure that loads acting from the soil surface are not concentrated at one point in the drainage device, but are instead distributed over a large area.

When the load distribution layer is a bonded MMVF layer, it is preferably hydrophilic, i.e. attracts water. The MMVF layer is in the form of a bound mass. Those. The MMVF layer is typically a bonded matrix of MMVF fibers that have been produced as is, but it can also be formed by granulating a plate of MMVF and compacting the granular material.

The water drainage device may further include a top layer above the load distribution layer. The top layer is preferably grass, dirt, artificial grass, sand, gravel, clay, or combinations thereof.

In one embodiment, the water drainage device may further include a liquid impermeable cover. A liquid-impermeable coating surrounds the water drainage device. The liquid impervious coating may include one or more openings at the locations of any conduit. For example, the liquid impervious coating may include a first opening for the first conduit described herein. It may also include a second opening for the second conduit described herein. This allows water to flow into or out of the device through the piping. However, exit is prevented

- 25 045582 water from the device in places other than near the pipelines, thanks to the liquid-impermeable coating.

This coating has been found beneficial when the drainage device is located in areas where it is not desirable for water to seep into the surrounding soil. This may require compliance with government regulations.

For example, rainwater that has been collected through a drainage system from hard surfaces such as road surfaces or parking lots is considered contaminated water. This is caused by residues on hard surfaces such as gasoline, diesel and hard metals that can be carried away by water. It is not desirable for such water to permeate the surrounding soil, but the water drainage device of the present invention is capable of preventing flooding by retaining excess water and transporting it securely through conduits to a water disposal site.

In addition, it may also be undesirable for water to be dispersed into the surrounding soil from a drainage device when the surrounding soil itself is unsuitable for percolation. This may be due to the fact that the surrounding soil is contaminated and such dispersed water would cause the distribution of contaminant elements in the soil. It may also be because the soil is unable to absorb water, for example if it contains a large amount of clay. Again, the water drainage device of the present invention can prevent flooding by retaining excess water and transporting it securely through pipes to a water disposal site.

The liquid impermeable coating of the invention may include a material selected from the following list: thermoplastic polymer, thermosetting polymer, elastomer, natural polymer, synthetic polymer, foil such as agricultural foil, bentonite, clay, compressed MMVF, or any other famous plastic. The liquid impermeable coating of the invention may include poly(paraphenylene)ether (PPE), polyethylene (PE), polyvinyl chloride (PVC), or ethylene propylene diene monomer (EPDM).

The liquid impervious covering may also be called a wrap or cuff. The water drainage device may include one or more layers of liquid impervious coating.

The present invention is also directed to a water drainage device comprising man-made vitreous fibers (MMVF) bonded by an aqueous binder composition, wherein the aqueous binder composition, before curing, comprises 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.

The water drainage device is as described above. This embodiment may have any of the advantageous features described above for the method according to the invention.

The present invention also relates to a group of at least two water drainage devices, wherein the water drainage devices include man-made vitreous fibers (MMVF) bonded by an aqueous binder composition, wherein the aqueous binder composition, before curing, includes 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.

In the group according to the invention, at least two water drainage devices can be identical. Alternatively, the at least two drainage devices may not be identical.

The group may consist of at least two drainage devices placed adjacent to each other, or in contact with each other, so that water can disperse from one drainage device to the next. There may be more than two drainage devices, for example as many devices as are required to occupy the desired area.

One or more water drainage devices may have any of the preferred features described above.

One of the at least two water drainage devices preferably includes a first pipeline as described above.

The second water drainage device preferably includes a second pipeline as described above.

One of the water drainage devices preferably includes a first end and a second end, and a channel that extends from a first opening at the first end to a second opening at the second end. In the group according to the present invention, one or more of the water drainage devices may include a channel.

In one embodiment, the first channel opening in the first drainage device may be in contact with the first end of the channel in the second drainage device. For example, two or more drainage devices may be in fluid communication with each other by being connected by a channel. The first channel opening in the first drainage device may be in communication with

- 26 045582 fluid with the first channel opening in the second water drainage device. The second channel opening in the first water drainage device may be in fluid communication with a first pipeline receiving water, for example, from roof gutters. The second channel opening in the second water drainage device may be in fluid communication with the first channel opening in the third water drainage device or may be in fluid communication with a second conduit for transferring water to a catch basin. In this way, a network structure of water drainage devices can be formed, all in fluid communication. The channels of two or more drainage devices are preferably lined up to form a longer channel.

The group according to the invention is preferred because it increases the volume of water that can be retained and then dispersed.

The present invention also relates to the use of a water drainage device for draining water, the water drainage device comprising man-made vitreous fibers (MMVF) bonded by an aqueous binder composition, wherein the aqueous binder composition, before curing, comprises 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.

This embodiment of the invention may have any of the additional features described above for the method according to the invention.

The present invention also relates to a method for producing a water drainage device. The method includes the steps of (i) providing artificial vitreous fibers;

(ii) spraying the artificial vitreous fibers with an aqueous binder composition; and (iii) collecting and compacting the artificial vitreous fibers and curing the aqueous binder composition to form a water drainage device, the aqueous binder composition, before curing, comprising 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.

The water drainage device may have any of the preferred features discussed in detail above.

