Stadium with shock-absorbing mats comprising lignin-based binders

Abstract

The invention relates to a sports field comprising: (i) a lower base layer; (ii) an upper grass layer and / or artificial grass layer; (iii) a shock-absorbing mat layer located between the base layer and the grass layer or artificial grass layer; wherein the shock-absorbing mat layer comprises at least one shock-absorbing mat comprising an adhering panel having an upper major surface and a lower major surface, wherein the adhering panel comprises at least one adhering layer comprising man-made vitreous fibres (MMVF) bonded with a cured aqueous binder composition; wherein the aqueous binder composition before curing comprises: - component (i) in the form of one or more than one oxidized lignin; - component (ii) in the form of one or more than one crosslinker; - component (iii) in the form of one or more than one plasticizer.

Description

Technical Field

[0001] This invention relates to a stadium comprising a shock-absorbing pad, and a method for manufacturing the stadium, wherein the shock-absorbing pad comprises a lignin-based adhesive. The invention also relates to a shock-absorbing pad and its use in absorbing vibrations in a stadium. Background Technology

[0002] Shock-absorbing pads are known to be included in stadiums, particularly in artificial turf fields used for team-based sports such as hockey or football. Generally, stadiums must meet specific requirements regarding performance, durability, and structure. For example, to ensure consistent sports performance, stadiums must conform to a set of standards concerning characteristics such as shock absorption, energy recovery, ball rebound, ball roll, ball deflection, and impact response. International sports governing bodies (such as FIFA for football and FIH for hockey) have established specific requirements that stadiums must meet to obtain official approval.

[0003] Shock-absorbing pads are used in stadiums, especially artificial surfaces, to meet the aforementioned standards. Shock-absorbing pads improve the durability of a stadium while also providing the resilience needed for sports activities. They can also be used to prevent injury by absorbing vibrations or shocks. Shock-absorbing pads are typically an essential component of any artificial sports field.

[0004] WO 04 / 033194 A1 discloses a padding system for artificial sports fields. The purpose of the padding is to provide an effective and safe sports field for sports such as football. The padding comprises three layers made of foam, rubber, or plastic.

[0005] WO 2013 / 060634 A1 discloses a shock-absorbing pad for artificial playing fields. The purpose of the shock-absorbing pad is to improve the vibration absorption and energy recovery characteristics of artificial turf systems. The shock-absorbing pad comprises a three-dimensional entangled pad of extruded filaments made of thermoplastic elastomer polymer.

[0006] WO 87 / 07520 A1 discloses a padding shock-absorbing mat for playgrounds and other areas where there is a risk of children falling. The purpose of the shock-absorbing mat is to prevent head injuries to children who fall. The mat is composed of mineral wool boards ranging from 30mm to 300mm in thickness and has a density of 70kg / m³. 3 Up to 300kg / m 3 However, because this type of shock-absorbing pad cannot meet a series of stringent requirements, it is unsuitable for use in artificial sports fields: the shock-absorbing pad is designed for playgrounds.

[0007] The goal is to produce a shock-absorbing pad that meets specific sports field requirements set by international sports governing bodies such as FIFA and FIH, and is made of materials that are more durable and environmentally friendly than existing foam, rubber, plastic, or polymer shock-absorbing pads.

[0008] The goal is to produce a shock-absorbing pad that is less sensitive to temperature conditions compared to existing foam, rubber, plastic, or polymer shock-absorbing pads.

[0009] The requirements for stadiums, especially artificial stadiums, also include the implementation of appropriate drainage and flood control systems. It is crucial to remove all surface water from the sports field at a controlled rate to prevent flooding. It is known that damping pads can be manufactured so that water can drain into the drainage system, as it is undesirable for the damping pads to impede the effective operation of the drainage system. There is a desire to produce damping pads that meet the specific sports field requirements set by international sports governing bodies such as FIFA and FIH, and that these pads can prevent or mitigate flooding, thus maintaining the same level of performance under all weather conditions.

[0010] One problem with artificial stadiums is that they can become extremely hot under certain weather conditions. For example, surface temperatures can reach as high as 90°C in some climates (natural grass typically reaches 30°C to 40°C). This is undesirable for the general area where the artificial stadium is located, as it increases air conditioning costs, thus amplifying peak summer energy demands. It is also undesirable for athletes, as the heat radiating from the artificial surface during matches is uncomfortable and can lead to injuries (e.g., heat cramps, fainting, heatstroke, or skin conditions). Overheating also reduces the durability of the artificial surface. The goal is to improve the usability of artificial stadiums by reducing surface temperature.

[0011] Artificial sports stadiums typically include an infill layer to provide the required performance and stabilize the artificial turf. Typically, the infill layer consists of a layer of sand (10mm to 20mm for stabilization) and a plastic layer (5mm to 50mm for performance). Plastics such as granulated styrene-butadiene rubber (SBR), ethylene propylene diene monomer (EPDM), or thermoplastic elastomers (TPE) are preferred. Studies have shown that microplastics from such plastic infill layers migrate into the surrounding environment, causing marine pollution. Therefore, some countries are enacting legislation to reduce or completely eliminate products that generate microplastic pollution. Consequently, there is a desire to create stadiums that do not require a plastic infill layer, i.e., stadiums that can meet the required performance levels without a plastic infill layer.

[0012] Furthermore, the preferred adhesives for synthetic fiberglass products are phenolic resins and phenolic urea resins. These adhesives are economically viable and offer excellent mechanical handling properties. This is crucial because the shock-absorbing pads are located underground and must be able to withstand pressure from above the ground (such as from athletes) during installation and subsequent use.

[0013] However, existing and proposed legislation aimed at reducing or eliminating formaldehyde emissions during manufacturing processes and in the workplace has led to the development of formaldehyde-free adhesives. Consumers are also increasingly preferring products made entirely or at least partially from renewable materials, thus creating a need for adhesives for shock-absorbing pads made from at least partially renewable materials. Furthermore, known formaldehyde-based adhesives often contain corrosive and / or harmful components. This necessitates protective measures for machinery and safety procedures for personnel operating such machinery.

[0014] Formaldehyde-free adhesives for man-made glass fiber (MMVF) products have been previously proposed. However, MMVF products prepared with these adhesives still have some disadvantages in terms of lower mechanical properties compared to those prepared with phenolic resins. Furthermore, these adhesives are typically made from expensive starting materials.

[0015] In addition, it is desirable to improve the water treatment performance of the shock-absorbing pads, such as buffering, permeability, and drainage.

[0016] Furthermore, MMVF products often contain wetting agents to enhance hydrophilicity. However, over time, some of these wetting agents may wash away from the MMVF products. This is particularly problematic because the damping pad is located on the ground, and the wetting agent may seep out and contaminate the surrounding surface. Additionally, as the wetting agent is washed away, the drainage performance of the damping pad changes significantly. Finally, for environmental and cost-effectiveness reasons, there has been a persistent desire to reduce the number of components required to manufacture damping pads.

[0017] There is a need for improved shock-absorbing pads for artificial sports fields compared to existing foam, rubber, plastic, or polymer pads. There is a need for a shock-absorbing pad that is more durable and / or more resilient than existing foam, rubber, plastic, or polymer pads. There is a need for a shock-absorbing pad that can do this while meeting the standards set by international sports governing bodies (such as FIFA for football and FIH for hockey). There is a need for a shock-absorbing pad that can improve the usability of artificial stadiums by absorbing water (e.g., rainwater). There is a need for a shock-absorbing pad that can actively prevent or manage flooding by absorbing water. There is a need for a shock-absorbing pad that can extend the usability of stadiums by reducing surface temperature. There is a need for a shock-absorbing pad that is environmentally acceptable and economical in terms of manufacturing, installation, and use.

[0018] Furthermore, there is a need for a shock-absorbing pad that can be installed in artificial stadiums without a plastic filler layer. The pad needs to have a formaldehyde-free adhesive but with the same or better mechanical handling properties (e.g., compressive strength) as phenolic adhesives. Improved water-holding properties (e.g., improved water cushioning, permeability, and drainage) are desired. Additionally, it is desirable that this adhesive be economically produced and primarily based on renewable resources. Finally, it is desirable that this adhesive does not require the addition of further wetting agents, thus preventing wetting agents from seeping into the surrounding ground. Summary of the Invention

[0019] In a first aspect, a stadium is provided, comprising:

[0020] (i) Lower base layer;

[0021] (ii) Upper grass layer and / or artificial turf layer;

[0022] (iii) A shock-absorbing pad layer located between the base layer and the grass or artificial turf layer;

[0023] The damping pad layer includes at least one damping pad, the damping pad including an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer, the adhesive layer including artificial glass fiber (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing includes:

[0024] - Component (i), which is one or more forms of oxidized lignin;

[0025] - Component (ii), which is in the form of one or more crosslinking agents;

[0026] - Component (iii), which is in the form of one or more plasticizers.

[0027] In a second aspect of the invention, a method for manufacturing a stadium is provided, comprising the following steps:

[0028] (i) Provide the lower base layer;

[0029] (ii) Provide a shock-absorbing pad layer above the base layer;

[0030] (iii) Provide an upper grass layer and / or artificial grass layer above the shock-absorbing pad;

[0031] The damping pad layer includes at least one damping pad, the damping pad including an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer, the adhesive layer including artificial glass fiber (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing includes:

[0032] - Component (i), which is one or more forms of oxidized lignin;

[0033] - Component (ii), which is in the form of one or more crosslinking agents;

[0034] - Component (iii), which is in the form of one or more plasticizers.

[0035] A third aspect of the invention provides a shock-absorbing pad comprising an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition prior to curing comprises:

[0036] - Component (i), which is one or more forms of oxidized lignin;

[0037] - Component (ii), which is in the form of one or more crosslinking agents;

[0038] - Component (iii), which is in the form of one or more plasticizers.

[0039] In a fourth aspect of the invention, a method for producing a shock-absorbing pad is provided, comprising the following steps:

[0040] (i) Provide synthetic glass fibers;

[0041] (ii) Spraying artificial glass fibers with an aqueous adhesive composition;

[0042] (iii) Collect and consolidate artificial glass fibers and cure the aqueous adhesive composition to form an adhesive layer;

[0043] (iv) Provide an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer;

[0044] The aqueous adhesive composition before curing includes:

[0045] - Component (i), which is one or more forms of oxidized lignin;

[0046] - Component (ii), which is in the form of one or more crosslinking agents;

[0047] - Component (iii), which is in the form of one or more plasticizers.

[0048] In a fifth aspect of the invention, a method is provided for using a shock-absorbing pad in a stadium to provide a vibration-absorbing surface, comprising the steps of: placing the shock-absorbing pad or a group of shock-absorbing pads below the surface of the stadium, wherein the shock-absorbing pad includes: an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing comprises:

[0049] - Component (i), which is one or more forms of oxidized lignin;

[0050] - Component (ii), which is in the form of one or more crosslinking agents;

[0051] - Component (iii), which is in the form of one or more plasticizers.

[0052] In a sixth aspect of the invention, a shock-absorbing pad is provided for use in a stadium to absorb vibrations, wherein the shock-absorbing pad comprises: an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing comprises:

[0053] - Component (i), which is one or more forms of oxidized lignin;

[0054] - Component (ii), which is in the form of one or more crosslinking agents;

[0055] - Component (iii), which is in the form of one or more plasticizers.

[0056] In a seventh aspect of the invention, a shock-absorbing pad is provided for use in a stadium for absorbing and / or draining water, wherein the shock-absorbing pad comprises: an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing comprises:

[0057] - Component (i), which is one or more forms of oxidized lignin;

[0058] - Component (ii), which is in the form of one or more crosslinking agents;

[0059] - Component (iii), which is in the form of one or more plasticizers.

[0060] An eighth aspect of the invention provides the use of a shock-absorbing pad for cooling the surface temperature of a stadium, wherein the shock-absorbing pad comprises: an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing comprises:

[0061] - Component (i), which is one or more forms of oxidized lignin;

[0062] - Component (ii), which is in the form of one or more crosslinking agents;

[0063] - Component (iii), which is in the form of one or more plasticizers.

[0064] The inventors of this invention have found that the shock-absorbing pad of this invention solves the above-mentioned problems.

[0065] The shock-absorbing pad according to the present invention is an improvement over existing foam, rubber, plastic, or polymer shock-absorbing pads. It is more durable and / or more resilient than existing foam, rubber, plastic, or polymer shock-absorbing pads, and also meets the standards set by international sports governing bodies (such as FIFA for football and FIH for hockey). The shock-absorbing pad according to the present invention can actively prevent or manage flooding by absorbing water. The shock-absorbing pad according to the present invention can retain water within its structure, thus improving the athletic performance of stadiums. The inventors have discovered that because water is absorbed and stored within the shock-absorbing pad, a plastic filler layer is no longer needed. The shock-absorbing pad according to the present invention also allows the stored water to evaporate, thereby cooling the surface temperature, through direct contact with temperature and wind via the upper layer or through water absorption by the upper layer. The shock-absorbing pad of the present invention is environmentally acceptable and economical in terms of production, installation, and use.

[0066] Crucially, the inventors have discovered an adhesive for shock-absorbing pads that is formaldehyde-free but possesses the same or better mechanical processing properties (e.g., compressive strength) as phenolic adhesives. The adhesive also exhibits improved water retention properties (e.g., improved water cushioning, permeability, and drainage, as well as horizontal water transport), can be produced economically, and is primarily based on renewable resources. Finally, the adhesive eliminates the need for further wetting agents, thus preventing wetting agents from seeping into the surrounding ground. Attached Figure Description

[0067] Figure 1 A shock-absorbing pad according to a first embodiment of the present invention is shown.

[0068] Figure 2 A shock-absorbing pad according to a second embodiment of the present invention is shown.

[0069] Figure 3A shock-absorbing pad according to the invention is shown installed on an artificial stadium floor.

[0070] Figures 4A to 4E The results of the compressive strength test are shown.

[0071] Figure 5 The results of the average water buffer are shown.

[0072] Figure 6 The results of average drainage are shown.

[0073] Figure 7 The results show the average water permeability.

[0074] Figure 8 A slice showing the possible lignin structure is displayed.

[0075] Figure 9 The lignin precursors and common inter-unit linkages are shown.

[0076] Figure 10 Four groups of technical lignins available on the market are shown.

[0077] Figure 11 This presents a summary of the properties of industrial lignin. Detailed Implementation

[0078] This invention relates to a stadium, preferably an artificial stadium, comprising a shock-absorbing pad. The term shock-absorbing pad has its usual meaning in the art. A shock-absorbing pad is a liner located below the surface of a stadium (usually directly below the surface).

[0079] Stadiums can also be called sports grounds, playing fields, or sports fields. Stadiums include football fields, hockey fields, rugby fields, cricket fields, cricket tennis fields, grass bowling alleys, grass tennis courts, golf courses, athletic grounds, and equestrian centers. The shock-absorbing pads according to the present invention are particularly suitable for football and hockey fields. This is because the shock-absorbing pads according to the present invention meet the standards set by football and hockey governing bodies such as FIFA and FIH.

[0080] Figure 1A first embodiment of the invention is shown. The shock-absorbing pad (1) according to the invention comprises an adhesive plate (2) having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer (3) comprising artificial glass fibers (MMVF) bonded to a cured adhesive composition. The shock-absorbing pad may further comprise an upper film layer (4a) bonded to the upper main surface of the adhesive plate (2) and optionally a lower film layer (4b) bonded to the lower main surface of the adhesive plate (2).

[0081] The upper and lower main surfaces of the adhesive plate are preferably flat or level. The shape of the adhesive plate is preferably cubic or rectangular.

[0082] The shock-absorbing pad can be any size suitable for use. For example, it can have a length of 0.5 meters to 10 meters, preferably 1 meter to 2 meters, and most preferably 1.2 meters. It can have a width of 0.2 meters to 10 meters, preferably 0.75 meters to 1.5 meters, and most preferably 1 meter.

[0083] The adhesive plate includes at least one adhesive layer. The adhesive layer includes artificial glass fibers (MMVF) bonded to a cured adhesive composition.

[0084] Man-made glass fiber (MMVF) can have any suitable oxide composition. The fiber can be glass fiber, ceramic fiber, basalt fiber, slag fiber, or rock or stone fiber. The fiber is preferably of the type commonly referred to as rock, stone, or slag fiber, with stone fiber being the most preferred.

[0085] Stone fibers typically contain the following oxides, expressed as a percentage by weight:

[0086] SiO2: 30 to 51

[0087] CaO: 8 to 30

[0088] MgO: 2 to 25

[0089] FeO (including Fe2O3): 2 to 15

[0090] Na₂O + K₂O: not exceeding 10

[0091] CaO+MgO: 10 to 30

[0092] In a preferred embodiment, the MMVF comprises the following elements in weight percent of the oxide:

[0093] SiO2: at least 30, 32, 35 or 37; not exceeding 51, 48, 45 or 43

[0094] Al2O3: at least 12, 16, or 17; not exceeding 30, 27, or 25

[0095] CaO: at least 8 or 10; not exceeding 30, 25 or 20

[0096] MgO: at least 2 or 5; not more than 25, 20 or 15

[0097] FeO (including Fe2O3): at least 4 or 5; not exceeding 15, 12 or 10

[0098] FeO+MgO: at least 10, 12 or 15; not exceeding 30, 25 or 20

[0099] Na₂O + K₂O: 0 or at least 1; not exceeding 10

[0100] CaO + MgO: at least 10 or 15; not exceeding 30 or 25

[0101] TiO2: 0 or at least 1; not exceeding 6, 4 or 2

[0102] TiO2+FeO: at least 4 or 6; not exceeding 18 or 12

[0103] B2O3: 0 or at least 1; not exceeding 5 or 3

[0104] P2O5: 0 or at least 1; not exceeding 8 or 5

[0105] Other: 0 or at least 1; not exceeding 8 or 5.