Artificial glassy fibers can be formed from a mineral melt. Mineral melt is obtained in a standard way, by obtaining mineral materials and melting them in a furnace. This furnace may be any type of furnace known for producing mineral melts for MMVF, for example a shaft furnace such as a cupola furnace, a bath furnace or a cyclone furnace.

Any suitable fiberization method can be used to form MMVF from a mineral melt. Fiberization may be a spinning process using a spinning bowl, in which the melt is centrifugally extruded through holes in the walls of the spinning bowl (the spinning bowl, also known as internal centrifugation). Alternatively, the fiberization may be centrifugal fiberization by forcing the melt onto the outside of a single grinding rotor to form fibers and spin thereon, or onto a cascade of multiple grinding rotors that rotate about a substantially horizontal axis (cascade spinning device).

Then the melt, thus formed into a fibrous mass, is entrained by air, and the fibers are collected into a belt on a conveyor and removed from the fiberizing device. The fiber tape is then compacted, which may include web formation, and/or longitudinal compression, and/or vertical compression, and/or winding around a mandrel to produce a cylindrical pipe insulation product. Compaction can also be accomplished in other ways.

The binder composition is preferably applied to the fibers when they are entrained in air in the form of a lump. Alternatively, it may be applied after collection on the conveyor, but this is less preferred.

After compaction, the compacted fiber ribbon is passed into a curing device to cure the binder material.

In one embodiment, curing is carried out at temperatures from 100 to 300°C, such as from 170 to 270°C, such from 180 to 250°C, such from 190 to 230°C.

In a preferred embodiment, curing occurs in a conventional mineral wool curing oven, preferably operating at a temperature of 150 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230 °C.

In one embodiment, curing occurs over a period of 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes.

- 27 045582

In a typical embodiment, curing occurs at a temperature of 150 to 250°C, for a time of 30 s to 20 min.

The curing process can begin immediately after applying the binder material to the fibers. Curing is defined as a process in which a binder composition is subjected to conditions of physical and/or chemical reaction, wherein the chemical reaction typically increases the molecular weight of the compounds in the binder composition and thereby increases the viscosity of the binder composition, typically until the binder composition reaches a solid state. condition. The cured binder composition binds the fibers to form a structurally bonded matrix of fibers.

In one embodiment, curing of the binder material in contact with mineral fibers occurs in a heat press.

Curing the binder material in contact with mineral fibers in a heat press has the particular advantage of producing high-density products.

In one embodiment, the curing process includes pressure drying. Pressure can be applied by forcing air or gas through or over the mixture of mineral fibers and binder material.

Detailed description of the figures

Fig. 5 shows an MMVF water drainage device 1 according to one aspect of the invention that has been buried in the ground 2 and adjacent to a building 3. The building 3 has roof gutters 4 that collect water from the roof 5 and directs it to the MMVF water drainage device 1 through a waste pipe 6 and pipeline 7. Pipeline 7 is in fluid communication with water drainage MMVF device 1. Pipeline 7 may be adjacent to water drainage MMVF device 1, but preferably it is partially embedded in water drainage MMVF device 1 to ensure that rock debris does not fall into the pipeline 7. In the part that is recessed into the water drainage MMVF device 1, the pipeline 7 can be provided with a hole 8 to enhance fluid communication between the pipeline 7 and the water drainage MMVF device 1.

Fig. 6 shows a water drainage device 100 with a channel 200 that extends from a first end of the water drainage MMVF device to a second end of the water drainage MMVF device. The channel is shifted towards the lower part of the MMVF water drainage device.

Examples

Example 1: Compressive strength.

Compressive strength (in the Y-direction) was determined on eight MMVF cubes with a density of 75 kg/m ³ and dimensions 10x10x10 cm. Table. 1 shows the results for cubes with 2.1 wt.% binder according to the invention and without any wetting agent. Table 2 shows the results for cubes with 2.1 wt.% binder according to the invention and with sodium lauryl ether sulfate (SLES) as a wetting agent.

The binder material according to the invention had the following composition:

AOL (ammonium oxidized lignin): 1000 kg (284 kg UPM BioPiva 100 lignin, 57 kg H ₂ O ₂ (35%), 53 kg NH4OH (24.7%), 506 kg water);

plasticizer (PEG 200): 44 kg;

crosslinker (Primid XL552 - crosslinker β-hydroxyalkylamide (HAA), supplied by EMS-Chemie AG): 22 kg.

Primid XL552 has the following structure:

HE

- 28 045582

Table 1

Binder material according to the invention without wetting agent

Sample Elastic modulus (Emod) (MPa) dl flow (mm) Fmax (N) dl Fmax (mm) F final (N) Fmax (kPa) 1 1.39 0.463 363.59 3.37 360.67 36.4 2 1.95 0.397 489.16 3.55 479.38 48.9 3 1.12 0.475 401.84 9.93 399.44 40.2 4 1.80 0.410 448.55 9.88 445.16 44.9 5 1.42 0.461 454.64 9.86 451.63 45.5 6 1.24 0.487 324.91 9.89 322.08 32.5 7 1.42 0.447 410.38 8.32 406.56 41.0 8 1.68 0.426 430.11 9.86 427.66 43.0 Average value 1.49 0.45 415 8.08 412 42 Standard deviation 0.32 0.03 53 2.90 51 5