[0106] The MMVF produced by the method of the present invention preferably has the following composition in weight percent:

[0107] SiO2 35 to 50

[0108] Al2O3 12 to 30

[0109] TiO2 at most 2

[0110] Fe2O3 3 to 12

[0111] CaO 5 to 30

[0112] MgO up to 15

[0113] Na2O 0 to 15

[0114] K2O 0 to 15

[0115] P2O5 at most 3

[0116] MnO at most 3

[0117] B2O3 at most 3

[0118] Another preferred composition of MMVF has the following weight percent:

[0119] SiO2 39% to 55%, preferably 39% to 52%.

[0120] Al2O3 16% to 27%, preferably 16% to 26%.

[0121] CaO 6% to 20%, preferably 8% to 18%

[0122] MgO 1% to 5%, preferably 1% to 4.9%

[0123] Na₂O 0 to 15%, preferably 2% to 12%

[0124] K2O 0 to 15%, preferably 2% to 12%

[0125] R2O (Na2O + K2O) 10% to 14.7%, preferably 10% to 13.5%.

[0126] P2O5 0 to 3%, preferably 0% to 2%

[0127] Fe2O3 (total iron) 3% to 15%, preferably 3.2% to 8%.

[0128] B2O3 0 to 2%, preferably 0 to 1%

[0129] TiO2 0 to 2%, preferably 0.4% to 1%

[0130] Others: 0 to 2.0%.

[0131] Glass fibers typically contain the following oxides, by weight percentage:

[0132] SiO2: 50 to 70

[0133] Al2O3: 10 to 30

[0134] CaO: not exceeding 27

[0135] MgO: not exceeding 12.

[0136] Glass fiber may also contain the following oxides, by weight percentage:

[0137] Na₂O + K₂O: 8 to 18, especially Na₂O + K₂O is greater than CaO + MgO.

[0138] B2O3: 3 to 12.

[0139] Some glass fiber compositions may contain less than 2% Al2O3.

[0140] The geometrically average fiber diameter is preferably in the range of 1.5 micrometers to 10 micrometers, particularly in the range of 2 micrometers to 8 micrometers, and more preferably in the range of 2 micrometers to 5 micrometers. The inventors have found that this range of geometrically average fiber diameters has a positive effect on capillary action, thereby improving the water absorption rate in the shock-absorbing pad.

[0141] The adhesive layer is preferably in the form of MMVF adhesive agglomerates, i.e., an MMVF matrix. That is, the adhesive layer is typically an adhesive matrix consisting of MMVF fibers bonded to a cured adhesive composition, which has been manufactured in this manner or formed by granulating and solidifying particulate material in an MMVF sheet. The adhesive matrix is ​​a single, homogeneous matrix.

[0142] The advantage of the shock-absorbing pad containing MMVF described in this invention is that it is more environmentally friendly than shock-absorbing pads made of plastic, foam, rubber or polymer materials.

[0143] The thickness of at least one adhesive layer can range from 12 mm to 60 mm, preferably from 15 mm to 40 mm, more preferably from 20 mm to 35 mm, and most preferably from 23 mm to 30 mm. Thickness refers to the dimension from the upper surface to the lower surface of the adhesive layer, i.e., the height of the adhesive layer when the damping pad is used. The advantage of a damping pad with an adhesive layer thickness of 12 mm to 60 mm is that it achieves the required water management performance (i.e., absorption, storage, and drainage of excess water; cooling of the surface of the artificial sports field) while simultaneously meeting the stringent requirements of international sports governing bodies for artificial sports fields. Furthermore, the dimensions conform to standard structural requirements, making the installation of the damping pad easier.

[0144] The density of at least one adhesive layer can be 175 kg / m³ 3 Up to 300kg / m 3 Within the range, preferably 220 kg / m 3 Up to 280kg / m 3 Within the range, the optimal value is 275 kg / m³. 3 Density is 175 kg / m³ 3 Up to 300kg / m 3 The advantage of shock-absorbing pads with adhesive layers within the specified range is that they achieve an optimal balance between durability and motion performance. The shock-absorbing pads according to the invention meet the motion performance requirements set by regulatory authorities and are also highly durable.

[0145] Prior to curing, the shock-absorbing pad according to the present invention comprises an aqueous adhesive composition, said aqueous adhesive composition comprising:

[0146] - Component (i), which is one or more forms of oxidized lignin;

[0147] - Component (ii), which is in the form of one or more crosslinking agents;

[0148] - Component (iii), which is in the form of one or more plasticizers.

[0149] In a preferred embodiment, the adhesive is formaldehyde-free.

[0150] For the purposes of this application, the term "formaldehyde-free" is defined as characterized in that the formaldehyde emission from the mineral wool product is less than 5 μg / m³. 2 Mineral wool products with a concentration of / h are preferred, preferably below 3μg / m 2 / h. Preferably, the test is conducted according to ISO 16000 to determine the amount of aldehyde released.

[0151] Component (i)

[0152] Component (i) is one or more forms of oxidized lignin.

[0153] Lignin, cellulose, and hemicellulose are the three main organic compounds in plant cell walls. Lignin can be considered the glue that holds cellulose fibers together. Lignin contains both hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, after cellulose, and is estimated to account for as much as 20% to 30% of the total carbon content in biomass, which contains more than 1 billion tons of carbon globally.

[0154] Figure 8 A slice showing the possible lignin structure is displayed.

[0155] There are at least four groups of industrial lignins available on the market. These four groups are... Figure 10 The text shows a possible fifth group, biorefined lignin, which is somewhat different because it is described not according to the extraction process but according to the source of the process, such as biorefining. Therefore, it may be similar to or different from any of the other groups mentioned above. Each group is distinct from the others and suited to different applications. Lignin is a complex, heterogeneous material, composed of up to three different phenylpropane monomers depending on its source. Cork lignin is primarily composed of coniferyl alcohol units; see [link to relevant documentation]. Figure 9 Therefore, they are more uniform than hardwood lignin, which has a higher eugenol content. See [link to relevant documentation]. Figure 9 The appearance and consistency of lignin are quite variable and depend heavily on the processing method.

[0156] Figure 11 The properties of these industrial lignins are summarized below.

[0157] Lignin sulfonates from the sulfite pulping process remain the largest commercially available source of lignin, with a capacity of 1.4 million tons. However, the sulfate process is currently the most widely used pulping process and is gradually replacing the sulfite process. It is estimated that 78 million tons of lignin are produced globally annually from sulfate pulp, but most of this is burned for steam and energy. Current sulfate recovery capacity is estimated at 160,000 tons, but reports indicate that only about 75,000 tons are actually being recovered. Sulfate lignin is developed from black liquor, the waste liquid from the sulfate or sulfate process. Currently, three well-known processes are used to produce sulfate lignin: LignoBoost, LignoForce, and SLRP. These three processes are similar in that they all involve adding CO2 to lower the pH to 9-10, followed by acidification to further lower the pH to about 2. The final step involves a combination of washing, leaching, and filtration to remove ash and other contaminants. These three processes are at different stages of commercialization globally.

[0158] The sulfate process introduces thiol groups and stilbenes while retaining some carbohydrates. Sodium sulfate also exists as an impurity because lignin is precipitated from the liquid by sulfuric acid, but this problem can potentially be avoided by altering the lignin separation method. The sulfate process results in the formation of a large number of phenolic hydroxyl groups, which, when ionized (above pH ~10), make the lignin soluble in water.

[0159] Commercial lignin sulfates are typically of higher purity than lignin sulfonates. Their molecular weight ranges from 1000 g / mol to 3000 g / mol.

[0160] Alkali lignin is derived from a sodium hydroxide pulping process and is primarily used in wheat straw, bagasse, and flax. The properties of alkali lignin are similar to those of sulfate lignin in terms of solubility and total glutaraldehyde (Tg). This process does not use sulfur, nor does it involve covalently bonded sulfur. Ash levels are very low. Alkali lignin has low solubility in neutral and acidic media, but dissolves completely at pH 12 or higher.

[0161] The lignin sulfonate process introduces a large number of sulfonate groups, making lignin soluble in both water and acidic aqueous solutions. Lignosulfonates have a sulfur content as high as 8%, making them sulfonates, while sulfate lignin contains 1% to 2% sulfur, primarily bound to lignin. The molecular weight of lignin sulfonates ranges from 15,000 g / mol to 50,000 g / mol. Compared to other types of lignin, this type contains more residual carbohydrates and has a higher average molecular weight. The typical hydrophobic core and abundant ionized sulfonate groups of lignin make it attractive as a surfactant, and it is frequently used in applications such as dispersing cement.

[0162] Another type of lignin is produced in biorefining processes, where carbohydrates are separated from the lignin through chemical or biochemical processes, resulting in a carbohydrate-rich fraction. This remaining lignin is called biorefined lignin. Biorefining plants focus on producing energy and alternatives to products derived from fossil fuels and petrochemicals, as well as lignin. The lignin produced in this process is generally considered a low-value product, or even waste, primarily used for thermal combustion, as low-grade animal feed, or otherwise disposed of.

[0163] The availability of organic solvent-based lignin is still being considered at the pilot-scale level. The process involves using water and various organic solvents (most commonly ethanol) as well as some organic acids to extract lignin. The advantage of this process is the high purity of the lignin obtained, but it is significantly more expensive than other industrial lignins, and the obtained lignin dissolves in organic solvents rather than water.

[0164] Previous attempts to use lignin as a base compound in mineral fiber adhesive compositions failed because it proved difficult to find suitable crosslinking agents to achieve the desired mechanical properties of cured mineral wool products while avoiding harmful and / or corrosive components. Currently, lignin is used as a substitute for petroleum-derived chemicals, such as phenol in adhesive applications or phenolic resins in asphalt. It is also used as an additive in cement and concrete, and in some applications as a dispersant.

[0165] Crosslinking of polymers is generally expected to provide better properties, such as mechanical, chemical, and heat resistance. Lignin is particularly abundant in phenolic and aliphatic hydroxyl groups, which can react to produce crosslinked structures. Different lignins will also have other available functional groups. Depending on the source, the presence of these other groups depends largely on how lignin is separated from cellulose and hemicellulose (thiols in sulfate lignin, sulfonates in lignin sulfonates, etc.).

[0166] It has been found that by using oxidized lignin, adhesive compositions for mineral fibers can be prepared, thereby giving the manufactured mineral fiber products excellent properties.

[0167] In one embodiment, component (i) is in the form of one or more oxidized sulfate lignins.

[0168] In one embodiment, component (i) is in the form of one or more oxidized alkali lignins.

[0169] In one embodiment, component (i) is in the form of one or more ammonia-oxidized lignins. For the purposes of this invention, the term "ammonia-oxidized lignin" should be understood as lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.

[0170] In an alternative embodiment, ammonia is partially or wholly replaced by alkali metal hydroxides, particularly sodium hydroxide and / or potassium hydroxide.

[0171] Hydrogen peroxide is a typical oxidizing agent used in the preparation of oxidized lignin.

[0172] In one embodiment, the ammonia-oxidized lignin comprises one or more compounds selected from ammonia, amines, hydroxides, or any salts thereof.

[0173] In one embodiment, based on the dry weight of component (i), the content of carboxylic acid groups in component (i) is from 0.05 mmol / g to 10 mmol / g, such as from 0.1 mmol / g to 5 mmol / g, such as from 0.20 mmol / g to 1.5 mmol / g, such as from 0.40 mmol / g to 1.2 mmol / g, such as from 0.45 mmol / g to 1.0 mmol / g.

[0174] In one embodiment, the average content of carboxylic acid groups in component (i) exceeds 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups.

[0175] The content of carboxylic acid groups in oxidized lignin is believed to play an important role in the unexpected advantages of mineral fibers in the aqueous adhesive compositions of the present invention. In particular, the carboxylic acid groups in oxidized lignin are believed to improve crosslinking properties, thus giving the cured mineral fiber products better mechanical properties.

[0176] Component (ii)

[0177] Component (ii) is in the form of one or more crosslinking agents.

[0178] In one embodiment, component (ii) includes one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

[0179] β-hydroxyalkylamide crosslinkers are curing agents for acid-functional macromolecules. They provide a rigid, durable, corrosion-resistant, and solvent-resistant crosslinked polymer network. β-hydroxyalkylamide crosslinkers are believed to cure via esterification to form multiple ester bonds. The hydroxyl functionality of the β-hydroxyalkylamide crosslinker should ideally be at least 2 on average, preferably greater than 2, and more preferably 2 to 4, to obtain optimal curing response.

[0180] Crosslinking agents containing oxazoline groups are polymers containing one or more oxazoline groups per molecule, and typically, crosslinking agents containing oxazoline groups can be readily obtained by polymerizing oxazoline derivatives. This process is disclosed in patent US6818699 B2.

[0181] In one embodiment, component (ii) is an epoxy oil based on fatty acid triglycerides.

[0182] It should be noted that epoxy oils based on fatty acid triglycerides are not considered harmful, and therefore the use of these compounds in the adhesive compositions according to the present invention does not make the handling of these compositions unsafe.

[0183] In one embodiment, component (ii) is a molecule having three or more epoxy groups.

[0184] In one embodiment, component (ii) is one or more flexible oligomers or polymers, such as low-Tg acrylic polymers, low-Tg vinyl polymers, or low-Tg polyethers, containing reactive functional groups such as carbodiimide groups, anhydride groups, oxazoline groups, amino groups, or epoxy groups.

[0185] In one embodiment, component (ii) is selected from the crosslinking agent participating in the curing reaction, such as the reaction product of hydroxyalkylamides, alkanolamines, alkanolamines, and polycarboxylic acids. The reaction product of alkanolamines and polycarboxylic acids can be found in US6706853B1.

[0186] Without intending to be bound by any particular theory, the inventors believe that the highly advantageous properties of the aqueous adhesive composition are due to the interaction between the oxidized lignin used as component (i) and the aforementioned crosslinking agent. It is believed that the presence of carboxylic acid groups in the oxidized lignin enables it to crosslink very effectively.

[0187] In one embodiment, component (ii) is one or more crosslinking agents selected from polyfunctional organic amines (such as alkanolamines), diamines (such as hexamethyldiamine), and triamines.

[0188] In one embodiment, component (ii) is one or more crosslinking agents selected from polyethyleneimine, polyethyleneamine, and fatty amines.

[0189] In one embodiment, component (ii) is one or more fatty amides.

[0190] In one embodiment, component (ii) is one or more crosslinking agents selected from dimethoxyacetaldehyde, glycolaldehyde, and glyoxylic acid.

[0191] In one embodiment, component (ii) is one or more crosslinking agents selected from polyester polyols, such as polycaprolactone.

[0192] In one embodiment, component (ii) is one or more crosslinking agents selected from starch, modified starch, and CMC.

[0193] In one embodiment, component (ii) is one or more crosslinking agents in the form of aliphatic polyfunctional carbodiimides.

[0194] In one embodiment, component (ii) is one or more crosslinking agents selected from melamine crosslinking agents, such as hexa(methylmethoxy)melamine (HMMM) crosslinking agents.

[0195] Examples of such compounds include Picassian XL 701, 702, and 725 (Stahl Polymers), such as... XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).

[0196] Component (ii) may also be any mixture of the above compounds.

[0197] In one embodiment, based on the dry weight of component (i), the adhesive composition according to the invention comprises from 1% to 40% by weight of component (ii), such as from 4% to 20% by weight, such as from 6% to 12% by weight.

[0198] Component (iii)

[0199] Component (iii) is one or more forms of plasticizer.

[0200] In one embodiment, component (iii) is one or more plasticizers selected from: polyols such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids such as adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactide, acrylic polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides (such as urea / urea), or any mixture thereof.

[0201] In one embodiment, component (iii) is in the form of one or more plasticizers selected from: carbonates such as ethylene carbonate, propylene carbonate, lactone, lactam, lactide, compounds having a lignin-like structure such as vanillin, acetylsalicylic acid, solvents used as coalescing agents such as alcohol ethers, and polyvinyl alcohol.

[0202] In one embodiment, component (iii) is in the form of one or more non-reactive plasticizers selected from: polyethylene glycol, polyethylene glycol ether, polyether, hydrogenated sugar, phthalates and / or other esters, solvents used as coalescing agents such as alcohol ethers, acrylic polymers, and polyvinyl alcohol.

[0203] In one embodiment, component (iii) is one or more reactive plasticizers selected from: carbonates such as ethylene carbonate, propylene carbonate, lactones, lactams, lactide, dicarboxylic acids or tricarboxylic acids such as adipic acid, or lactic acid, and / or vanillic acid and / or ferulic acid, polyurethane dispersions, acrylic polymers having free carboxyl groups, compounds having a lignin-like structure (such as vanillin), and acetylsuccinone.

[0204] In one embodiment, component (iii) is in the form of one or more plasticizers selected from fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.

[0205] In one embodiment, component (iii) includes one or more plasticizers selected from polyethylene glycol and polyethylene glycol ether.