table 2

Binder material according to the invention with a wetting agent

Sample Emod (MPa) dl flow (mm) Fmax (I) dl Fmax (mm) F final (N) Fmax (kPa) 1 1.46 0.473 431.06 9.87 426.86 43.1 2 1.42 0.485 458.25 9.93 456.24 45.8 3 1.14 0.501 344.85 9.86 342.79 34.5 4 0.98 0.534 328.68 9.69 326.83 32.9 5 1.35 0.473 389.8 3.82 370.93 39.0 6 1.29 0.520 427.97 9.83 425.19 43.8 7 1.67 0.488 473.18 9.73 468.93 47.3 8 1.17 0.498 375.65 9.80 372.34 37.6 Average value 1.27 0.50 404 9.07 399 41 Standard deviation 0.18 0.02 52 2.12 53 5

The compressive strength of water drainage devices with a bonding material according to the invention with and without a wetting agent is comparable to other mineral wool samples with a density of 75 kg/m ³ .

Example 2.

Six different substrates were prepared and analyzed for compressive strength.

Product 1. MMVF substrate including 2.1 wt.% formaldehyde-free binder material according to the present invention; density 76 kg/ ^m3 ; 3.5 l/t wetting agent (Texapon®). The binder material in this product had the following composition:

AOL (ammonium oxidized lignin): 1000 kg (284 kg UPM BioPiva 100 lignin, 57 kg H2O2 (35% strength), 53 kg NH ₄ OH (24.7% strength), 506 kg water);

plasticizer (PEG 200): 44 kg;

crosslinker (Primid XL552 - crosslinker (3-hydroxyalkylamide (HAA), available from EMS-Chemie AG): 22 kg.

Product 2. MMVF substrate comprising 2.1 wt.% formaldehyde-free binder material according to the present invention; density 76 kg/ ^m3 ; without wetting agent. The binder material in this product is the same as described in Product 1 above.

- 29 045582

Comparative Product 1: MMVF substrate including 2.6 wt.% urea phenol formaldehyde resin (PUF) binder material; density 77 kg/ ^m3 ; 5.7 l/t wetting agent (linear alkylbenzenesulfonate). The binder material in this product was formed from the following:

329 l of urea-phenol-formaldehyde resin;

1337 liters of water;

l aqueous ammonia;

30.5 l ammonium sulfate;

1.6 l of aminosilane VS-142 from Momentive.

Comparative Product 2: MMVF substrate comprising 2.6 wt.% PUF binder material; density 77 kg/ ^m3 ; 3.5 l/t wetting agent (Texapon®). The binder material in this product is the same as that described in Comparative Product 1 above.

Comparative Product 3: MMVF substrate including 2.8 wt.% formaldehyde-free binder material; density 78 kg/ ^m3 ; 6.7 l/t wetting agent (linear alkyl sulfonate). The binder in this product was formed by the reaction of the following components with each other:

185 kg AAA resin;

239 kg dextrose: 575 kg water;

1.1 kg silane.

AAA resin was prepared as follows:

kg of diethanolamine (DEA) was placed in a 400 L reactor and heated to 60°C. Then 75 kg of tetrahydrophthalic anhydride (THPA) was added. After increasing the temperature and maintaining it at 130°C for 1 hour, 50 kg of trimellitic anhydride (TMA) was added. The reaction mixture was cooled to 95°C, water was added and the mixture was stirred for 1 hour.

Comparative Product 4: MMVF substrate comprising 2.8 wt.% formaldehyde-free binder material; density 78 kg/ ^m3 ; 3.5 l/t wetting agent (Texapon®). The binder material in this product is the same as that described above in comparative product 3.

The results are shown in Fig. 1A-1E. The compression was measured in both wet and dry conditions according to the EN826 standard of 1996 for insulating materials with the following deviations: in the EN 826 standard, the initial deformation X ₀ and the critical compressive strength σ _ε and σ _e are not calculated.

European (EN) standards for insulating materials require that test specimens be stored and measured at (23±5)°C. In case of doubt, storage and measurement should be carried out at (23±2)°C and (50±5)% relative humidity (R.H.) as this is considered to have no effect on the mineral wool.

The amount of binder material used in products 1 and 2 according to the invention is significantly lower than the amounts used in comparative products 1-4. However, despite this, comparative compression results are visible when compared with a PUF binder material and another formaldehyde-free binder material. Therefore, using smaller amounts of binder material according to the invention, equivalent compressive strength is achieved. It would be expected that increasing the amount of binder material according to the invention to 2.8 wt.% would lead to an increase in compressive strength. However, achieving comparable compressive strength with lower amounts has the added benefit of reducing the total amount of binder material in the product.

Example 3.

Storage, average drainage, and average seepage values of MMVF samples were measured.

Storage, drainage and seepage were measured as discussed below.

First, a plexiglass column is formed using sand and the MMVF test sample. The column is first filled with sand to a height of approximately 25 cm. The drainage device is then placed on top of the sand. The column is then filled with water from a nearby reservoir.

The weight gain and the amount of time taken to add 5 L of water to the column are recorded. The column is filled until water can be seen on top of the mineral wool. Then the addition of water is stopped. Now all the water has accumulated in the cotton wool.