[0206] Another particularly unexpected aspect of the invention is that the use of plasticizers with boiling points exceeding 100°C, particularly 140°C to 250°C, significantly improves the mechanical properties of the mineral fiber articles according to the invention, although, given their boiling points, these plasticizers are likely to evaporate at least partially during the curing process of the aqueous adhesives in contact with the mineral fibers.

[0207] In one embodiment, component (iii) includes one or more plasticizers with a boiling point exceeding 100°C, such as 110°C to 280°C, more preferably 120°C to 260°C, and even more preferably 140°C to 250°C.

[0208] The effectiveness of these plasticizers in water-based adhesive compositions is believed to be related to their effect of increasing the flowability of oxidized lignin during curing. Increased flowability of lignin or oxidized lignin during curing is thought to contribute to effective crosslinking.

[0209] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 g / mol to 50,000 g / mol, particularly 150 g / mol to 4,000 g / mol, more particularly 150 g / mol to 1,000 g / mol, preferably 150 g / mol to 500 g / mol, and more preferably 200 g / mol to 400 g / mol.

[0210] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4,000 g / mol to 25,000 g / mol, particularly 4,000 g / mol to 15,000 g / mol, and even more particularly 8,000 g / mol to 12,000 g / mol.

[0211] In one embodiment, component (iii) is capable of forming covalent bonds with components (i) and / or (ii) during the curing process. This component does not evaporate and remains as part of the composition, but is effectively altered to avoid introducing unwanted side effects, such as water absorption in the cured article. Non-limiting examples of such components are caprolactone and acrylic polymers having free carboxyl groups.

[0212] In one embodiment, component (iii) is selected from fatty alcohols, monohydroxy alcohols such as pentanol, and stearyl alcohol.

[0213] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from alkoxylates such as ethoxylates, butanol ethoxylates, butoxytriethylene glycol.

[0214] In one embodiment, component (iii) is selected from one or more propylene glycols.

[0215] In one embodiment, component (iii) is selected from one or more ethylene glycol esters.

[0216] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from: adipate, acetate, benzoate, cyclobenzoate, citrate, stearate, sorbate, decanoate, azelaic acid ester, butyrate, valerate.

[0217] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from phenol derivatives such as alkyl or aryl substituted phenols.

[0218] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from: silanols, siloxanes.

[0219] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from: sulfate esters such as alkyl sulfate esters, sulfonates such as alkyl aryl sulfonates such as alkyl sulfonates, phosphate esters such as tripolyphosphate, such as tributyl phosphate.

[0220] In one embodiment, component (iii) is selected from one or more hydroxy acids.

[0221] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from: monomeric amides such as acetamide, benzamide, fatty acid amides such as tallowamide.

[0222] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from quaternary ammonium compounds such as trimethylglycine and distearate dimethylammonium chloride.

[0223] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from vegetable oils such as castor oil, palm oil, flaxseed oil, tall oil, and soybean oil.

[0224] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from hydrogenated oils and acetylated oils.

[0225] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0226] In one embodiment, component (iii) is selected from one or more plasticizers, said plasticizer being selected from: alkyl polysaccharides, glucosamide, aminoglucosamide, sucrose esters, and dehydrated sorbitol esters.

[0227] It has been unexpectedly discovered that the addition of plasticizers to the water-based adhesive composition significantly improves the mechanical properties of the shock-absorbing pads according to the present invention.

[0228] The term plasticizer refers to a substance added to a material to make it softer, more flexible (by lowering the glass transition temperature Tg) and easier to process.

[0229] Component (iii) may also be any mixture of the above compounds.

[0230] In one embodiment, based on the dry weight of component (i), the content of component (iii) is from 0.5% to 50% by weight, preferably from 2.5% to 25% by weight, and more preferably from 3% to 15% by weight.

[0231] Aqueous adhesive compositions for mineral fibers comprise components (i) and (iia).

[0232] One embodiment of the invention relates to an aqueous adhesive composition for mineral fibers, comprising:

[0233] - Component (i), which is one or more forms of oxidized lignin;

[0234] - Component (iia), which is in the form of one or more modifiers.

[0235] The inventors have discovered that excellent adhesive properties can also be achieved through a two-component system comprising one or more components in the form of oxidized lignin (i) and one or more components in the form of modifiers (iia), and optionally any other components mentioned above and below.

[0236] In one embodiment, component (iia) is a modifier, which is in the form of one or more compounds selected from fatty acid triglyceride-based epoxy oils.

[0237] In one embodiment, component (iia) is a modifier, which is one or more compounds selected from molecules having three or more epoxy groups.

[0238] In one embodiment, component (iia) is a modifier that is in the form of one or more flexible oligomers or polymers, such as low-Tg acrylic polymers, low-Tg vinyl polymers, or low-Tg polyethers, containing reactive functional groups such as carbodiimide groups, anhydride groups, oxazoline groups, amino groups, or epoxy groups.

[0239] In one embodiment, component (iia) is one or more modifiers selected from polyethyleneimine, polyethyleneamine, and fatty amines.

[0240] In one embodiment, component (iia) is one or more modifiers selected from aliphatic polyfunctional carbodiimides.

[0241] Component (iia) can also be any mixture of the above compounds.

[0242] Without intending to be bound by any particular theory, the inventors believe that the superior adhesive properties achieved by the adhesive composition of mineral fibers comprising components (i) and (iia) and optionally other components are at least in part due to the modifier used as component (iia) serving at least in part as a plasticizer and crosslinking agent.

[0243] In one embodiment, based on the dry weight of component (i), the aqueous adhesive composition comprises 1% to 40% by weight of component (iia), such as 4% to 20% by weight, such as 6% to 12% by weight.

[0244] Other components

[0245] In some embodiments, the aqueous adhesive composition contains other components.

[0246] In one embodiment, the aqueous adhesive composition comprises a catalyst selected from inorganic acids, such as sulfuric acid, aminosulfonic acid, nitric acid, boric acid, hypophosphoric acid and / or phosphoric acid, and / or any salt thereof, such as sodium hypophosphite, and / or ammonium salts, such as ammonium salts of sulfuric acid, aminosulfonic acid, nitric acid, boric acid, hypophosphoric acid and / or phosphoric acid. The presence of such a catalyst can improve the curing properties of the aqueous adhesive composition.

[0247] In one embodiment, the aqueous adhesive composition includes a catalyst selected from Lewis acids that can accept electron pairs from a donor compound to form Lewis adducts, such as ZnCl2, Mg(ClO4)2, and Sn[N(SO2-n-C8F17)2]4.

[0248] In one embodiment, the aqueous adhesive composition comprises a catalyst selected from metal chlorides, such as KCl, MgCl2, ZnCl2, FeCl3, and SnCl2.

[0249] In one embodiment, the aqueous adhesive composition includes a catalyst selected from organometallic compounds, such as titanate catalysts and tin catalysts.

[0250] In one embodiment, the aqueous adhesive composition comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, and copper ions.

[0251] In one embodiment, the aqueous adhesive composition further includes other components (iv) in the form of one or more silanes.

[0252] In one embodiment, the aqueous adhesive composition comprises other components (iv) in the form of one or more coupling agents, such as organofunctional silanes.

[0253] In one embodiment, component (iv) is selected from organofunctional silanes, such as primary or secondary amino-functionalized silanes, epoxy-functionalized silanes, such as polymeric or oligomeric epoxy-functionalized silanes, methacrylate-functionalized silanes, alkyl and aryl-functionalized silanes, urea-functionalized silanes, or vinyl-functionalized silanes.

[0254] In one embodiment, the aqueous adhesive composition further includes component (v), which is in the form of one or more components selected from ammonia, amines, or any salts thereof.

[0255] The inventors have found that when oxidized lignin is used in component (i), it is particularly useful to add ammonia, amines, or any salts thereof as other components, wherein the oxidized lignin is not oxidized in the presence of ammonia.

[0256] In one embodiment, based on the dry weight of component (i), the aqueous adhesive composition further includes other components in the form of urea, particularly in amounts of 5% to 40% by weight, such as 10% to 30% by weight, or 15% to 25% by weight.

[0257] In one embodiment, the aqueous adhesive composition further includes one or more other components in the form of carbohydrates selected from sucrose, reducing sugars, especially glucose, polysaccharides and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, even more preferably glucose syrup with a glucose equivalent value of DE = 30 to less than 100, such as DE = 60 to less than 100, such as DE = 60-99, such as DE = 85-99, such as DE = 95-99.

[0258] In one embodiment, the aqueous adhesive composition further includes other components in the form of one or more carbohydrates selected from sucrose and reducing sugars, in an amount of 5% to 50% by weight, such as 5% to less than 50% by weight, such as 10% to 40% by weight, such as 15% to 30% by weight, based on the dry weight of component (i).

[0259] In the context of this invention, adhesive compositions with a sugar content of 50% by weight or more are considered sugar-based adhesives based on the total dry weight of the adhesive components. In the context of this invention, adhesive compositions with a sugar content of less than 50% by weight are considered non-sugar-based adhesives based on the total dry weight of the adhesive components.

[0260] In one embodiment, the aqueous adhesive further includes other components in the form of one or more surfactants, said surfactants being in the form of nonionic and / or ionic emulsifiers, such as polyoxyethylene (4) lauryl ether, such as soybean lecithin, such as sodium dodecyl sulfate.

[0261] In one embodiment, the aqueous adhesive composition comprises:

[0262] - Component (i), which is one or more forms of amino-oxidized lignin, has a carboxylic acid group content of 0.05 mmol / g to 10 mmol / g, such as 0.1 mmol / g to 5 mmol / g, such as 0.20 mmol / g to 1.5 mmol / g, such as 0.40 mmol / g to 1.2 mmol / g, such as 0.45 mmol / g to 1.0 mmol / g, based on the dry weight of component (i);

[0263] - Component (ii), which is in the form of one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents, and / or in the form of one or more crosslinking agents selected from polyfunctional organic amines such as alkanolamines, diamines such as hexamethyldiamine, and triamines;

[0264] - Component (iii), which is in the form of one or more polyethylene glycols having an average molecular weight of 150 g / mol to 50,000 g / mol, particularly 150 g / mol to 4,000 g / mol, more specifically 150 g / mol to 1,000 g / mol, preferably 150 g / mol to 500 g / mol, more preferably 150 g / mol to 300 g / mol, or is in the form of one or more polyethylene glycols having an average molecular weight of 4,000 g / mol to 25,000 g / mol. l, particularly 4000 g / mol to 15000 g / mol, more specifically 8000 g / mol to 12000 g / mol; wherein, based on the dry weight of component (i), the preferred aqueous adhesive composition contains component (ii) in an amount of 1 wt% to 40 wt%, such as 4 wt% to 20 wt%, 6 wt% to 12 wt%, and based on the dry weight of component (i), the content of (iii) is 0.5 wt% to 50 wt%, preferably 2.5 wt% to 25 wt%, more preferably 3 wt% to 15 wt%.

[0265] In one embodiment, the aqueous adhesive composition comprises:

[0266] - Component (i), which is one or more forms of amino-oxidized lignin, has a carboxylic acid group content of 0.05 mmol / g to 10 mmol / g, such as 0.1 mmol / g to 5 mmol / g, such as 0.20 mmol / g to 1.5 mmol / g, such as 0.40 mmol / g to 1.2 mmol / g, such as 0.45 mmol / g to 1.0 mmol / g, based on the dry weight of component (i);

[0267] - Component (iia), which is in the form of one or more modifiers selected from epoxy oils based on fatty acid triglycerides.

[0268] In one embodiment, the aqueous adhesive composition comprises:

[0269] - Component (i), which is one or more forms of ammoniated lignin, wherein the average content of carboxylic acid groups per macromolecule of component (i) exceeds 1.5 groups, such as 2 or more groups, such as 2.5 or more groups;

[0270] - Component (ii), which is in the form of one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents, and / or in the form of one or more crosslinking agents selected from polyfunctional organic amines such as alkanolamines, diamines such as hexamethyldiamine, and triamines;

[0271] - Component (iii), which is in the form of one or more polyethylene glycols having an average molecular weight of 150 g / mol to 50,000 g / mol, particularly 150 g / mol to 4,000 g / mol, more specifically 150 g / mol to 1,000 g / mol, preferably 150 g / mol to 500 g / mol, more preferably 150 g / mol to 300 g / mol, or is in the form of one or more polyethylene glycols having an average molecular weight of 4,000 g / mol to 25,000 g / mol. l, particularly 4000 g / mol to 15000 g / mol, more specifically 8000 g / mol to 12000 g / mol; wherein, based on the dry weight of component (i), the preferred aqueous adhesive composition contains component (ii) in an amount of 1 wt% to 40 wt%, such as 4 wt% to 20 wt%, 6 wt% to 12 wt%, and based on the dry weight of component (i), the content of (iii) is 0.5 wt% to 50 wt%, preferably 2.5 wt% to 25 wt%, more preferably 3 wt% to 15 wt%.

[0272] In one embodiment, the aqueous adhesive composition comprises:

[0273] - Component (i), which is one or more forms of ammonia-oxidized lignin, wherein the average content of carboxylic acid groups per macromolecule of component (i) exceeds 1.5 groups, such as 2 or more groups, such as 2.5 or more groups.

[0274] - Component (iia), which is in the form of one or more modifiers selected from epoxy oils based on fatty acid triglycerides.

[0275] In one embodiment, the aqueous adhesive composition is essentially composed of the following substances:

[0276] - Component (i), which is one or more forms of oxidized lignin;

[0277] - Component (ii), which is in the form of one or more crosslinking agents;

[0278] - Component (iii), which is in the form of one or more plasticizers.

[0279] - Component (iv), which is in the form of one or more coupling agents, such as organofunctional silanes;

[0280] -Optional components, which are in the form of one or more compounds selected from ammonia, amines or any salts thereof;

[0281] - Optional component, which is in the form of urea;

[0282] -Optional components, which may be in the form of more reactive or non-reactive polysiloxanes;

[0283] -Optional hydrocarbon oil;

[0284] - Choose one or more surfactants;

[0285] -water.

[0286] In one embodiment, the aqueous adhesive composition is essentially composed of the following substances:

[0287] - Component (i), which is one or more forms of oxidized lignin;

[0288] - Component (iia), which is in the form of one or more modifiers selected from epoxy oils based on fatty acid triglycerides.

[0289] - Component (iv), which is in the form of one or more coupling agents, such as organofunctional silanes;

[0290] -Optional components, which are in the form of one or more compounds selected from ammonia, amines or any salts thereof;

[0291] - Optional component, which is in the form of urea;

[0292] -Optional components, which may be in the form of more reactive or non-reactive polysiloxanes;

[0293] -Optional hydrocarbon oil;

[0294] -Choose one or more surfactants;

[0295] -water.

[0296] Based on the weight of the adhesive layer, at least one adhesive layer preferably comprises 1.0 wt% to 6.0 wt% of a cured adhesive composition, preferably 2.5 wt% to 3.5 wt%, and most preferably 3.0 wt% to 3.8 wt%. The advantage associated with this range of 3.0 wt% to 3.8 wt% is that it allows the damping pad to have the desired stiffness and elasticity. The adhesive content is determined according to DS / EN13820:2003. The adhesive content is taken as the loss on ignition. The adhesive content includes any adhesive additives.

[0297] The preparation method of the above-mentioned oxidized lignin in the aqueous adhesive composition is as follows.

[0298] Method I Preparation of Oxidized Lignin

[0299] Oxidized lignin, which can be used as a component of the adhesive of the present invention, can be prepared by the following method, the method comprising contacting the following substances:

[0300] - Component (a), which includes one or more lignins;

[0301] - Component (b), which includes ammonia, one or more amine components and / or any salts thereof;

[0302] - Component (c), which includes one or more oxidizing agents.

[0303] Component (a)

[0304] Component (a) includes one or more lignins.

[0305] In one embodiment, component (a) comprises one or more sulfate lignins, one or more alkali lignins, one or more lignin sulfonate lignins, one or more organic solvent lignins, one or more lignins obtained by a biorefining process of lignocellulose raw materials, or any mixture thereof.

[0306] In one embodiment, component (a) comprises one or more sulfate lignins.

[0307] Component (b)

[0308] In one embodiment, component (b) comprises ammonia, one or more amino components and / or any salts thereof. Without intending to be bound by any particular theory, the inventors believe that replacing the alkaline hydroxides used in previously known lignin oxidation processes with ammonia, one or more amino components and / or any salts thereof plays an important role in improving the properties of oxidized lignin prepared according to the method of the present invention.

[0309] The inventors unexpectedly discovered that lignin oxidized by an oxidizing agent in the presence of ammonia or amine contains a significant amount of nitrogen as part of the oxidized lignin structure. Without intending to be bound by any particular theory, the inventors believe that when oxidized lignin is used in articles in which it is included in adhesive compositions, the improved fire resistance of the oxidized lignin is at least in part due to the nitrogen content of the oxidized lignin structure.

[0310] In one embodiment, component (b) includes ammonia and / or any salt thereof.

[0311] Without wishing to be bound by any particular theory, the inventors believe that the improved stability of the derivatized lignin prepared according to the present invention is at least in part due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused. In contrast, it has been shown that it is difficult to remove residual amounts of alkaline hydroxides used in previously known oxidation processes.

[0312] However, in the method, it is advantageous for component (b) to include, in addition to ammonia, one or more amino components and / or any salts thereof, a relatively small amount of alkali and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0313] In the embodiments, component (b) includes an alkali and / or alkaline earth metal hydroxide, such as sodium hydroxide and / or potassium hydroxide, as a component other than ammonia, one or more amino components and / or any salts thereof. The amount of the alkali and / or alkaline earth metal hydroxide is generally small, based on ammonia, such as 5 parts by weight to 70 parts by weight, such as 10 parts by weight to 20 parts by weight of the alkali and / or alkaline earth metal hydroxide.