Then the column is drained. For every 2 liters of water drained from the column, time and weight are noted. This is carried out for approximately 2 hours. The drainage valve is then closed.

The remaining water seeps into the sand filler, which exits the column through a hose into buckets. Weight and time after removing 2 liters of water are measured for as long as possible.

The cycle of accumulation, drainage and seepage is repeated.

The substrates described below in the table were tested. 3 and the results are shown in FIG. 2, 3 and 4.

- 30 045582

Table 3

Sample Type Density (kg/m ³ ) Wetting agent 1 Binding material according to the invention; without wetting agent 75 No 2 Binder material according to the invention, wetting agent (Teharop®) 75 yes (Teharope) 3 PUF binder material; wetting agent (Rewopal) 120 yes (Rewopal) 4 PUF binder material: no wetting agent 120 No 5 PUF binder material; without wetting agent 75 No

The binder material according to the invention and the PUF binder material were prepared as described above in Example 2.

From the results it can be seen that the samples according to the invention with or without a wetting agent exhibit similar properties. Therefore, the wetting agent does not have a significant effect.

The samples according to the invention (samples 1 and 2) accumulate faster than all other types of mineral wool compared.

Drainage with samples 1 and 2 (according to the invention) occurs faster than with samples 3 and 4, and similar to sample 5.

Percolation through samples 1 and 2 (according to the invention) occurs faster than through all comparable types of mineral wool.

Example 4.

The binder material used in the water drainage device according to the invention was prepared as follows.

3267 kg of water is charged into a 6000 l reactor and then 287 kg of aqueous ammonia (24.7%) is added. 1531 kg of UPM BioPiva 100 lignin is then added slowly over a period of 30 to 45 minutes. The mixture is heated to 40°C and maintained at this temperature for 1 hour. After 1 hour, the presence of undissolved lignin is checked. This is done by checking the solution on a glass plate or with a Hegman device. Undissolved lignin is visible as fine particles in the brown binder material. During the dissolution stage, the lignin solution will change color from brown to shiny black.

After the lignin has completely dissolved, add 1 liter of defoamer (Skumd^mper 11-10 from NCA-Verodan). The batch temperature is maintained at 40°C.

The addition of 307.5 kg of 35% hydrogen peroxide is then started. Hydrogen peroxide is dosed at a rate of 200-300 l/h. The first half of hydrogen peroxide is added at a rate of 200 l/h, after which the dosing rate is increased to 300 l/h.

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

After 15 minutes of reaction at 65°C, the reaction mixture is cooled to a temperature below 50°C. A resin is thereby obtained having a COOH value of 1.2 mmol/g solids.

From the above AOL resin, a binder material was formed by adding 270 kg of polyethylene glycol 200 and 433 kg of a 31% solution of Primid XL-552 in water.

Analysis of the final binder material showed the following data:

solids content 18.9%;

pH value: 9.7;

viscosity 25.5 mPa-s;

density 1.066 kg/l.

Examples of lignin oxidation.

Examples I.

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

The amounts of ingredients used according to example IA are given in table. IA1.1 and IA1.2.

Although kraft lignin is soluble in water at a relatively high pH, it is known that at a certain percentage by weight the viscosity of the solution will increase sharply. Usually,

- 31 045582 it appears that the reason for the increase in viscosity is a combination of the formation of strong hydrogen bonds and the interaction of π electrons of the numerous aromatic rings present in lignin. For kraft lignin, a sharp increase in viscosity was observed at a content of about

21-22 wt.% in water and in the presented example 19 wt.% kraft lignin was used.

An aqueous solution of ammonia was used as a base in the pH adjustment step. The amount was fixed at 4 wt.% based on the total weight of the reaction mixture. The pH value after the pH adjustment step and at the beginning of oxidation was 10.7.

Table IA2 shows elemental analysis results for CHNS before and after kraft lignin oxidation. Before analysis, the samples were heat treated at 160°C to remove adsorbed ammonia. Analysis showed that a certain amount of nitrogen became part of the oxidized lignin structure during the oxidation process.

During testing in batches of experiments, it was determined that oxidation was favored by adding the entire amount of hydrogen peroxide over a short period of time, as opposed to adding hydrogen peroxide in small portions over a long period of time. In the present example, 2.0 wt.% H ₂ O ₂ was used based on the total weight of the reaction mixture.

Oxidation is an exothermic reaction and an increase in temperature was noted when peroxide was added. In this example, the temperature was maintained at 60°C for a three hour reaction.

After oxidation, the number of lignin functional groups per gram of sample increased, as determined by ³¹ P NMR and titration in an aqueous medium. Sample preparation for ^{the 31} P NMR spectrum was performed using 2-chloro-4,4,5,5-tetramethyl-1,2,3-dioxaphospholane (TMDP) as the phosphitylation reagent and cholesterol as the internal standard. NMR spectra of kraft lignin were recorded before and after oxidation, and the results are summarized in Table. IA3.

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

|„ _ (g ₂ 5, ml ^- Gi _|ML ) - _ml - P1 £>, ml) * Acid. mol/l ^(COOH, mmol/g) ^- ~ '%,g where V _2s and V _1s represent predetermined final volumes of the sample; whereas

V _2b and V _1b represent the volume for the control experiment;

The _acid is a 0.1 M HCl solution in this case; and m _s represents the weight of the sample.