[0314] Component (c)

[0315] In the methods described herein, component (c) includes one or more oxidizing agents.

[0316] In one embodiment, component (c) comprises one or more oxidants, said oxidant being in the form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen-containing oxidants, or any mixture thereof.

[0317] In the initial step of oxidation, the active free radical from the oxidant typically extracts a proton from the phenolic group because this bond has the lowest dissociation energy in lignin. Since lignin has the potential to stabilize the free radical through mesoscopic isomerism, there are multiple pathways through which the reaction can be continued (but also terminated), yielding a variety of intermediates and final products. Due to this complexity (and the conditions of choice), the average molecular weight can increase and decrease; in their experiments, the inventors typically observed a modest increase in the average molecular weight of approximately 30%.

[0318] In one embodiment, component (c) includes hydrogen peroxide.

[0319] Hydrogen peroxide is perhaps the most commonly used oxidant due to its combination of low cost, high efficiency, and relatively low environmental impact. When using hydrogen peroxide in the absence of a catalyst, alkaline conditions and temperature are important because the following reactions lead to the formation of free radicals:

[0320]

[0321]

[0322] The inventors have discovered that, due to the oxidation process, the derivatized lignin prepared by the method described herein contains an increased amount of carboxylic acid groups. Without intending to be bound by any particular theory, the inventors believe that the content of carboxylic acid groups in the oxidized lignin prepared by the method described herein plays an important role in the ideal reactivity of the derivatized lignin prepared by the method described herein.

[0323] Another advantage of the oxidation process is that oxidized lignin is more hydrophilic. Higher hydrophilicity can enhance solubility in water and promote adhesion to polar matrices such as mineral fibers.

[0324] Other components

[0325] In one embodiment, the method for preparing oxidized lignin preferably includes other components, particularly components (d) in the form of an oxidation catalyst, such as one or more transition metal catalysts, such as ferric sulfate, or catalysts containing manganese, palladium, selenium, or tungsten.

[0326] This oxidation catalyst can increase the reaction rate, thereby improving the performance of oxidized lignin.

[0327] Component mass ratio

[0328] Those skilled in the art will use the relative amounts of components (a), (b), and (c) to achieve the desired degree of lignin oxidation.

[0329] In one implementation scheme

[0330] - Component (a) contains one or more lignins

[0331] - Component (b), containing ammonia

[0332] - Component (c) contains one or more oxidants in the form of hydrogen peroxide.

[0333] Based on the dry weight of lignin, the mass ratio of lignin, ammonia, and hydrogen peroxide is such that the amount of ammonia is 0.01 parts by weight to 0.5 parts by weight, such as 0.1 parts by weight to 0.3 parts by weight, or 0.15 parts by weight to 0.25 parts by weight, and based on the dry weight of lignin, the amount of hydrogen peroxide is 0.025 parts by weight to 1.0 parts by weight, such as 0.05 parts by weight to 0.2 parts by weight, or 0.075 parts by weight to 0.125 parts by weight.

[0334] process

[0335] There is more than one possibility to bring components (a), (b), and (c) into contact to achieve the desired oxidation reaction.

[0336] In one implementation, the method includes the following steps:

[0337] - The step of providing component (a) and / or a dispersion of multiple lignins in the form of an aqueous solution, wherein the lignin content of the aqueous solution is from 1% to 50% by weight, such as 5% to 25% by weight, such as 15% to 22% by weight, such as 18% to 20% by weight, based on the total weight of the aqueous solution.

[0338] - The step of adjusting the pH by adding an aqueous solution of ammonia, one or more amine components and / or any salts thereof (b);

[0339] - An oxidation step by adding a component (c) including an oxidant.

[0340] In one embodiment, a pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH ≥ 9, such as ≥ 10, such as ≥ 10.5.

[0341] In one embodiment, a pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH in the range of 10.5 to 12.

[0342] In one implementation, a pH adjustment step is performed to raise the temperature to ≥25°C, and then the temperature is controlled within the range of 25°C to 50°C, such as 30°C to 45°C, or 35°C to 40°C.

[0343] In one embodiment, during the oxidation step, the temperature is raised to ≥35°C and then controlled within the range of 35°C to 150°C, such as 40°C to 90°C, or 45°C to 80°C.

[0344] In one embodiment, the oxidation step is carried out for a period of 1 second to 48 hours, such as 10 seconds to 36 hours, such as 1 minute to 24 hours, such as 2 hours to 5 hours.

[0345] Method II for preparing oxidized lignin

[0346] Oxidized lignin used as a component of the adhesive used in this invention can be prepared by a method comprising contacting the following substances:

[0347] - Component (a), which includes one or more lignins;

[0348] - Component (b), which includes ammonia, and / or one or more amine components, and / or any salts and / or bases and / or alkaline earth metal hydroxides thereof, such as sodium hydroxide and / or potassium hydroxide;

[0349] - Component (c), which includes one or more oxidizing agents.

[0350] - Component (d), which is in the form of one or more plasticizers.

[0351] Component (a)

[0352] Component (a) includes one or more lignins.

[0353] In one embodiment of the method for preparing oxidized lignin, component (a) includes one or more sulfate lignins, one or more alkali lignins, one or more lignin sulfonate lignins, one or more organic solvent lignins, one or more lignins obtained by a biorefining process of lignocellulose raw materials, or any mixture thereof.

[0354] In one embodiment, component (a) comprises one or more sulfate lignins.

[0355] Component (b)

[0356] In one embodiment of the preparation of oxidized lignin, component (b) includes ammonia, one or more amino components and / or any salts and / or bases and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0357] "Ammonia-oxidized lignin" should be understood as lignin oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.

[0358] In one embodiment, component (b) includes ammonia and / or any salt thereof.

[0359] Without intending to be bound by any particular theory, the inventors believe that the improved stability of the derivatized lignin prepared according to the invention, in which component (b) is ammonia and / or any salt thereof, is at least in part due to the fact that ammonia is a volatile compound and can therefore be easily evaporated from the final product or removed and reused.

[0360] However, in the method for preparing oxidized lignin in this embodiment, it is advantageous that component (b) includes, in addition to ammonia, one or more amino components and / or any salts thereof, a relatively small amount of alkali and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0361] In some embodiments, component (b) includes an alkali and / or alkaline earth metal hydroxide, such as sodium hydroxide and / or potassium hydroxide, as a component other than ammonia, one or more amino components and / or any salts thereof. The amount of the alkali and / or alkaline earth metal hydroxide is typically small, based on ammonia, such as 5 to 70 parts by weight, or 10 to 20 parts by weight of the alkali and / or alkaline earth metal hydroxide.

[0362] Component (c)

[0363] In the method for preparing oxidized lignin, component (c) includes one or more oxidizing agents.

[0364] In one embodiment, component (c) includes one or more oxidants, said oxidant being in the form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen-containing oxidants, or any mixture thereof.

[0365] In the initial step of oxidation, the active free radical from the oxidant typically extracts a proton from the phenolic group because this bond has the lowest dissociation energy in lignin. Since lignin has the potential to stabilize the free radical through mesoscopic isomerism, there are multiple pathways through which the reaction can be continued (but also terminated), yielding a variety of intermediates and final products. Due to this complexity (and the conditions of choice), the average molecular weight can increase and decrease; in their experiments, the inventors typically observed a modest increase in the average molecular weight of approximately 30%.

[0366] In one embodiment, component (c) includes hydrogen peroxide.

[0367] Hydrogen peroxide is perhaps the most commonly used oxidant due to its combination of low cost, high efficiency, and relatively low environmental impact. When using hydrogen peroxide in the absence of a catalyst, alkaline conditions and temperature are important because the following reactions lead to the formation of free radicals:

[0368]

[0369]

[0370] The inventors have discovered that, due to the oxidation process, the derivatized lignin prepared by the method described herein contains an increased amount of carboxylic acid groups. Without intending to be bound by any particular theory, the inventors believe that the content of carboxylic acid groups in the oxidized lignin prepared according to the method of the present invention plays an important role in the ideal reactivity of the derivatized lignin prepared by the method described herein.

[0371] Another advantage of the oxidation process is that oxidized lignin is more hydrophilic. Higher hydrophilicity can enhance solubility in water and promote adhesion to polar matrices such as mineral fibers.

[0372] Component (d)

[0373] Component (d) includes one or more plasticizers.

[0374] In one embodiment, component (d) comprises one or more plasticizers in the form of polyols, such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids such as adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactide, acrylic polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides (such as urea / urea), or any mixture thereof.

[0375] The inventors have discovered that the addition of component (d) in the form of one or more plasticizers provides a reduction in the viscosity of the reaction mixture, thereby allowing for the production of oxidized lignin in a very efficient manner.

[0376] In one embodiment of the invention, component (d) comprises one or more plasticizers in the form of polyols, such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyvinyl alcohol, acrylic polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups, polyamides, amides (such as urea / urea) or any mixture thereof.

[0377] In one embodiment of the invention, component (d) includes one or more plasticizers selected from polyethylene glycol, polyvinyl alcohol, urea, or any mixture thereof.

[0378] Other components

[0379] In one embodiment, the method for preparing oxidized lignin preferably includes other components, particularly component (v), which is in the form of an oxidation catalyst, such as one or more transition metal catalysts, such as ferric sulfate, or catalysts containing manganese, palladium, selenium, or tungsten.

[0380] This oxidation catalyst can increase the reaction rate, thereby improving the properties of oxidized lignin prepared by the method.

[0381] Component mass ratio

[0382] Those skilled in the art will use the relative amounts of components (a), (b), (c), and (d) to achieve the desired degree of lignin oxidation.

[0383] In one implementation, the method is carried out such that the method includes:

[0384] - Component (a) includes one or more lignins;

[0385] - Component (b) includes ammonia;

[0386] - Component (c) includes one or more oxidants in the form of hydrogen peroxide;

[0387] - Component (d) includes one or more plasticizers selected from polyethylene glycol.

[0388] The mass ratio of lignin, ammonia, hydrogen peroxide, and polyethylene glycol is as follows: based on the dry weight of lignin, the amount of ammonia is 0.01 parts by weight to 0.5 parts by weight, for example 0.1 parts by weight to 0.3 parts by weight, for example 0.15 parts by weight to 0.25 parts by weight of ammonia (25% by weight aqueous solution); and based on the dry weight of lignin, the amount of hydrogen peroxide (30% by weight aqueous solution) is 0.025 parts by weight to 1.0 parts by weight, for example 0.07 parts by weight to 0.50 parts by weight, for example 0.15 parts by weight to 0.30 parts by weight of hydrogen peroxide; and based on the dry weight of lignin, the amount of polyethylene glycol is 0.03 parts by weight to 0.60 parts by weight, for example 0.07 parts by weight to 0.50 parts by weight, for example 0.10 parts by weight to 0.40 parts by weight of polyethylene glycol.

[0389] For the purposes of this invention, the "dry weight of lignin" is preferably defined as the weight of lignin in the provided form.

[0390] method

[0391] There is more than one possibility to bring components (a), (b), (c) and (d) into contact to achieve the desired oxidation reaction.

[0392] In one implementation, the method includes the following steps:

[0393] - The step of providing component (a) in the form of an aqueous solution and / or a dispersion of one or more lignins, wherein the lignin content of the aqueous solution is from 5% to 90% by weight, such as from 10% to 85% by weight, such as from 15% to 70% by weight, based on the total weight of the aqueous solution;

[0394] - The step of adjusting the pH by adding component (b);

[0395] - The step of adding component (d);

[0396] - An oxidation step by adding a component (c) including an oxidant.

[0397] In one embodiment, a pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH ≥ 9, such as ≥ 10, such as ≥ 10.5.

[0398] In one embodiment, a pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH in the range of 9.5 to 12.

[0399] In one implementation, a pH adjustment step is performed to raise the temperature to ≥25°C, and then the temperature is controlled within the range of 25°C to 50°C, such as 30°C to 45°C, or 35°C to 40°C.

[0400] In one embodiment, during the oxidation step, the temperature is raised to ≥35°C and then controlled within the range of 35°C to 150°C, such as 40°C to 90°C, or 45°C to 80°C.

[0401] In one embodiment, the oxidation step is carried out for a time ranging from 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.

[0402] The inventors have discovered that the method described herein allows for the production of reaction mixtures with high dry matter content, thus enabling high yields in the process of the present invention, which allows the reaction products in the form of oxidized lignin to be used as components in industrially mass-produced articles such as mineral fiber products.

[0403] In one embodiment, the method is carried out such that the dry matter content of the reaction mixture is 20% to 80% by weight, such as 40% to 70% by weight.

[0404] In one embodiment, the method is carried out such that the viscosity of the oxidized lignin has a value of 100 cP to 100,000 cP, such as 500 cP to 50,000 cP, such as 1,000 cP to 25,000 cP.

[0405] For the purposes of this invention, viscosity is dynamic viscosity, defined as the resistance of a liquid / paste to changes in shape, or the resistance of adjacent portions to movement relative to each other. Viscosity is measured in centipoises (cP), equivalent to 1 mPa·s (million Pascals per second). Viscosity is measured using a viscometer at 20°C. For the purposes of this invention, dynamic viscosity can be measured at 20°C using a cone-plate well Brookfield viscometer.

[0406] In one embodiment, the method is implemented such that it includes a rotor-stator assembly.

[0407] In one implementation, the method is carried out such that it is performed as a continuous or semi-continuous process.

[0408] Apparatus for performing the method

[0409] The present invention also relates to an apparatus for performing the above-described method.

[0410] In one embodiment, the apparatus for performing the method includes:

[0411] -Rotor-stator assembly,

[0412] - A premixing device for components (a), (b), and (d).

[0413] - One or more inlets for water, components (a), (b), (c), and (d),

[0414] - One or more outlets for oxidized lignin.

[0415] In one embodiment, the device is configured such that the inlets for the premixed components (a), (b), and (d) extend to the rotor-stator assembly, and the device further includes chambers.

[0416] The chamber has an inlet for component (c), and

[0417] The chamber has an outlet for oxidizing lignin.

[0418] A rotor-stator assembly is a device for processing materials, comprising a stator configured as an inner cone with a toothed ring. The stator is used in conjunction with a rotor having arms extending from a hub. Each of these arms has teeth that mesh with the teeth of the stator's toothed ring. With each rotor revolution, the material to be processed is conveyed outward a distance, subjected to intense shearing, mixing, and redistribution. The upright rotor arms and adjacent container chambers of the assembly allow for permanent rearrangement of the material from the inside out and provide multiple processing options for dried and / or highly viscous substances. Therefore, the assembly is highly effective for intensive mixing, kneading, fiberizing, decomposition, and similar processes important in industrial production. The upright arrangement of the housing facilitates the return of material from the periphery to the center of the equipment.

[0419] In one embodiment, the rotor-stator device used in the method according to the invention comprises a stator with a gear ring and a rotor with teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator device features a guide funnel protruding between the rotor arms, concentrating the incoming material flow into the central region of the container. The outer surface of the guide funnel defines an annular gap, throttling the material flow. A feed screw is provided on the rotor to feed material into the working area of ​​the device. The guide funnel retains the workpiece in the working area of ​​the device, while the feed screw generates increased material pressure in the central region.

[0420] For more details on the rotor-stator assembly used in one embodiment of the method, refer to US 2003 / 0042344 A1, which is incorporated herein by reference.

[0421] In one embodiment, the method is implemented using a rotor-stator assembly. In this embodiment, the mixing and reaction of the components take place within the same rotor-stator assembly.

[0422] In one embodiment, the method is implemented such that it uses two or more rotor-stator devices, wherein at least one rotor-stator device is used for mixing the components, and at least one rotor-stator device is used for reacting the components.

[0423] The method can be divided into two steps:

[0424] 1. Preparation of lignin substances (a) + (b) + (d);

[0425] 2. Oxidation of lignin.

[0426] Typically, two different types of rotor / stator machines are used:

[0427] 1. An open rotor / stator machine suitable for incorporating lignin powder into water at very high concentrations (30% to 50% by weight). The mixing intensity is relatively low, but special auxiliary equipment (inlet funnel, screw, etc.) is used to process high-viscosity materials. The circumferential speed is relatively low (up to 15 m / s). The machine can be used as a batch processing system or a continuous system.

[0428] 2. The inline rotor / stator machine has higher shear forces (circumferential speeds up to 55 m / s) – creating favorable conditions for very rapid chemical reactions. The machine should be used continuously.

[0429] In an open rotor / stator system, a high concentration (45 wt% to 50 wt%) of lignin / aqueous mass is prepared. Lignin powder is slowly added to warm water (30°C to 60°C) with the correct amounts of ammonia and / or alkali base added. This can be done in batch mode or by adding material intermittently / continuously, resulting in a continuous material flow to the next step.

[0430] The resulting material should be maintained at a temperature of approximately 60 degrees Celsius to keep the viscosity as low as possible, thus making the material pumpable. The lignin / water hot material with a pH of 9 to 12 is then transferred to the oxidation step using a suitable pump (such as a screw pump or other positive displacement pump).

[0431] In one embodiment, oxidation is carried out as a continuous online reaction in a closed rotor / stator system. An aqueous solution of ammonia and / or alkali is injected into the rotor / stator chambers using a metering pump at the point of highest turbulence / shear. This ensures a rapid oxidation reaction. The oxidized material (AOL) exits the online reactor and is collected in a suitable tank.

[0432] reaction products

[0433] The inventors unexpectedly discovered that the prepared oxidized lignins have very desirable reactivity, while exhibiting improved fire resistance when used in articles in which they are included in adhesive compositions, and improved long-term stability compared to previously known oxidized lignins.

[0434] Oxidized lignin also exhibits improved hydrophilicity.

[0435] An important parameter for the reactivity of the prepared oxidized lignin is the content of carboxylic acid groups in the oxidized lignin.

[0436] In one embodiment, the carboxyl content of the prepared oxidized lignin is 0.05 mmol / g to 10 mmol / g, such as 0.1 mmol / g to 5 mmol / g, such as 0.20 mmol / g to 2.0 mmol / g, such as 0.40 mmol / g to 1.5 mmol / g, such as 0.45 mmol / g to 1.0 mmol / g, based on the dry weight of component (a).

[0437] Another way to describe the content of carboxylic acid groups is to use the average content of carboxylic acid groups per lignin macromolecule according to the following formula:

[0438]

[0439] In one embodiment, in the prepared oxidized lignin, the average content of carboxylic acid groups in the macromolecule of each component (a) exceeds 1.5 groups, such as more than 2 groups, such as more than 2.5 groups.

[0440] Method III for preparing oxidized lignin

[0441] Oxidized lignin used as a component of the adhesive in this invention can be prepared by a method comprising contacting the following substances:

[0442] - Component (a), which includes one or more lignins;

[0443] - Component (b), which includes ammonia, and / or one or more amine components, and / or any salts thereof, and / or bases and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide;

[0444] - Component (c), which includes one or more oxidizing agents,

[0445] - Optional component (d), which is in the form of one or more plasticizers,

[0446] And a mixing / oxidation step, wherein an oxidized mixture is produced, followed by an oxidation step, wherein the oxidized mixture is allowed to continue reacting for a residence time of 1 second to 10 hours, such as 10 seconds to 6 hours, such as 30 seconds to 2 hours.

[0447] Components (a), (b), (c) and (d) are as defined above in Method II for the preparation of oxidized lignin.

[0448] In one embodiment, the method includes a premixing step that brings the components into contact with each other.

[0449] During the premixing step, the following components may come into contact with each other:

[0450] - Component (a) and component (b), or

[0451] - Component (a) and component (b) and component (c), or

[0452] - Component (a) and component (b) and component (d), or

[0453] - Components (a), (b), (c), and (d).

[0454] In this embodiment, the premixing step can be performed as a separate step, followed by a mixing / oxidation step. In this embodiment of the invention, it is particularly advantageous to contact components (a) and (b), and optionally component (d), with each other in the premixing step. In the subsequent mixing / oxidation step, component (c) is then added to the premix produced in the premixing step.

[0455] In this embodiment, the premixing step may correspond to the mixing / oxidation step. In the embodiment of the invention described above, components such as component (a), component (b), and component (c) are mixed and the oxidation process is started simultaneously. The subsequent residence time may be performed in the same apparatus as the equipment used to perform the mixing / oxidation step. This embodiment of the invention is particularly advantageous if component (c) is air.

[0456] The inventors have discovered that by following a mixing / oxidation step with an oxidation step, wherein the reaction mixture is preferably not further mixed, the oxidation rate can be controlled in a very efficient manner. Furthermore, since the oxidation step following the mixing / oxidation step requires less complex equipment, the cost of performing the method is reduced.

[0457] Another advantage is the exceptional stability of the resulting lignin oxide. Another unexpected advantage is the excellent adjustability of the viscosity of the resulting lignin oxide. Yet another unexpected advantage is the potential for very high concentrations of lignin oxide.

[0458] In one embodiment, the residence time is selected to allow the oxidation reaction to proceed to the desired degree of completion, preferably to complete completion.

[0459] System I for executing method III

[0460] In one implementation, the system for performing the method includes:

[0461] -At least one rotor-stator assembly,

[0462] - One or more inlets for water and components (a) and (b),

[0463] -One or more outlets of the rotor-stator assembly

[0464] - At least one reaction device, particularly at least one reaction tube, is arranged downstream of at least one or more outlets in the process flow direction.

[0465] In one embodiment, the system includes one or more inlets for component (c) and / or component (d).

[0466] In one embodiment, the system includes a premixing device.

[0467] 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).

[0468] In one embodiment of the invention, the premixing device includes inlets for water and components (a) and (b).

[0469] In the premixing step, component (c) may also be mixed with the three components mentioned above (water, component (a), and component (b)). The premixing device may then have additional inlets for component (c). If component (c) is air, the premixing device may be formed of an open mixing container, in which case component (c) has already come into contact with the other components (water, component (a), and component (b)) through the openings of the container. Also in the described embodiment of the invention, the premixing device may optionally include an inlet for component (d).

[0470] In one implementation, the system is constructed in such a way that:

[0471] The inlets for components (a), (b), and (d) are the inlets for the premixing device, particularly for open rotor-stator devices.

[0472] Therefore, the system also includes an additional rotor-stator assembly.

[0473] The additional rotor-stator assembly has an inlet for component (c) and an outlet for lignin oxidation.

[0474] The premixing step and the mixing / oxidation step can be performed simultaneously. In this case, the premixing unit and the mixing / oxidation unit are a single unit, namely the rotor-stator unit.

[0475] In one embodiment, a rotor-stator device for use with the method according to the invention includes a stator having a gear ring and a rotor having teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator device features a guide funnel protruding between the rotor arms to concentrate the incoming material flow into a central region of the container. The outer surface of the guide funnel defines an annular gap to throttle the material flow. A feed screw is provided on the rotor to feed material into the working area of ​​the device. The guide funnel retains the workpiece in the working area of ​​the device, while the feed screw generates increased material pressure in the central region.

[0476] System II for executing method III

[0477] In one implementation, the system for performing the method includes:

[0478] - One or more inlets for water, components (a) and (b),

[0479] - At least one mixing and oxidation device having one or more outlets, and

[0480] - At least one mixer / heat exchanger is arranged downstream of at least one or more outlets in the process flow direction, wherein the mixer / heat exchanger includes a temperature control device.

[0481] In one implementation, the system includes one or more additional inlets for component (c) and / or component (d).

[0482] In one embodiment, the system includes a premixing device.

[0483] 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).

[0484] In one embodiment, the premixing device includes inlets for water and components (a) and (b).

[0485] In the premixing step, component (c) may also be mixed with the three components mentioned above (water, component (a), and component (b)). The premixing device may then have additional inlets for component (c). If component (c) is air, the premixing device may be formed of an open mixing container, in which case component (c) has already come into contact with the other components (water, component (a), and component (b)) through the openings of the container. Also in this embodiment of the invention, the premixing device may optionally include an inlet for component (d).

[0486] In one embodiment, the system is constructed such that the inlets for components (a), (b), and (d) are inlets for an open rotor-stator assembly, thereby the system also includes a mixer / heat exchanger having an inlet for component (c) and an outlet for oxidizing lignin.

[0487] The premixing step and the mixing / oxidation step can be performed simultaneously. In this case, the premixing unit and the mixing / oxidation unit are a single unit.

[0488] In one embodiment, a rotor-stator device for the method of the present invention includes a stator having a gear ring and a rotor having teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator device features a guide funnel protruding between the rotor arms to concentrate the incoming material flow into a central region of the container. The outer surface of the guide funnel defines an annular gap to throttle the material flow. A feed screw is provided on the rotor to feed material into the working area of ​​the device. The guide funnel retains the workpiece in the working area of ​​the device, while the feed screw generates increased material pressure in the central region.

[0489] Of course, other devices can also be used as premixing devices. Furthermore, the premixing step can be carried out in a mixing and oxidation device.

[0490] 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 the components. One design of a static mixer is a plate mixer, and another common type consists of mixing elements contained within a cylindrical (tube) or square housing.

[0491] In one embodiment, the mixer / heat exchanger is configured as a multi-tube heat exchanger with mixing elements. The mixing elements are preferably stationary devices through which the mixture must flow, thereby being mixed as a result of the flow. The mixer / heat exchanger can also be configured as a reciprocating flow reactor.

[0492] The adhesive layer is hydrophilic, meaning it attracts water. Hydrophilicity has its usual meaning in this field.

[0493] The hydrophilicity of at least one adhesive layer can be defined by its contact angle with water. Preferably, the MMVF of at least one adhesive layer has a contact angle with water of less than 90°. The contact angle is measured by a seated drop method. Any seated drop method can be used, such as a contact angle goniometer. In practice, a droplet is placed on a solid surface, and an image of the droplet is recorded promptly. The static contact angle is then defined by fitting the Yang-Laplace equation around the droplet. The contact angle is given by the angle between the calculated droplet shape function and the sample surface, and its projection in the droplet image is called the baseline. The equilibrium contact angle is used for further evaluation and calculation of the surface free energy using the Owens-Wendt-Rabel-Kaeble method. Methods for calculating the contact angle of materials with water are well known to those skilled in the art.

[0494] The hydrophilicity of an MMVF matrix sample can also be determined by measuring its sinking time. An MMVF matrix sample with dimensions of 100x100x100 mm is required to determine the sinking time. A container with a minimum size of 200x200x200 mm is filled with water. The sinking time is the time from the moment the sample first contacts the water surface until the sample is completely submerged. The sample is brought into contact with water so that a 100x100 mm cross-section initially contacts the water. The sample then needs to sink a distance of more than 100 mm to be completely submerged. The faster the sample sinks, the stronger its hydrophilicity. If the sinking time is less than 120 seconds, the MMVF matrix is ​​considered hydrophilic. A sinking time of less than 60 seconds is preferred. In practice, the sinking time of a drainage device may be a few seconds, for example, less than 15 seconds.

[0495] The advantage of a hydrophilic adhesive layer is that it allows the damping pad to absorb, store, and drain water. Using the damping pad according to this embodiment extends the usability of artificial stadiums because the pad absorbs and stores moisture, thereby improving the stadium's athletic performance without the need for a plastic infill layer. The damping pad can actively prevent or manage flooding by absorbing water. The damping pad of the present invention can extend the usability of stadiums by lowering the surface temperature, i.e., surface cooling. This is because the damping pad can store water and can transport it upwards to the infill layer (if present) or expose it to direct contact with the air for evaporation. Therefore, the area between the stadium surfaces (i.e., the artificial turf) remains moist and maintains a stable temperature through evaporation.

[0496] The adhesive layer of the shock-absorbing pad according to the invention may optionally contain a wetting agent. The wetting agent has its general meaning in the art and may be a cationic, anionic, or nonionic surfactant.

[0497] The adhesive layer of the shock-absorbing pad may contain nonionic wetting agents such as...

[0498] The adhesive layer of the shock-absorbing pad may contain an ionic surfactant, more preferably an alkyl ether sulfate surfactant wetting agent. The wetting agent can be an alkali metal alkyl ether sulfate or an alkyl ether ammonium sulfate. Sodium alkyl ether sulfate is a preferred wetting agent. Commercially available alkyl ether sulfate surfactant wetting agents are... Wetting agents can also be linear alkylbenzene sulfonate anionic surfactants.

[0499] Over time, some nonionic wetting agents may wash away from the adhesive layer of the shock-absorbing pad. Therefore, ionic wetting agents, especially anionic wetting agents such as linear alkylbenzene sulfonates or... These will not be washed away from the adhesive layer of the damping pad to the same extent.

[0500] The adhesive layer of the shock-absorbing pad may contain 0.01% to 1% by weight of a wetting agent, preferably 0.05% to 0.5% by weight, and more preferably 0.1% to 0.3% by weight.

[0501] However, the inventors discovered that a wetting agent is not necessary for the adhesive layer of the shock-absorbing pad according to the invention. This is believed to be due to the nature of the adhesive composition. Therefore, it is preferable that the adhesive layer of the shock-absorbing pad does not contain any wetting agent. This means that the adhesive layer of the shock-absorbing pad preferably does not contain a wetting agent, i.e., contains 0% by weight of a wetting agent.

[0502] This has several advantages. First, it reduces the amount of additives in the damping pad, which is environmentally friendly and also saves costs. Wetting agents are often made from non-renewable resources, so avoiding their use is beneficial. Furthermore, wetting agents can be washed off the damping pad. This is problematic because the wetting agent can contaminate the surrounding ground. When the wetting agent is washed off, it also alters the properties of the damping pad's adhesive layer, often changing cushioning, drainage, and permeability, making it difficult to predict the pad's performance. Avoiding the use of wetting agents avoids these problems.

[0503] The water-holding capacity of the adhesive layer is preferably at least 50% of its volume, more preferably at least 60%, and most preferably at least 70% or at least 80%. The greater the water-holding capacity, the more water can be stored in a given volume of adhesive layer. Due to the open porous structure of MMVF, the adhesive layer has a high water-holding capacity.

[0504] Preferably, when discharging water, the amount of water retained by the adhesive layer is less than 20% by volume, more preferably less than 10% by volume, and most preferably less than 5% by volume, based on the volume of the adhesive layer. The retained water can be from 2% to 20% by volume, for example from 5% to 10% by volume. The lower the amount of water retained by the adhesive layer, the greater its ability to absorb more water.

[0505] The preferred buffering capacity of the adhesive layer, i.e., the difference between the maximum amount of water it can hold and the amount of water retained when the adhesive layer releases water, is at least 60% by volume, preferably at least 70% by volume, and most preferably at least 80% by volume. Based on the volume of the adhesive layer, the buffering capacity can be from 60% to 90% by volume, for example, from 60% to 85% by volume. The advantage of this high buffering capacity is that the adhesive layer can buffer a greater volume of water for a given amount; that is, the adhesive layer can store a large amount of water when needed and release a large amount of water to the filler layer (if present), or by evaporating a large amount of water from the surface. The buffering capacity is so high because the MMVF matrix requires low suction pressure to remove moisture from the MMVF adhesive layer.

[0506] The water-holding capacity, water retention capacity and buffering capacity of the adhesive layer can be measured according to EN 13041:1999.

[0507] Preferably, at least one adhesive layer is substantially oil-free. This means that the adhesive layer contains less than 1% by weight of oil, preferably less than 0.5% by weight of oil. Most preferably, the adhesive layer is oil-free. This means that the adhesive layer contains 0% by weight of oil. Oil is typically added to MMVF substrates used for purposes such as sound insulation, electrical insulation, thermal insulation, and fire resistance. However, the inventors unexpectedly discovered that when the adhesive board is oil-free or substantially oil-free, its hydrophilicity is sufficient to absorb and expel moisture.

[0508] The hydrophilicity of the adhesive layer can be defined by its hydroconductivity. Preferably, at least one adhesive layer has a hydroconductivity of 5 m / day to 200 m / day, more preferably 10 m / day to 50 m / day. The hydroconductivity is determined according to ISO 17312:2005. The advantage of this hydroconductivity is that the shock-absorbing pad can absorb excess water and remove it from the stadium at a sufficient speed to prevent flooding. As mentioned above, this can be achieved by including an adhesive sheet that is oil-free or substantially oil-free and / or by including an adhesive according to the invention.

[0509] At least one adhesive layer can be made by any method known to those skilled in the art for producing MMVF articles. Typically, a mineral charge is provided and melted in a furnace to form a mineral melt. The melt is then formed into fibers by centrifugal fiberization, for example using a spinning cup or cascade spinning machine, thereby forming fiber clumps. These fibers are then collected and consolidated. A binder is typically added during the fiberization stage by spraying it into the fiber-forming clumps. These methods are well known in the art.

[0510] In one embodiment, the adhesive plate comprises only one adhesive layer. Preferably, the adhesive plate is formed by one adhesive layer, i.e., no other layers exist.

[0511] In another embodiment, the adhesive plate may include at least two adhesive layers: a first adhesive layer and another adhesive layer. This embodiment is shown in... Figure 2 The shock-absorbing pad (10) includes an adhesive plate (20) having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer (30a) comprising artificial glass fibers (MMVF) bonded with a cured adhesive composition according to the invention. The adhesive plate (20) also includes another adhesive layer (30b) comprising artificial glass fibers (MMVF) bonded with a cured adhesive composition according to the invention.

[0512] The shock-absorbing pad also includes an upper film layer (40a) bonded to the upper main surface of the adhesive plate (20) and a lower film layer (40b) bonded to the lower main surface of the adhesive plate (20).

[0513] In this embodiment, the first adhesive layer is preferably as described above, i.e., at least one adhesive layer. The advantage of an adhesive plate with two adhesive layers is that it can be used to improve the durability of the shock-absorbing pad while meeting the requirements for motion performance (e.g., vibration absorption and energy recovery).

[0514] In this embodiment, the thickness of the other adhesive layer is preferably in the range of 3 mm to 10 mm, more preferably 5 mm to 8 mm. This means that when the adhesive plate includes two adhesive layers, the total thickness of the adhesive plate is preferably 15 mm to 50 mm.

[0515] In this embodiment, the density of the other adhesive layer is preferably 175 kg / m³. 3 Up to 300kg / m 3 Within the range, preferably 200kg / m 3 Up to 260kg / m 3 Within the range, the optimal value is 235 kg / m³. 3 Preferably, the density of the other adhesive layer is different from the density of the first adhesive layer. More preferably, the density of the other adhesive layer is lower than the density of the first adhesive layer.