The values obtained by titration in an aqueous medium before and after oxidation are shown in table. IA4.

Average COOH functionality can also be quantified by the saponification number, which represents the number of mg of KOH required to saponify 1 g of lignin. This method can be found in the instructions of the American Petrochemical Society AOCS Official Method Cd 3-25.

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

Example IB. Scaling up lignin oxidation in ammonia with hydrogen peroxide to semi-plant scale.

Oxidation of lignin by hydrogen peroxide is an exothermic process, and significant temperature increases have been noted with the addition of peroxide even on a laboratory scale. This naturally poses a problem when scaling chemical processes, since the amount of heat generated scales with size to the third power (by volume), whereas cooling typically increases with size only to the square power (by area). In addition, due to the high viscosity of sticky intermediates, processing equipment must be carefully selected or designed. Thus, the scaling was carefully designed and carried out in several stages.

The first scaling step was carried out from 1 L (lab scale) to 9 L, using a professional stainless steel mixer with very efficient mechanical stirring. Scale-up resulted in only a slightly higher final temperature than that obtained at laboratory scale, which was attributed to efficient air cooling of the reactor and slow addition of hydrogen peroxide.

The next scale-up step was carried out in a closed 200 L reactor with an efficient water jacket and an efficient propeller stirrer. The scale at this time was 180 L and hydrogen peroxide was added in two stages at approximately 30 minute intervals. This scale-up proved to be relatively successful, although quite significant foaming was a problem due to the high reactor filling ratio. To control foaming, a small amount of food grade defoamer was sprayed onto the foam. The most important thing was

- 32 045582 achieving controlled temperatures, and using external water cooling, final temperatures below 70°C were achieved.

The pilot-scale reactions were carried out in an 800 L reactor with a water-cooled jacket and stirred using a double-bladed propeller mixer. 158 kg of Lignin (UPM LignoBoost TM BioPiva 100) with a dry matter content of 67 wt.% was crushed to break up lumps and suspended in 224 kg of water and mixed to form a homogeneous suspension. With continuous stirring, 103 kg of a 25% ammonia solution in water was pumped into the reactor and stirred for an additional 2 hours to form a dark, viscous lignin solution.

140 kg of 7.5 wt.% hydrogen peroxide at a temperature of 20-25°C was added to the stirred lignin solution over 15 minutes. The temperature and foam level were carefully controlled during and after the addition of hydrogen peroxide, and cooling water was supplied to the cooling jacket to maintain acceptable foam levels and a temperature rise of less than 4°C/min and a final temperature below 70°C. Once the temperature had stopped rising, refrigeration was turned off and the product mixture was stirred for an additional 2 hours before transferring to the shipping container.

Based on scale-up experiments, one could conclude that even if the reactions are exothermic, most of the heat of reaction is actually balanced by the heat capacity of the water being heated from room temperature to about 60°C, and only the latter part must be removed by cooling. It should be noted that due to this and due to the short reaction time, this method would be ideal for scale-up and intensification using continuous reactors such as inline mixers, tube reactors or CSTR reactors. This would provide good temperature control and a more well-defined reaction process.

Tests on scaled batches showed that the resulting oxidized lignin had properties consistent with those produced in the laboratory.

Table IA1.1

Quantities of materials used in the form of their delivery

Material Weight.% Kraft lignin UPM BioPiva 100 28 H2O2, 30% by weight solution in water 6.6 NH3, 25% by weight aqueous solution 16 Water 49.4

Table IA1.2

Amounts of active material used

Material Weight.% Kraft lignin 19 H ₂ O ₂ 2 NH ₃ 4 Water 75

Table IA2

Elemental analysis of kraft lignin before and after oxidation

Sample N (wt.%) C (wt.%) N (wt.%) S (wt.%) Kraft lignin 0.1 64.9 5.8 1.7 Ammonium oxidized kraft lignin 1.6 65.5 5.7 1.6

- 33 045582

Table IA3

Distribution of functional groups in kraft lignin before and after oxidation, obtained by ³¹ P NMR method

Concentration (mmol/g) Sample Aliphatic OH Phenolic OH Acidic OH Kraft lignin 1.60 3.20 0.46 Ammonium Oxidized Kraft Lignin 2.11 3.60 0.80

Table IA4

Content of COOH groups in mmol/g as determined by titration in an aqueous medium

Sample COOH groups (mmol/g) Kraft lignin 0.5 Ammonium Oxidized Kraft Lignin 0.9

Table IA5 Number average (Mn) and weight average (Mw) molecular weights, as determined by gel permeation chromatography, expressed in g/mol, together with the average content of carboxylic acid groups per lignin macromolecule before and after oxidation

Sample MP, g/mol Mw, g/mol Average COOH functionality Kraft lignin 1968 21105 0.9 Ammonium oxidized kraft lignin 2503 34503 2.0

Examples II.

In the following examples, some oxidized lignins were prepared.

The following properties of oxidized lignins were determined.

Content of solid components.

The content of each component in a given solution of oxidized lignin is given based on the anhydrous mass of the components or as indicated below.