[0516] In this embodiment, it is preferable to bond the second adhesive layer to the first adhesive layer. This can be achieved by producing both layers simultaneously and curing them together. Preferably, the second adhesive layer is located below the first adhesive layer. Preferably, the second adhesive layer forms the lower surface of the adhesive plate, and the first adhesive layer forms the upper surface of the adhesive plate.

[0517] The other adhesive layer may have any of the preferred features described above for at least one adhesive layer.

[0518] Preferably, based on the weight of the adhesive layer, another adhesive layer comprises 1.0 wt% to 6.0 wt% of a cured adhesive composition, preferably 2.5 wt% to 4.5 wt%, and most preferably 3.0 wt% to 3.8 wt%. An advantage associated with this 3.0 wt% to 3.8 wt% range is that this range allows the shock-absorbing pad to have the desired stiffness and elasticity.

[0519] Preferably, the adhesive layer is hydrophilic, meaning it absorbs water. For at least one adhesive layer, the hydrophilicity of the MMVF matrix sample can be determined as described above.

[0520] Another advantage of the adhesive layer being hydrophilic is that it allows the damping pad to absorb, store, and drain water. Using the damping pad according to this embodiment, the usability of the artificial stadium is extended due to the damping pad's absorption and storage of water, thereby improving the stadium's athletic performance. The damping pad can actively prevent or manage flooding by absorbing water. The damping pad according to the invention can extend the stadium's usability by lowering the surface temperature (i.e., surface cooling). This is because the damping pad can store water and can transport the water upwards to the infill layer (if present) or allow it to evaporate through direct contact with the air. Therefore, the area between the stadium surfaces (i.e., the artificial turf) remains moist, maintaining a stable temperature through evaporation.

[0521] Another adhesive layer of the shock-absorbing pad may include 0.01% to 1% by weight of a wetting agent, preferably 0.05% to 0.5% by weight, more preferably 0.1% to 0.3% by weight. However, the inventors have found that a wetting agent is not necessary for the adhesive layer of the shock-absorbing pad of the present invention. This is believed to be due to the nature of the adhesive composition. Therefore, it is preferred that the other adhesive layer of the shock-absorbing pad does not contain any wetting agent. This means that the other adhesive layer of the shock-absorbing pad preferably does not contain a wetting agent, i.e., contains 0% by weight of a wetting agent.

[0522] The hydrophilicity of the other adhesive layer can be defined based on its contact angle with water. Preferably, the contact angle of the other MMVF layer with water is less than 90°. The contact angle is measured as described above.

[0523] Preferably, the other adhesive layer is substantially oil-free. This means that the other adhesive layer contains less than 1% by weight of oil, preferably less than 0.5% by weight of oil. Most preferably, the other adhesive layer is oil-free. This means that the other adhesive layer has 0% by weight of oil. Oil is typically added to MMVF substrates used for purposes such as sound insulation, insulation, heat insulation, and fire retardancy. However, the inventors have unexpectedly discovered that when the adhesive sheet is oil-free or substantially oil-free, it has sufficient hydrophilicity to absorb and drain water. In this embodiment, as described above, the adhesive composition can be hydrophilic, amphiphilic, or hydrophobic. Preferably, when the adhesive composition is hydrophobic or amphiphilic, the adhesive sheet is oil-free or substantially oil-free.

[0524] The hydrophilicity of the adhesive layer can be defined by its hydrodynamic conductivity. Preferably, the hydrodynamic conductivity of the other adhesive layer is from 5 m / day to 200 m / day, more preferably from 10 m / day to 50 m / day. The hydrodynamic conductivity is determined according to ISO 17312:2005. This hydrodynamic conductivity has the advantage that the shock-absorbing pad can absorb excess water and remove it from the stadium at a sufficient speed to prevent flooding. As mentioned above, this can be achieved by comprising an adhesive plate that is oil-free or substantially oil-free and / or the adhesive of the present invention.

[0525] In a preferred embodiment, at least one adhesive layer has a thickness of 15 mm and a density of 275 kg / m³. 3 Furthermore, the thickness of the other adhesive layer is 5 mm to 8 mm, and the density is 235 kg / m³. 3 The advantage of this implementation is that it improves the durability of the shock-absorbing pad while meeting the requirements of athletic performance (e.g., shock absorption and energy recovery). The top layer improves durability, while the bottom layer optimizes shock absorption and energy recovery.

[0526] Preferably, the adhesive plate is hydrophilic. For at least one adhesive layer, it can be implemented as described above.

[0527] Preferably, the adhesive plate is vertically compressed to less than 10% of its initial vertical thickness, more preferably 1% to 9%, and most preferably 3% to 8%. This is achieved through a compression treatment or pretreatment. The advantage of this treatment is that the shock-absorbing pad deforms less when properly positioned in the stadium; that is, it results in reduced vertical deformation. Standards that artificial fields for football and hockey must meet include specific vertical deformation values. The inventors unexpectedly discovered that compressing the adhesive plate reduces the vertical deformation value of the shock-absorbing pad in use, in which the adhesive plate is compressed to less than 10% of its initial vertical thickness.

[0528] Compression can be performed by any method; however, it is preferred to compress the adhesive plate by one or more pairs of rollers.

[0529] The adhesive plate according to the invention is bonded to the upper film layer and / or the lower film layer. The upper film layer may be bonded to the upper main surface of the adhesive plate. The lower film layer may be bonded to the lower main surface of the adhesive plate.

[0530] The advantage of having a top membrane layer is that it absorbs point loads from above. For example, when using a stadium, this will apply pressure to the damping pad. The top membrane layer enables the damping pad to meet the stringent requirements of artificial turf fields for hockey and football.

[0531] The advantage of having a lower membrane layer is that it absorbs point loads from below. For example, a damping pad might be placed on an uneven surface in the ground, such as on a gravel layer. When a stadium is used, this will create point loads on the bottom layer of the damping pad. The lower membrane layer enables the damping pad to meet the stringent requirements of artificial turf fields for hockey and football.

[0532] The advantage of having upper and lower films bonded to the adhesive layer is that, compared to non-adhesive films, the upper and lower films bonded to the adhesive layer provide significantly higher point load resistance. Installing individual products is also easier, simplifying the installation process.

[0533] The upper and lower film layers are preferably bonded or heat-melted onto the adhesive plate. Ethylene vinyl acetate (EVA) or polyethylene (PE) adhesive is most preferably used to bond the upper and lower film layers to the adhesive plate.

[0534] Preferably, the upper film layer extends across and adheres to the entire upper surface of the adhesive plate. Preferably, the lower film layer extends across and adheres to the entire lower surface of the adhesive plate. This produces a more stable and durable shock-absorbing pad.

[0535] Preferably, the upper film layer comprises glass fibers, polymer fibers, glass microfibers, or mixtures thereof. Most preferably, the upper film layer comprises a glass fiber layer, preferably a nonwoven glass fiber layer.

[0536] Furthermore, the upper film layer preferably comprises a mesh layer, wherein the mesh layer contains glass fibers, polymer fibers, or mixtures thereof. Most preferably, the upper film layer comprises a mesh of glass fibers, wherein the yarns in the mesh have a density of 25 tex to 40 tex, more preferably 32 tex to 36 tex.

[0537] Preferably, the upper film layer comprises an integral (i.e., bonded together) nonwoven glass fiber layer and a mesh layer.

[0538] Preferably, the lower film layer comprises glass fibers, polymer fibers, glass microfibers, or mixtures thereof.

[0539] This invention relates to a shock-absorbing pad for artificial stadiums. The shock-absorbing pad is as described above. It may have any of the preferred features described herein.

[0540] This invention also relates to a method for manufacturing a shock-absorbing pad. The method includes the following steps:

[0541] (i) Provide synthetic glass fibers;

[0542] (ii) Spraying artificial glass fibers with an aqueous adhesive composition;

[0543] (iii) Collect and consolidate artificial glass fibers and cure the aqueous adhesive composition to form an adhesive layer;

[0544] (iv) Provide an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer;

[0545] The adhesive composition before curing includes:

[0546] - One or more components in the form of oxidized lignin (i);

[0547] - Components in the form of one or more crosslinking agents (ii);

[0548] - One or more components in the form of plasticizers (iii).

[0549] The shock-absorbing pad may have any of the preferred features discussed in detail above.

[0550] Man-made glass fibers can be made from mineral melts. Mineral melts are provided in a conventional manner by supplying mineral materials and melting them in a furnace. The furnace can be any type of furnace known for producing MMVF mineral melts, such as a shaft furnace, cupola furnace, pot furnace, or cyclone furnace.

[0551] MMVFs can be formed from mineral melts by any suitable method. Fiberization can be carried out via a spinning cup process, in which the melt is centrifugally extruded through orifices in the wall of a rotating cup (spinning cup, also known as an internal centrifuge). Alternatively, fiberization can be carried out by centrifugal fiberization, by spraying the melt onto the outer surface of a fiberizing rotor and peeling it off, or by peeling it off from a cascade of multiple fiberizing rotors rotating about a substantially horizontal axis (cascaded spinnerets).

[0552] The melt is thus formed into a cloud of fibers entrained in the air, and the fibers are collected as a web on a conveyor belt and carried away from the fiberizing device. The fiber web is then consolidated, which may include cross-laying and / or longitudinal compression and / or vertical compression and / or winding onto a mandrel to produce cylindrical articles for pipe insulation. Other consolidation processes may also be performed.

[0553] The adhesive composition is preferably applied to the fibers while they are clouds carried in the air. Alternatively, it can be applied after they have been collected onto a conveyor belt, but this is less preferred.

[0554] After consolidation, the consolidated fiber web is fed into a curing device to cure the adhesive.

[0555] In one embodiment, curing is carried out at temperatures ranging from 100°C to 300°C, such as 170°C to 270°C, 180°C to 250°C, or 190°C to 230°C.

[0556] In a preferred embodiment, curing is carried out in a conventional curing oven used for mineral wool production, preferably at a temperature of 150°C to 300°C, such as 170°C to 270°C, 180°C to 250°C, or 190°C to 230°C.

[0557] In one implementation, the curing time is from 30 seconds to 20 minutes, such as from 1 minute to 15 minutes, such as from 2 minutes to 10 minutes.

[0558] In a typical implementation, curing is carried out at a temperature of 150°C to 250°C for 30 seconds to 20 minutes.

[0559] The curing process can begin immediately after the adhesive is applied to the fibers. Curing is defined as a process in which the adhesive composition undergoes physical and / or chemical reactions. In the case of chemical reactions, the molecular weight of the compounds in the adhesive composition is typically increased, thereby increasing the viscosity of the adhesive composition, usually until the adhesive composition reaches a solid state. The cured adhesive composition bonds the fibers to form a structurally adhered fibrous matrix.

[0560] In one embodiment, the adhesive in contact with the mineral fibers is cured in a hot press.

[0561] Curing adhesives that come into contact with mineral fibers in a hot press has a unique advantage: it allows for the production of high-density products.

[0562] In one embodiment, the curing process includes pressure drying. Pressure can be applied by blowing air or gas over / on the mixture of mineral fibers and adhesive.

[0563] Preferably, the method according to the invention further includes a step of pre-treating the adhesive plate by compression, wherein the compression vertical deformation of the adhesive plate is less than 10%, preferably 1% to 9%, more preferably 3% to 8%. This is achieved through compression treatment or pre-treatment. The advantage of this treatment is that the deformation will be smaller when the shock-absorbing pad is placed in the stadium, i.e., it results in a reduction in vertical deformation. Standards that artificial fields for football and hockey must meet include specific vertical deformation values. The inventors unexpectedly discovered that compressing the adhesive plate, wherein it is compressed to less than 10% of its original vertical thickness, reduces the vertical deformation value of the shock-absorbing pad in use.

[0564] Compression can be performed by any method; however, it is preferred to compress the adhesive plate by one or more pairs of rollers.

[0565] The method may also include the following steps:

[0566] (i) Adhere the upper film layer to the upper surface of the adhesive plate; and / or

[0567] (ii) Adhere the lower film layer to the lower surface of the adhesive plate.

[0568] In a preferred embodiment, the bonding in steps (i) and / or (ii) is performed by glue or adhesive.

[0569] In an alternative implementation, the bonding in steps (i) and / or (ii) is performed by placing an adhesive between the film layer and the adhesive plate and curing the adhesive.

[0570] The present invention also relates to a method of using shock-absorbing pads in a stadium to provide a vibration-absorbing surface, comprising the steps of: placing a shock-absorbing pad or a group of shock-absorbing pads below the surface of the stadium, wherein the shock-absorbing pad comprises: an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing comprises:

[0571] - Component (i), which is one or more forms of oxidized lignin;

[0572] - Component (ii), which is in the form of one or more crosslinking agents;

[0573] - Component (iii), which is in the form of one or more plasticizers.

[0574] The present invention also relates to the use of a shock-absorbing pad in a stadium for absorbing vibrations, wherein the shock-absorbing pad comprises: an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing comprises:

[0575] - Component (i), which is one or more forms of oxidized lignin;

[0576] - Component (ii), which is in the form of one or more crosslinking agents;

[0577] - Component (iii), which is in the form of one or more plasticizers.

[0578] The shock-absorbing pad may have any of the preferred features discussed in detail above.

[0579] The present invention also relates to the use of a shock-absorbing pad in a stadium for absorbing and / or draining water, wherein the shock-absorbing pad comprises: an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing comprises:

[0580] - Component (i), which is one or more forms of oxidized lignin;

[0581] - Component (ii), which is in the form of one or more crosslinking agents;

[0582] - Component (iii), which is in the form of one or more plasticizers.

[0583] The shock-absorbing pad may have any of the preferred features discussed in detail above.

[0584] The shock-absorbing pad can absorb rainwater from the ground or water supplied by an underground irrigation system. In cases of excessive rainfall, the pad can drain water to the underlying subbase. The pad provides horizontal drainage, meaning water can be drained and collected on both sides of the stadium.

[0585] The present invention also relates to the use of a shock-absorbing pad for cooling the surface temperature of a stadium, wherein the shock-absorbing pad comprises: an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing comprises:

[0586] - Component (i), which is one or more forms of oxidized lignin;

[0587] - Component (ii), which is in the form of one or more crosslinking agents;

[0588] - Component (iii), which is in the form of one or more plasticizers.

[0589] The damping pad may have any of the preferred features discussed in detail above. The term “cooling” has its usual meaning in this field, namely, reducing temperature. This means reducing the temperature of the stadium and its surrounding environment. This is achieved by the damping pad layer absorbing water, such as rainwater from the ground above or water from underground irrigation systems. This water is retained in the damping pad and transferred to the surface, where it evaporates due to air temperature and wind.

[0590] This invention relates to a stadium, comprising:

[0591] (i) Lower base layer;

[0592] (ii) Upper grass layer and / or artificial turf layer;

[0593] (iii) A shock-absorbing pad layer located between the base layer and the grass or artificial turf layer;

[0594] The damping pad layer includes at least one damping pad, the damping pad including an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer, the adhesive layer including artificial glass fiber (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing includes:

[0595] - Component (i), which is one or more forms of oxidized lignin;

[0596] - Component (ii), which is in the form of one or more crosslinking agents;

[0597] - Component (iii), which is in the form of one or more plasticizers.

[0598] The shock-absorbing pad may have any of the preferred features discussed in detail above.

[0599] The inventors have discovered that the shock-absorbing pad according to the present invention can be used to form sports fields without the need for a plastic filler layer. This is because the shock-absorbing pad can absorb and store moisture. The water-retaining capacity of the shock-absorbing pad means that the required sports performance can be achieved without a plastic filler layer. Therefore, this results in the numerous benefits mentioned above. Furthermore, without the need for a plastic filler layer, there is no microplastic pollution to the environment (including the marine environment).

[0600] Preferably, the base layer comprises stone, more preferably compacted gravel or concrete. The depth of the base layer is preferably 20 cm to 50 cm. Preferably, the base layer is applied to a level surface.

[0601] The upper layer may comprise grass, artificial grass, or a combination of grass and artificial grass. Preferably, the upper layer comprises artificial grass. It may be 100% artificial grass or a blend of natural and synthetic grass. The depth of this layer is preferably 40 mm to 70 mm. The artificial grass fibers are preferably provided in the form of a mat, but can be fabricated on-site by tufting the artificial grass into a matrix layer above the shock-absorbing mat. The artificial grass fibers are preferably made of synthetic fibers, optionally coated with polysiloxane.

[0602] like Figure 3 As shown. As described herein, the damping pad (100) is placed above the base layer (200). Then, the top layer of grass or artificial grass (300) is placed on top of the damping pad.

[0603] The stadium may also include: (iv) an infill layer, situated between or within the shock-absorbing pad layer and the grass and / or artificial turf layer, wherein the infill layer comprises sand or a non-plastic material. The optional infill layer is primarily intended to stabilize the grass or artificial turf, rather than specifically meeting athletic performance requirements. The weight of the sand or non-plastic material prevents the grass or artificial turf layer from shifting out of position and holds the grass fibers in place.

[0604] Non-plastic materials include silica particles, cork, or biological materials such as granular corn cobs.

[0605] Preferably, the filler layer does not contain any plastic material, meaning it contains less than 5% plastic, preferably less than 2%, and more preferably less than 1%.