Kraft lignin was supplied by UPM as BioPiva100™ in dry powder form. 25% NH ₄ OH Solution was purchased from Sigma-Aldrich and used as supplied. H2O2, 30% Solution (CAS No. 7722-84-1) was purchased from Sigma-Aldrich and used as supplied or diluted with water. PEG 200 was purchased from Sigma-Aldrich, considered anhydrous for simplicity, and used as is. PVA (Mw 89000-98000, Mw 85000-124000, Mw 130000, Mw 146000-186000) (CAS No. 9002-89-5) were purchased from Sigma-Aldrich, considered anhydrous for simplicity and used as is. Urea (CAS No. 57-13-6) was purchased from Sigma-Aldrich and used as supplied or diluted with water. Glycerol (CAS No. 56-81-5) was purchased from Sigma-Aldrich, considered anhydrous for simplicity, and used as is.

Solid components of oxidized lignin.

The oxidized lignin content after heating to 200°C for 1 hour is designated as dry solid material and is reported as the percentage of the remaining weight after heating.

Disc-shaped rock wool samples (diameter: 5 cm; height 1 cm) were cut from the rock wool and preheated at 580°C for at least 30 min to remove all organic components. Binder mixture solids were measured by spreading a sample of the binder mixture (approximately 2 g) onto a heat-treated rock wool disk in a tin foil container. The weight of a tin foil container containing a disc of rock wool was determined before and immediately after the addition of the binder mixture. Two such binder-containing rock wool discs were prepared in tin foil containers and then heated at 200°C for 1 hour. After cooling and standing at room temperature for 10 minutes, the samples were weighed and the solid content was calculated as the average of two results.

Content of COOH groups.

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

„ _ (^25, ML (^2b,ML ^1b,Ml) * ^acid, mol/l ^L (COOH, mmol/g) ~ ~

- 34 045582 where V _2s and V _1s represent predetermined final volumes of the sample; whereas

V _2b and V _1b represent the volume for the control experiment;

C _acid represents 0.1 M HCl solution in this case, and ms represents the weight of the sample.

Method for producing oxidized lignin.

1) Water and lignin were mixed in a 3-neck glass round-bottom flask in a water bath at room temperature (20-25°C) while stirring, connected to a refrigerator and a temperature recording device. Stirring was carried out for 1 hour.

2) Add ammonia in 1 portion while stirring.

3) Raise the temperature to 35°C by heating if the slightly exothermic reaction with ammonia did not provide an increase in temperature.

4) The pH value was measured.

5) Add plasticizer PEG200 and mix for 10 minutes.

6) After the lignin had completely dissolved after approximately 1 hour, 30% H ₂ O ₂ was added slowly in one portion.

7) The exothermic reaction by adding H ₂ O ₂ increased the temperature in the glass round bottom flask; if the temperature of the reaction mixture was below 60°C, the temperature was increased to 60°C and the sample was kept at 60°C for 1 hour.

8) The round bottom flask was then removed from the water bath and allowed to cool to room temperature.

9) Samples were taken to determine dry solids content, COOH, viscosity, density and pH.

Compositions of oxidized lignin.

The following are code numbers for an example of oxidized lignin, corresponding to the code numbers used in the table. II.

Example IIA.

71.0 g of UPM Biopiva 100 Lignin was dissolved in 149.0 g of water at 20°C, and 13.3 g of 25% NH4OH was added, and stirred for 1 hour on a magnetic stirrer, after which 16.8 g were slowly added 30% H ₂ O ₂ with stirring. The temperature was increased to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled and thereby stopped the reaction. The resulting material was analyzed for COOH, dry solids content, pH, viscosity and density.

Example IIE.

71.0 g of UPM Biopiva 100 lignin was dissolved in 88.8 g of water at 20°C, and 13.3 g of 25% NH4OH was added and stirred for 1 hour on a magnetic stirrer. PEG 200, 22.8 g was added and stirred for 10 min, after which 16.7 g of 30% H2O2 was slowly added with stirring. The temperature was increased to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled and thereby stopped the reaction. The resulting material was analyzed for COOH, dry solids content, pH, viscosity and density.

Example IIC.

71.0 g of UPM Biopiva 100 Lignin was dissolved in 57.1 g of water at 20°C and 13.3 g of 25% NH ₄ OH was added and stirred for 1 hour using a mechanical stirrer, after which 16 .6 g of 30% H2O2 with stirring. The temperature was increased to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled and thereby stopped the reaction. The resulting material was analyzed for COOH, dry solids content, pH, viscosity and density.

Example IIF.

71.0 g of UPM Biopiva 100 Lignin was dissolved in 57.1 g of water at 20° C. and 13.3 g of 25% NH ₄ OH was added and stirred for 1 hour using a mechanical stirrer. PEG 200, 19.0 g was added and stirred for 10 minutes, after which 16.6 g of 30% H ₂ O ₂ was slowly added with stirring. The temperature was increased to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled and thereby stopped the reaction. The resulting material was analyzed for COOH, dry solids content, pH, viscosity and density.