[0606] The present invention also relates to a method for constructing a stadium, comprising the following steps:

[0607] (i) Provide the lower base layer;

[0608] (ii) Provide a shock-absorbing pad layer above the base layer;

[0609] (iii) Provide an upper grass layer and / or artificial grass layer above the shock-absorbing pad;

[0610] The damping pad layer includes at least one damping pad, the damping pad including an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer, the adhesive layer including artificial glass fiber (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing includes:

[0611] - Component (i), which is one or more forms of oxidized lignin;

[0612] - Component (ii), which is in the form of one or more crosslinking agents;

[0613] - Component (iii), which is in the form of one or more plasticizers.

[0614] Example 1

[0615] Six different matrices were prepared and their compressive strength was analyzed.

[0616] Product 1: MMVF matrix containing 2.1% by weight of formaldehyde-free adhesive according to the present invention; density 76 kg / m³ 3 3.5 liters / ton wetting agent The adhesive in this product has the following composition:

[0617] -AOL (ammonia-oxidized lignin): 1000kg (284kg lignin UPM BioPiva100, 57kg H2O2 (35%), 53kg NH4OH (24.7%), 506kg water)

[0618] - Plasticizer (PEG 200): 44 kg

[0619] - Crosslinking agent (Primid XL552-β-hydroxyalkyl-amide (HAA) crosslinking agent provided by EMS-Chemie AG): 22kg.

[0620] The Primid XL552 has the following structure:

[0621]

[0622] Product 2: MMVF matrix containing 2.1% by weight of formaldehyde-free adhesive according to the present invention; density 76 kg / m³ 3 No wetting agent. The adhesive in this product is the same as that in product 1 above.

[0623] Comparative Product 1: MMVF matrix containing 2.6% by weight PUF adhesive; density 77 kg / m³ 3 5.7 liters / ton wetting agent (linear alkyl sulfonate). The adhesive in this product is made from the following materials:

[0624] -Phenolic urea-formaldehyde resin: 329 liters

[0625] Water: 1337 liters

[0626] - Ammonia water: 13 liters

[0627] - Ammonium sulfate: 30.5 liters

[0628] Aminosilane VS-142 from Momentive: 1.6 liters.

[0629] Comparative Product 2: MMVF matrix containing 2.6% by weight PUF adhesive; density 77 kg / m³ 3 3.5 liters / ton wetting agent The adhesive in this product is the same as the adhesive in the comparative product 1 described above.

[0630] Comparative product 3: MMVF growth substrate containing 2.8% by weight of formaldehyde-free binder; density 78 kg / m³ 3 6.7 liters / ton of wetting agent (linear alkyl sulfonate). The adhesive in this product is made by reacting the following substances together:

[0631] 185kg AAA resin: 239kg glucose: 575kg water: 1.1kg silane.

[0632] The preparation method of AAA resin is as follows:

[0633] 90 kg of diethanolamine (DEA) was charged into a 400 L reactor and heated to 60 °C. Then, 75 kg of tetrahydrophthalic anhydride (THPA) was added. After heating and maintaining the temperature 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.

[0634] Comparative product 4: MMVF growth substrate containing 2.8% by weight of formaldehyde-free binder; density 78 kg / m³ 3 3.5 liters / ton of wetting agent The adhesive in this product is the same as the adhesive in the comparative product 3 mentioned above.

[0635] The results are as follows Figures 4A to 4E As shown, wet and dry compression tests were performed on the insulating material according to the 1996 standard EN826, and the deviations are as follows:

[0636] -In EN 826, the initial deformation X0 and the critical compressive strength σ are not calculated. c and σ e .

[0637] - EN standards for insulating materials require that test specimens be stored and measured at (23±5) °C. In case of dispute, they should be stored and measured at (23±2) °C and (50±5)% relative humidity, as this is considered to have no effect on mineral wool.

[0638] The amount of adhesive used in articles 1 and 2 of the present invention is significantly lower than that used in comparative articles 1 to 4. However, despite this, comparable compression results are observed compared to PUF adhesive and another formaldehyde-free adhesive. Therefore, equivalent compressive strength can be achieved using a smaller amount of the adhesive of the present invention. It is anticipated that increasing the amount of adhesive in the present invention to 2.8% by weight will further improve the compressive strength. However, achieving comparable compression results at a lower amount provides the additional advantage of reducing the total amount of adhesive in the articles.

[0639] Example 2

[0640] The average buffer, average drainage, and average permeability of the MMVF sample were measured.

[0641] The following measures buffering, drainage, and seepage are described:

[0642] - First, a Plexis glass column is prepared using sand and the MMVF sample to be tested. The column is first filled with sand to a height of approximately 25 cm. Next, a drainage device is placed on top of the sand. Then, the column is filled with water from an adjacent tank.

[0643] - Note the time required for the weight to increase and for 5 liters of water to be added to the column. Fill the column until water is visible at the top of the mineral wool. Then stop adding water. Now all the water is buffered within the mineral wool.

[0644] Next, drain the column. Record the time and weight for every 2 liters of water drained from the column. This process takes approximately 2 hours. Then close the drain valve.

[0645] - Remaining water seeps into the filler sand, which exits the column through a hose and enters the bucket. Measure the weight and time after reducing 2 liters of water for as long as possible.

[0646] - Repeatedly measure the cycles of buffering, drainage, and seepage.

[0647] The matrices described in Table 1 below were tested, and the results are as follows: Figure 5 , 6 As shown in Figure 7.

[0648] Table 1

[0649]

[0650] The adhesive and PUF adhesive of the present invention are prepared according to the above Example 1.

[0651] The results show that the samples of the present invention, with or without wetting agent, exhibited similar properties. Therefore, the wetting agent had no significant effect.

[0652] The samples of this invention (samples 1 and 2) are faster than all other comparisons using mineral wool type buffers.

[0653] Samples 1 and 2 (according to the present invention) drained water faster than samples 3 and 4, and were similar to sample 5.

[0654] Samples 1 and 2 (according to the present invention) permeated faster than all other mineral wool types used in the comparison.

[0655] Example 3

[0656] The adhesive used to prepare the shock-absorbing pad of the present invention is as follows:

[0657] 3267 kg of water was added to a 6000 L reactor, followed by 287 kg of ammonia (24.7%). Then, 1531 kg of Lignin UPM BioPiva 100 was slowly added over a period of 30 to 45 minutes. The mixture was heated to 40°C and maintained at that temperature for 1 hour. After 1 hour, the insoluble lignin was examined. This was done by examining the solution on a glass plate or a Hegman gauge. The insoluble lignin was visible as small particles in a brown binder. During the dissolution step, the color of the lignin solution changed from brown to a glossy black.

[0658] After the lignin is completely dissolved, add 1 liter of defoamer (from... of 11-10). Maintain the batch temperature at 40°C.

[0659] Then, 307.5 kg of 35% hydrogen peroxide was added. The hydrogen peroxide was fed at a rate of 200 L / h to 300 L / h. The first half of the hydrogen peroxide was added at a rate of 200 L / h, and then the feed rate was increased to 300 L / h.

[0660] During the addition of hydrogen peroxide, the temperature in the reaction mixture is controlled by heating or cooling so that the final reaction temperature reaches 65°C.

[0661] After reacting at 65°C for 15 minutes, the reaction mixture was cooled to below 50°C. The resulting resin had a COOH value of 1.2 mmol / g solids.

[0662] An adhesive was prepared from the above AOL resin by adding 270 kg of polyethylene glycol 200 and 433 kg of a 31% solution of Primid XL-552 to water.

[0663] Analysis of the final adhesive revealed the following data:

[0664] Solid content: 18.9%; pH: 9.7; Viscosity: 25.5 mPa·s; Density: 1.066 kg / l

[0665] Examples of Lignin Oxidation

[0666] Example I

[0667] Example 1A – Lignin oxidation in ammonia solution using hydrogen peroxide:

[0668] The amounts of ingredients used according to Example IA are provided in Tables IA 1.1 and IA 1.2.

[0669] Although sulfate lignin is soluble in water at relatively high pH values, it is known that the viscosity of the solution increases dramatically at certain weight percentages. This increase in viscosity is generally attributed to the combined effect of strong hydrogen bonding and the π-electron interactions of the numerous aromatic rings present in lignin. For sulfate lignin, a sudden increase in viscosity in water of approximately 21% to 22% by weight was observed, and 19% by weight of sulfate lignin was used in the examples.

[0670] In the pH adjustment step, an aqueous ammonia solution was used as the base. The amount was fixed at 4% by weight based on the total reaction weight. The pH value after the pH adjustment step and at the start of oxidation was 10.7.

[0671] Table IA2 shows the CHNS elemental analysis results of sulfate lignin before and after oxidation. Prior to analysis, the samples were heat-treated at 160°C to remove adsorbed ammonia. Analysis indicates that a certain amount of nitrogen becomes part of the oxidized lignin structure during the oxidation process.

[0672] In batch experiments, it was determined that adding the full amount of hydrogen peroxide over short time intervals was more beneficial for oxidation than adding small amounts of peroxide over long periods. In this example, 2.0 wt% H₂O₂ was used based on the total reaction weight.

[0673] Oxidation is an exothermic reaction, and an increase in temperature will be observed after the addition of the peroxide. In the examples, the temperature was maintained at 60°C for three hours during the reaction.

[0674] After oxidation, the amount of lignin functional groups per gram of sample increases, as shown by... 31 The results were determined by P NMR and water titration. The phosphorylation reagent was 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxophosphazenecyclopentane (TMDP), and cholesterol was used as an internal standard. 31 The NMR spectra of the samples were analyzed before and after the oxidation of sulfate lignin, and the results are summarized in Table IA3.

[0675] The change in COOH groups was determined by water titration and using the following formula:

[0676]

[0677] Where V 2s and V 1s It is the final volume of the sample, while V 2b and V 1b This is the volume of the blank control. In this case, C 酸 It is 0.1M HCl, m s This represents the weight of the sample. The values ​​obtained from water titration before and after oxidation are shown in Table IA4.

[0678] The average COOH functionality can also be quantified by the saponification value, which represents the number of milligrams of KOH required to saponify 1 gram of lignin. This method can be found in AOCS Official Method Cd 3-25.

[0679] The average molecular weight was determined before and after oxidation using a PSS PolarSil column (9:1 (v / v) dimethyl sulfoxide / water eluent, 0.05 M LiBr) and a UV detector at 280 nm. The combination of COOH concentration and average molecular weight also allowed for the calculation of the average carboxylic acid group content per lignin macromolecule, and these results are shown in Table IA5.

[0680] Example IB – The lignin oxidation process in ammonia using hydrogen peroxide will be scaled up to a pilot-scale operation.

[0681] Hydrogenation of lignin with peroxide is an exothermic process; even on a laboratory scale, a significant temperature increase is observed after the addition of peroxide. This is a natural consideration when scaling up chemical processes, as the heat generated is cubic in size (volume), while cooling typically increases only with square size (area). Furthermore, due to the high viscosity of the binder intermediates, process equipment must be carefully selected or designed. Therefore, scaling up is meticulously planned and carried out in several steps.

[0682] The first scale-up step involved using a specialized stainless steel mixer with highly efficient mechanical mixing to increase the volume from 1 liter (laboratory scale) to 9 liters. The final temperature after the scale-up was only slightly higher than the laboratory scale, thanks to the reactor's efficient air cooling and the slow addition of hydrogen peroxide.

[0683] The next scale-up step was carried out in a closed 200L reactor equipped with a high-efficiency water jacket and a high-efficiency propeller agitator. This time, the scale-up was 180L, with hydrogen peroxide added in two steps and separation taking approximately 30 minutes. This scale-up proceeded relatively smoothly, although considerable foaming was a problem, partly due to the reactor's high packing density. To control foaming, a small amount of food-grade defoamer was sprayed onto the foam. Crucially, external water cooling was used to achieve a controllable temperature and a final temperature below 70°C.

[0684] The pilot-scale reaction was carried out in an 800L reactor equipped with a water-cooled jacket and a two-blade propeller agitator. 158 kg of lignin (UPM LignoBoost™ BioPiva 100) with a dry matter content of 67% by weight was pulverized and suspended in 224 kg of water and stirred to form a homogeneous suspension. Stirring continued, and 103 kg of 25% ammonia solution was pumped into the reactor, followed by stirring for another 2 hours until a dark, viscous lignin solution was formed.

[0685] Add 140 kg of 7.5% by weight hydrogen peroxide to the stirred lignin solution over 15 minutes at 20°C to 25°C. During and after adding hydrogen peroxide and cooling water to the cooling jacket, carefully monitor the temperature and foam level to maintain an acceptable foam level, a heating rate below 4°C per minute, and a final temperature below 70°C. After heating is stopped, turn off the cooling, stir the product mixture again for 2 hours, and then transfer it to a transport container.

[0686] Based on scale-up operation, it can be concluded that even though the reaction is exothermic, most of the heat of reaction is effectively balanced by the hydrothermal capacity from room temperature to approximately 60°C, with only the final portion requiring cooling for removal. It should be noted that, due to this, and because of the short reaction time, this process is well-suited for scaling up and process intensification using continuous reactors (such as in-line mixers, tubular reactors, or CSTR-type reactors). This will ensure good temperature control and a more defined reaction process.

[0687] Large-scale batch testing showed that the produced oxidized lignin had the same properties as the batches produced in the laboratory.

[0688] Table IA 1.1

[0689] Quantity of material used in the form provided:

[0690]

[0691] Table IA 1.2

[0692] Dosage of active material:

[0693]

[0694] Table IA 2

[0695] Elemental analysis of sulfate lignin before and after oxidation:

[0696]

[0697] Table IA 3

[0698] pass 31 P-NMR analysis revealed the functional group distribution of sulfate lignin before and after oxidation:

[0699]

[0700] Table IA4

[0701] COOH group content (mmol / g) determined by water titration:

[0702]

[0703] Table IA5

[0704] Table IA5. Number-average molar mass (Mn) and weight determined by size exclusion chromatography average molar mass (Mw), expressed in g / mol, and the average content of carboxylic acid groups in each lignin macromolecule before and after oxidation.

[0705]

[0706]

[0707] Example II

[0708] In the following examples, several types of oxidized lignin were prepared. The following properties of the oxidized lignin were determined:

[0709] Solid content of components:

[0710] The content of each component in a given oxidized lignin solution is based on the anhydrous mass of the component or as described below.

[0711] Sulfate lignin from UPM as BioPiva100 TM Supplied as dry powder. NH4OH 25% supplied by Sigma-Aldrich and used as supplied. H2O2, 30% (Cas no. 7722-84-1) supplied by Sigma-Aldrich and used as supplied or diluted with water. PEG 200 supplied by Sigma-Aldrich, assumed to be anhydrous and used as is for simplicity. PVA (Mw 89.000-98.000, Mw 85.000-124.000, Mw 130.000, Mw 146.000-186.000) (Cas no. 9002-89-5) supplied by Sigma-Aldrich, assumed to be anhydrous and used as is for simplicity. Urea (Cas no. 57-13-6) supplied by Sigma-Aldrich and used as supplied or diluted with water. Glycerin (Cas no. 56-81-5) supplied by Sigma-Aldrich is assumed to be anhydrous and used as is for simplicity.

[0712] Oxidized lignin solids

[0713] The content of oxidized lignin after heating to 200℃ for 1 hour is called "dry solids," expressed as a percentage of the remaining weight after heating.

[0714] A disc-shaped rock wool sample (diameter: 5 cm; height: 1 cm) was cut from the rock wool and heat-treated at 580°C for at least 30 minutes to remove all organic matter. The solids of the adhesive mixture were measured by distributing a sample (approximately 2 g) of the adhesive mixture onto the heat-treated rock wool disc in a foil container. The foil container containing the rock wool disc was weighed directly before and after the addition of the adhesive mixture. Two such adhesive mixtures were prepared in the foil container, loaded with rock wool discs, and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the sample was weighed and the dry solids content was calculated as the average of the two results.

[0715] COOH group content

[0716] The change in COOH group content was also determined by water titration and using the following formula:

[0717]

[0718] Where V 2s and V 1s It is the final volume of the sample, while V 2b and V 1b This is the volume of the blank sample. In this case, C 酸 It is 0.1M HCl, m s,g This is the weight of the sample.

[0719] Methods for producing oxidized lignin:

[0720] 1) While stirring, mix water and lignin in a three-necked glass-bottom flask connected to a condenser and a temperature recording device in a water bath at room temperature (20°C to 25°C). Stir for 1 hour.

[0721] 2) Add ammonia in one portion during the stirring process.

[0722] 3) If the slightly exothermic reaction with ammonia does not raise the temperature, then heat the mixture to raise the temperature to 35°C.

[0723] 4) Measure the pH value.

[0724] 5) Add plasticizer PEG200 and stir for 10 minutes.

[0725] 6) After the lignin has completely dissolved for about 1 hour, slowly add 1 part of 30% H2O2.

[0726] 7) The exothermic reaction of adding H2O2 increases the temperature in the glass-bottom flask - if the reaction temperature is below 60°C, raise the temperature to 60°C and place the sample at 60°C for 1 hour.

[0727] 8) Then remove the round-bottom flask from the water bath and cool it to room temperature.

[0728] 9) Take out the sample and measure the dry solids content, COOH, viscosity, density and pH value.

[0729] Oxidized Lignin Composition

[0730] In the following text, the entry numbers for the oxidized lignin examples correspond to the entry numbers used in Table II.

[0731] Example IIA

[0732] 71.0 g of lignin UPM Biopiva 100 was dissolved in 149.0 g of water at 20 °C. 13.3 g of 25% NH4OH was added, and the mixture was stirred with a magnetic stirrer for 1 hour. Then, 16.8 g of 30% H2O2 was slowly added while stirring. The temperature was raised to 60 °C in a water bath. After oxidation for 1 hour, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solids, pH, viscosity, and density.