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PA table

Example PA example Example PV PS example Example IID Example PE Example IIF Example IIG Example PN Example III Example Ш PC example IIL Example IM example Example ΠΝ Sample software PR example Example IIQ Example IIR IIS Example Materials, weight in grams: Lignin O O O O O O O O O O O O O O O O O 112.3 149.5 Water 149.0 88.8 H 88.8 H 88.8 ι/h H 00 ι/h 88.8 H O NH4OH (25 wt.%, solution in water) £ 2 £ h £ h H H 2 h H 2 h h 22 h h η ci H2O2 (30 wt.%, solution in water) O <4 O h H O Yu 45 h 45 45 O h O O 45 h SC £ PEG200 O. O. O. O. 22.8 O ? O. CO With ABOUT O ABOUT O. O. O. O. PVA ABOUT ABOUT ABOUT ABOUT O ABOUT O Emergency O £ ABOUT O O ABOUT O O ABOUT ABOUT ABOUT Urea (25 wt.%, solution in water) O ABOUT ABOUT O O ABOUT O ABOUT ABOUT O H OS O ABOUT ABOUT ABOUT O ABOUT ABOUT Glycerol O ABOUT O O O O O O O O O O O ABOUT 21.0 o' O O O Sorbitol O O O O O O O O O O O O O O O O O 21.0 30.0 Dry solids %, 200°C, 1 hour X sch O o' O se O 00 34.4 46.3 ci O 40.2 ci ri o' ri O oo pH O O O O O? σ? ABOUT ABOUT σ? σΓ O O O O O O Viscosity, 20°С, cP o' 25000 above 100000 above 100000 15000 25000 50000 15000 25000 50000 15000 25000 50000 ooo 25000 50000 15000 25000 50000 Appearance * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * COOH, mmol/g h OU 00 o' h ^{1 1 1 1 1 1 1 1 1 1 1 1 1} Initial lignin, conc. Weight fraction of aqueous solution 0.32 0.44 0.55 0.80 0.44 0.55 0.80 0.44 o' 0.80 0.44 ^P o' 0.80 O 0.55 0.80 0.44 0.55 o 00 o

* Heterogeneous black thick solution.

** Black solution.

*** Homogeneous black thick solution.

Example III.

Mix 8.5 liters of hot water (50°C) and 1.9 liters of NH ₄ OH (24.7%) and then slowly add 9.0 kg of lignin (UPM biopiva 100) over 10 minutes with vigorous stirring (660 rpm, 44 Hz).

The temperature increased due to high shear loads. After 30 minutes, 4 L of hot water was added and the material was stirred for an additional 15 minutes before adding the remainder of the hot water (5 L). Samples were taken for analysis of undissolved lignin using the Hegman scale and pH measurements.

This pre-mixture was then transferred to the rotor-stator and reaction apparatus where oxidation was performed using H ₂ O ₂ (17.5 vol.%). Device for

-36045582 reaction apparatus used in this case has, at least in part, a reaction tube and a reaction vessel. The premix dosage was 150 l/h and H2O2 was dosed at 18 l/h.

In this case, a Cavitron CD1000 rotor-stator device was used to carry out the mixing/oxidation step. The rotor-stator device operated at a speed of 250 Hz (with a peripheral speed of 55 m/s) with a back pressure of 2 bar (0.2 MPa). The holding time in the reaction tube was 3.2 minutes and in the reaction tank - 2 hours.

The premix temperature was 62°C and during the oxidation stage the temperature increased to 70°C.

The final product was analyzed for COOH groups, dry solids, pH, viscosity and residual H2O2.

Table III

Example Dry solid material, 200°C, 1 hour, % COOH, mmol/g solids substances pH Viscosity III 22.3 1.13 9.6 average

Example IV.

484 L of hot water (70°C) and 47.0 L of NH ₄ OH (24.7%) were mixed and then 224.0 kg of lignin (UPM biopiva 100) was slowly added over 15 minutes with vigorous stirring. Samples were collected for undissolved lignin analyzes using the Hegman scale 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 dosage of the premix was 600 l/h, and H ₂ O ₂ was dosed at a flow rate of 17.2 l/h. The residence time in the mixer/heat exchanger was 20 minutes.

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

The final product was analyzed for COOH groups, dry solids, pH, viscosity and residual H ₂ O ₂ .

A binder material was prepared from this AOL: 49.3 g AOL (19.0% solids), 0.8 g Primid XL552 (100% solids) and 2.4 g PEG200 (100% solids) mixed with 0 .8 g water to obtain 19% solids; and then used to test the mechanical properties in rod tests.

Rod tests.

The mechanical strength of the binder materials was tested in a rod test. For each binder material, 16 rods were prepared from a mixture of binder material and batches of rock wool from the rock wool spinning process.

A sample of this binder solution having 15% dry solids (16.0 g) was thoroughly mixed into portions (80.0 g). The resulting mixture was then filled into four grooves in a heat-resistant silicone mold to produce small rods (4x5 grooves per mold; top groove size: length=5.6 cm, width=2.5 cm; bottom groove size: length=5.3 cm, width=2.2 cm; groove height=1.1 cm). The mixtures placed in the grooves were then pressed with a suitably sized flat metal rod to form smooth surfaces of the rods. In this way, 16 rods were prepared from each binder material. Then the resulting rods were cured at 200°C. The curing time was 1 hour. After cooling to room temperature, the rods were carefully removed from the containers. Five of the rods were kept in a water bath at 80°C for 3 h.