[0733] Example IIE

[0734] 71.0 g of lignin UPM Biopiva 100 was dissolved in 88.8 g of water at 20 °C. 13.3 g of 25% NH4OH was added, and the mixture was stirred with a magnetic stirrer for 1 hour. 22.8 g of PEG 200 was added, and the mixture was stirred for 10 minutes. Then, 16.7 g of 30% H2O2 was slowly added while stirring. The temperature was raised to 60 °C in a water bath. After oxidation for 1 hour, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solids, pH, viscosity, and density.

[0735] Example IIC

[0736] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 g of water at 20 °C. 13.3 g of 25% NH4OH was added, and the mixture was stirred mechanically for 1 hour. Then, 16.6 g of 30% H2O2 was slowly added while stirring. The temperature was raised to 60 °C in a water bath. After oxidation for 1 hour, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solids, pH, viscosity, and density.

[0737] Example II F

[0738] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 g of water at 20 °C, and 13.3 g of 25% NH4OH was added. The mixture was stirred for 1 hour using a mechanical stirrer. 19.0 g of PEG 200 was added and stirred for 10 minutes, followed by the slow addition of 16.6 g of 30% H2O2 while stirring. The temperature was raised to 60 °C in a water bath. After oxidation for 1 hour, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solids, pH, viscosity, and density.

[0739] Table IIA

[0740]

[0741]

[0742] Example III:

[0743] 8.5 L of hot water (50 °C) and 1.9 L of NH4OH (24.7%) were mixed, and then 9.0 kg of lignin (UPM biopiva 100) was slowly added over 10 minutes with high stirring (660 rpm, 44 Hz).

[0744] The temperature rose due to high shear stress. After 30 minutes, 4 L of hot water was added, and the material was stirred for another 15 minutes before the remaining 5 L of hot water was added. The sample was removed, and undissolved lignin was analyzed using a Hegman gauge and pH measurement.

[0745] The premix is ​​then transferred to the rotor-stator unit and the reaction apparatus, where it is oxidized using H2O2 (17.5 vol%). The reaction apparatus used in this case at least partially comprises reaction tubes and a reaction vessel. The feed rate of the premix is ​​150 L / h, and the feed rate of H2O2 is 18 L / h.

[0746] In this embodiment, a Cavitron CD1000 rotor-stator unit is used for the mixing / oxidation step. The rotor-stator unit operates at 250 Hz (55 m / s circumferential speed) and a back pressure of 2 bar. The residence time in the reaction tube is 3.2 minutes, and the residence time in the reaction vessel is 2 hours.

[0747] The premix temperature is 62℃, and the oxidation step raises the temperature to 70℃.

[0748] Analyze the COOH group content, dry solids content, pH, viscosity and residual H2O2 of the final product.

[0749] Table III:

[0750]

[0751] Example IV:

[0752] 484 L of hot water (70 °C) and 47.0 L of NH4OH (24.7%) were mixed, and then 224.0 kg of lignin (UPM biopiva 100) was slowly added over 15 minutes with high stirring. The sample was removed, and undissolved lignin was analyzed using a Hegman gauge and pH measurement.

[0753] The premix was then transferred to a static mixer and a mixer / heat exchanger, where it was oxidized using H2O2 (35 vol%). The premix was fed at a rate of 600 L / h, and the H2O2 was fed at a rate of 17.2 L / h. The residence time in the mixer / heat exchanger was 20 minutes.

[0754] During the oxidation step, the temperature of the mixture is raised to as high as 95°C.

[0755] Analyze the COOH group content, dry solids content, pH, viscosity and residual H2O2 of the final product.

[0756] AOL-based adhesive preparation: 49.3g AOL (19.0% solids), 0.8g primid XL552 (100% solids) and 2.4g PEG200 (100% solids) were mixed with 0.8g water to produce a 19% solids content; this was then used for mechanical property testing in bar stock testing.

[0757] Bar testing

[0758] The mechanical strength of the adhesive was tested in the bar test. For each adhesive, 16 bars were manufactured using a mixture of the adhesive and rock wool pellets produced from rock wool spinning.

[0759] A sample of the adhesive solution (16.0 g) containing 15% dry solids was thoroughly mixed with pellets (80.0 g). The resulting mixture was then filled into four slots in the form of heat-resistant silicone to create small rods (4 x 5 slots per shape; top slot dimensions: length = 5.6 cm, width = 2.5 cm; bottom slot dimensions: length = 5.3 cm, width = 2.2 cm; slot height = 1.1 cm). The mixture placed in the slots was then pressed with a flat metal rod of appropriate size to produce a uniform rod surface. Sixteen rods for each adhesive were made in this manner. The resulting rods were then cured at 200°C for 1 hour. After cooling to room temperature, the rods were carefully removed from the container. Five of the rods were then aged in an 80°C water bath for 3 hours.

[0760] After drying for 1 to 2 days, the aged bars and 5 unaged bars broke in a 3-point bending test (test speed: 10.0 mm / min; fracture degree: 50%; nominal strength: 30 N / mm). 2 Support distance: 40mm; Maximum deflection: 20mm; Nominal electronic module body: 10000N / mm 2 The mechanical strength was studied on a Bent Tram machine. When the bar was placed in the machine, the "top surface" (i.e. the surface with dimensions of length = 5.6 cm and width = 2.5 cm) faced upwards.

[0761]

Claims

1. A stadium comprising: (i) Lower base layer; (ii) The upper grass layer and / or artificial turf layer; (iii) A shock-absorbing pad layer located between the base layer and the grass layer and / or artificial turf layer; The damping pad layer includes at least one damping pad, the damping pad including an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer, the adhesive layer including artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing includes: - Component (i), which is one or more forms of oxidized lignin; - Component (ii), which is in the form of one or more crosslinking agents; - Component (iii), which is in the form of one or more plasticizers.

2. The stadium according to claim 1, wherein the component (i) is in the form of one or more ammoniacal lignin (AOL).

3. The stadium according to claim 1 or 2, wherein the component (ii) comprises one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

4. The stadium according to claim 1 or 2, wherein component (ii) comprises: - One or more crosslinking agents selected from polyethyleneimine, polyethyleneamine, and fatty amines; and / or - One or more crosslinking agents, which are in the form of fatty amides; and / or - One or more crosslinking agents selected from dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid; and / or - One or more crosslinking agents selected from polyester polyols; and / or - One or more crosslinking agents selected from starch, modified starch, CMC; and / or - One or more crosslinking agents, which are in the form of aliphatic polyfunctional carbodiimides; and / or - One or more crosslinking agents selected from melamine-based crosslinking agents.

5. The stadium according to claim 4, wherein the polyester polyol is polycaprolactone.

6. The stadium according to claim 4, wherein the melamine crosslinking agent is a hexa(methylmethoxy)melamine (HMMM) crosslinking agent.

7. The stadium according to claim 1 or 2, based on the dry weight of component (i), comprising a quantity of component (ii) ranging from 1 wt% to 40 wt%.

8. The stadium according to claim 7, wherein the dry weight of component (i) comprises 4% to 20% by weight of component (ii).

9. The stadium according to claim 7, wherein the dry weight of component (i) comprises 6% to 12% by weight of component (ii).

10. The stadium according to claim 1 or 2, wherein component (iii) comprises one or more plasticizers selected from polyethylene glycol, polyethylene glycol ether, polyether, hydrogenated sugar, phthalates and / or acids, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactone, lactam, lactide, acrylic polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups.

11. The stadium according to claim 10, wherein the acid is adipic acid, vanillic acid, lactic acid and / or ferulic acid.

12. The stadium according to claim 1 or 2, wherein component (iii) comprises: - One or more plasticizers selected from fatty alcohols; and / or - One or more plasticizers selected from alkoxylates; and / or - One or more plasticizers in the form of propylene glycol; and / or - One or more plasticizers in the form of ethylene glycol esters; and / or - One or more plasticizers, selected from benzoic acid esters, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacic acid esters, azelaic acid esters, butyrates, valerates; and / or - One or more plasticizers selected from phenol derivatives; and / or - One or more plasticizers selected from silanols, siloxanes; and / or - One or more plasticizers selected from sulfate esters, sulfonates and / or phosphate esters; and / or - One or more plasticizers in the form of hydroxy acids; and / or - One or more plasticizers selected from monomeric amides; and / or - One or more plasticizers selected from quaternary ammonium compounds; and / or - One or more plasticizers selected from vegetable oils; and / or - One or more plasticizers selected from hydrogenated oils, acetylated oils; and / or - One or more plasticizers selected from acid methyl esters; and / or - One or more plasticizers selected from alkyl polysaccharides, glucosamides, aminoglucosamides, sucrose esters, and dehydrated sorbitol esters; and / or - One or more plasticizers selected from polyethylene glycol and polyethylene glycol ether.

13. The stadium according to claim 12, wherein the fatty alcohol is a monohydroxy alcohol.

14. The stadium according to claim 13, wherein the monohydroxy alcohol is pentanol or stearyl alcohol.

15. The stadium according to claim 12, wherein the alkoxylate is an ethoxylate.

16. The stadium according to claim 15, wherein the ethoxylate is butanol ethoxylate.

17. The stadium according to claim 16, wherein the butanol ethoxylate is butoxytriethylene glycol.

18. The stadium according to claim 12, wherein the phenol derivative is an alkyl or aryl substituted phenol.

19. The stadium according to claim 12, wherein the sulfate is an alkyl sulfate.

20. The stadium according to claim 12, wherein the sulfonate is an alkyl aryl sulfonate or an alkyl sulfonate.

21. The stadium according to claim 12, wherein the phosphate ester is a tripolyphosphate ester.

22. The stadium according to claim 12, wherein the monomeric amide is acetamide, benzamide, or fatty acid amide.

23. The stadium according to claim 22, wherein the fatty acid amide is tallolamid.

24. The stadium according to claim 12, wherein the quaternary ammonium compound is trimethylglycine or distearate dimethylammonium chloride.

25. The stadium according to claim 12, wherein the vegetable oil is castor oil, palm oil, flaxseed oil, tall oil, or soybean oil.

26. The stadium according to claim 1 or 2, wherein the content of component (iii) is from 0.5% by weight to 50% by weight based on the dry weight of component (i).

27. The stadium according to claim 26, wherein the content of component (iii) is from 2.5% to 25% by weight based on the dry weight of component (i).

28. The stadium according to claim 27, wherein the content of component (iii) is from 3% to 15% by weight based on the dry weight of component (i).

29. The stadium according to claim 1 or 2, wherein the aqueous adhesive composition comprises: The other component (iv) exists in the form of one or more coupling agents.

30. The stadium according to claim 29, wherein the coupling agent is an organofunctional silane.

31. The stadium according to claim 1 or 2, wherein the aqueous adhesive composition comprises: Component (v) is in the form of one or more components selected from ammonia, amines or any salts thereof.

32. The stadium according to claim 1 or 2, wherein the aqueous adhesive composition comprises: The other component is in the form of urea.

33. The stadium according to claim 32, wherein the additional component is based on the dry weight of component (i) and is in an amount of 5% to 40% by weight.

34. The stadium according to claim 33, wherein the additional component is based on the dry weight of component (i) and is in an amount of 10% to 30% by weight.

35. The stadium according to claim 34, wherein the additional component is based on the dry weight of component (i) and is present in an amount of 15% to 25% by weight.

36. The stadium according to claim 1 or 2, wherein the adhesive composition comprises the following components: - Component (i), which is one or more forms of oxidized lignin; - Component (ii), which is in the form of one or more crosslinking agents; - Component (iii), which is in the form of one or more plasticizers; - Component (iv), which is in the form of one or more coupling agents; - Optional components, which are in the form of one or more compounds selected from ammonia, amines or any salts thereof; - Optional component, in the form of urea; - Optional components, which may be in the form of more reactive or non-reactive polysiloxanes; - Optional hydrocarbon oil; - One or more surfactants may be selected; - water.

37. The stadium according to claim 36, wherein the coupling agent is an organofunctional silane.

38. The stadium according to claim 1 or 2, wherein the shock-absorbing pad further comprises: An upper film layer adhered to the upper main surface of the adhesive plate; and / or a lower film layer adhered to the lower main surface of the adhesive plate.

39. The stadium according to claim 1 or 2, wherein the thickness of the at least one adhesive layer is in the range of 12 mm to 60 mm.

40. The stadium according to claim 39, wherein the thickness of the at least one adhesive layer is in the range of 15 mm to 40 mm.

41. The stadium according to claim 40, wherein the thickness of the at least one adhesive layer is in the range of 20 mm to 35 mm.

42. The stadium according to claim 41, wherein the thickness of the at least one adhesive layer is in the range of 23 mm to 30 mm.

43. The stadium according to claim 1 or 2, wherein the density of at least one adhesive layer is 175 kg / m³. 3 Up to 300kg / m 3 Within the range.

44. The stadium according to claim 43, wherein the density of at least one adhesive layer is 220 kg / m³. 3 Up to 280kg / m 3 Within the range.

45. The stadium according to claim 44, wherein the density of at least one adhesive layer is 275 kg / m³. 3 .

46. ​​The stadium according to claim 1 or 2, wherein at least one adhesive layer has a water conductivity of 5 m / day to 200 m / day and / or a contact angle with water of less than 90°.

47. The stadium according to claim 46, wherein the water conductivity of at least one adhesive layer is 10 m / day to 50 m / day.

48. The stadium according to claim 1 or 2, wherein at least one adhesive layer comprises MMVF with a geometric fiber diameter of 1.5 micrometers to 10 micrometers.

49. The stadium of claim 48, wherein at least one adhesive layer comprises MMVF with a geometric fiber diameter of 2 to 8 micrometers.

50. The stadium of claim 49, wherein at least one adhesive layer comprises MMVF with a geometric fiber diameter of 2 to 5 micrometers.

51. The stadium according to claim 1 or 2, wherein at least one adhesive layer does not contain any wetting agent.

52. The stadium according to claim 1 or 2, further comprising: (iv) A filler layer between or within the shock-absorbing pad layer and the grass layer and / or artificial grass layer, wherein the filler layer comprises sand or a non-plastic material.

53. A method for constructing a stadium, comprising the following steps: (i) Provide the lower-level base; (ii) Provide a shock-absorbing pad layer above the base layer; (iii) Provide an upper grass layer and / or artificial grass layer above the shock-absorbing pad layer; The damping pad layer includes at least one damping pad, the damping pad including an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer, the adhesive layer including artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing includes: - Component (i), which is one or more forms of oxidized lignin; - Component (ii), which is in the form of one or more crosslinking agents; - Component (iii), which is in the form of one or more plasticizers.

54. The method of claim 53 further comprises providing a filler layer between the shock-absorbing pad layer and the upper grass layer or artificial grass layer, wherein the filler layer comprises sand or a non-plastic material.

55. A shock-absorbing pad, the shock-absorbing pad comprising an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein, The aqueous adhesive composition prior to curing comprises: - Component (i), which is one or more forms of oxidized lignin; - Component (ii), which is in the form of one or more crosslinking agents; - Component (iii), which is in the form of one or more plasticizers.

56. The shock-absorbing pad according to claim 55, further comprising any of the features described in claims 2 to 52.

57. A method for manufacturing a shock-absorbing pad, comprising the following steps: (i) Provide artificial glass fibers; (ii) Spray the artificial glass fiber with an aqueous adhesive composition; (iii) Collect and consolidate the artificial glass fibers, and cure the aqueous adhesive composition to form an adhesive layer; (iv) Provide an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer; The aqueous adhesive composition prior to curing includes: - Component (i), which is one or more forms of oxidized lignin; - Component (ii), which is in the form of one or more crosslinking agents; - Component (iii), which is in the form of one or more plasticizers.

58. A method for using shock-absorbing pads in a stadium to provide a vibration-absorbing surface, comprising the following steps: A shock-absorbing pad or assemblies are placed below the surface of a stadium, wherein the shock-absorbing pad comprises: an adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate comprises at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition; wherein the aqueous adhesive composition before curing comprises: - Component (i), which is one or more forms of oxidized lignin; - Component (ii), which is in the form of one or more crosslinking agents; - Component (iii), which is in the form of one or more plasticizers.

59. The use of shock-absorbing pads in stadiums for absorbing vibrations, wherein the shock-absorbing pads include: An adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition. The aqueous adhesive composition prior to curing includes: - Component (i), which is one or more forms of oxidized lignin; - Component (ii), which is in the form of one or more crosslinking agents; - Component (iii), which is in the form of one or more plasticizers.

60. The use of shock-absorbing pads in stadiums for absorbing water and / or draining water, wherein said shock-absorbing pads comprise: An adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition. The aqueous adhesive composition prior to curing includes: - Component (i), which is one or more forms of oxidized lignin; - Component (ii), which is in the form of one or more crosslinking agents; - Component (iii), which is in the form of one or more plasticizers.

61. The use of shock-absorbing pads for cooling the surface temperature of a stadium, wherein the shock-absorbing pads comprise: An adhesive plate having an upper main surface and a lower main surface, wherein the adhesive plate includes at least one adhesive layer comprising artificial glass fibers (MMVF) bonded to a cured aqueous adhesive composition. The aqueous adhesive composition prior to curing includes: - Component (i), which is one or more forms of oxidized lignin; - Component (ii), which is in the form of one or more crosslinking agents; - Component (iii), which is in the form of one or more plasticizers.

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