After drying for 1-2 days, the aged specimens, as well as five unaged rods, were fractured at 3 points by a bending test (test speed: 10.0 mm/min; fracture level: 50%; nominal strength: 30 N/ ^mm2 ; support distance: 40 mm; maximum deflection 20 mm; nominal modulus of elasticity 10000 N/mm ² ;) on the Bent Tram device, to study their mechanical strength. The rods were placed into the device with the top surface facing up (i.e., the surface with dimensions of length = 5.3 cm, width = 2.5 cm).

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Claims (10)

AOL Features Rod tests Sample name Solid materials, 200°C, 1 hour, % COOH (mmol/g solids) Viscosity Initial strength (kN) Strength after aging (kN) Example IV 17.7 1.69 low 0.28 0.11 CLAIM 1. A method of water drainage, comprising the steps of providing a water drainage device, the water drainage device comprising man-made vitreous fibers (MMVF) bonded with a cured aqueous binder composition; and placing a water drainage device in contact with the ground, the water drainage device absorbing water and releasing water into a receptacle; wherein the aqueous binder composition, before curing, includes component (i) in the form of one or more oxidized lignins; component (iia) in the form of one or more modifiers. 2. The method according to claim 1, wherein component (i) is in the form of one or more ammonium oxidized lignins (AOL). 3. The method according to claim 1 or 2, in which component (iia) includes one or more modifiers selected from the group consisting of epoxidized fatty acid triglyceride oils; molecules having 3 or more epoxy groups; one or more flexible oligomers or polymers containing functional groups, where preferably (a) a low Tg acrylic based polymer, a low Tg vinyl based polymer, a low Tg polyester, and/or (b) the reactive functional groups are selected from carbodiimide groups, anhydride groups, oxazoline groups, amino groups, epoxy groups; polyethyleneimine, polyvinylamine or fatty amines; aliphatic polyfunctional carbodiimides. 4. The method according to any preceding claim, wherein the aqueous binder composition includes component (iia) in an amount of from 1 to 40 wt.%, preferably from 4 to 20 wt.%, more preferably from 6 to 12 wt.%, based on dry weight of component (i). 5. The method according to any of the preceding paragraphs, further comprising component (ii) in the form of one or more cross-linking agents; and component (iii) in the form of one or more plasticizers. 6. The method according to claim 5, wherein component (ii) includes at least one of the following components: one or more cross-linking agents selected from β-hydroxyalkylamide cross-linking agents and/or oxazoline cross-linking agents; one or more cross-linking agents selected from the group consisting of polyethylenimine, polyvinylamine, 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 dimethoxyethanal, glycolaldehyde, glyoxalic 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, carboxymethylcellulose (CMC); and/or one or more cross-linking agents in the form of aliphatic polyfunctional carbodiimides; and/or one or more cross-linkers selected from melamine-based cross-linkers, such as hexakis(methylmethoxy)melamine (HMMM) cross-linkers. 7. The method according to claim 5 or 6, wherein component (iii) includes at least one of the following components: - 38 045582 one or more plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and/or acids such as adipic acid, vanillic acid, lactic acid and/or ferulic acid, acrylic polymers , polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic-based polymers with free carboxyl groups and/or polyurethane dispersions with free carboxyl groups; and/or one or more plasticizers selected from the group consisting of aliphatic alcohols, monohydric 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 plasticizers in the form of glycol esters; and/or one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelainates, butyrates, valerates; and/or one or more plasticizers selected from the group consisting of phenolic derivatives such as alkyl- or aryl-substituted phenols; and/or one or more plasticizers selected from the group consisting of silanols, siloxanes; and/or one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkylaryl sulfonates such as alkyl; and/or sulfonates, phosphates such as tripolyphosphates; and/or one or more plasticizers in the form of hydroxy acids; 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, distearyldimethylammonium 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, soybean oil; and/or one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils; and/or one or more plasticizers selected from the group consisting of methyl acid esters; and/or one or more plasticizers selected from the group consisting of alkyl polyglucosides, gluconamides, aminoglucosamides, sugar esters, sorbitan esters; and/or one or more plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers. 8. The method according to any one of claims 5 to 7, in which (a) component (ii) is present in an amount of from 1 to 40 wt.%, preferably from 4 to 20 wt.%, more preferably from 6 to 12 wt. %, based on the dry weight of component (i); and/or (b) component (iii) is present in an amount of from 0.5 to 50% by weight, preferably from 2.5 to 25% by weight, more preferably from 3 to 15% by weight, based on the dry weight of the component (i). 9. The method according to any preceding claim, wherein the aqueous binder composition includes one or more of additional component (iv) in the form of one or more binders such as organofunctional silanes; and/or component (v) in the form of one or more components selected from the group of ammonia, amines or any of their salts; and/or an additional component in the form of urea, in particular in an amount of 5 to 40% by weight, such as 10 to 30% by weight, such as 15 to 25% by weight, based on the dry weight of the component (i ). 10. The method according to any preceding claim, wherein the aqueous binder composition essentially consists of component (i) in the form of one or more oxidized lignins; component (iia) in the form of one or more modifiers selected from epoxidized fatty acid triglyceride oils; 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 of ammonia, amines or any salts thereof; optionally a urea component; optionally a component in the form of more reactive or non-reactive silicones; optionally hydrocarbon oil; optionally one or more surfactants; And -