Acoustic product

Abstract

The present invention relates to a method of manufacturing an acoustic product and a novel acoustic product, wherein the acoustic product is manufactured by bonding a facing to a first main surface of an acoustic insulation element using an adhesive and curing the adhesive. The adhesive is an aqueous adhesive composition comprising: a component (i) in the form of one or more oxidized lignin; -a component (ii) in the form of one or more cross-linking agents; -a component (iii) in the form of one or more plasticizers.

Description

[0001] This patent application is application number 202080101614.2 and application date is April 2020

[0002] On the 3rd, a divisional application for a patent application with the invention title “Acoustic Product” was filed. Technical Field

[0003] The present invention relates to an acoustic product for sound insulation and sound absorption. In particular, the present invention relates to a method for manufacturing such an acoustic product and a system comprising such an acoustic product. Background Art

[0004] It is well known to provide acoustic products for sound insulation and sound absorption. A common form of such a product is an acoustic element in the form of a panel with a facing adhered to a major surface of the panel.

[0005] It is important that the adhesive used to bond the facing to the panel has appropriate properties. It is particularly important that the bond strength (usually defined as peel strength) is sufficient.

[0006] Phenolic resins are often used as binders for facings. This is particularly useful for acoustic panels formed from a matrix of man-made vitreous fibers (MMVF) bonded by a binder, as phenolic resins have often been used as binders for such products. Phenolic binders work well and are commonly used in commercial practice.

[0007] Phenolic resins can be produced economically and can be extended with urea prior to use as an adhesive. However, existing and proposed legislation aimed at reducing or eliminating formaldehyde emissions has led to the development of formaldehyde-free adhesives, such as adhesive compositions based on polycarboxy polymers and polyols or polyamines, such as those disclosed in EP-A-583086, EP-A-990727, EP-A-1741726, US-A-5,318,990 and US-A-2007 / 0173588.

[0008] Another group of non-phenolic adhesives are addition / elimination reaction products of aliphatic and / or aromatic anhydrides with alkanolamines, such as those disclosed in WO 99 / 36368, WO 01 / 05725, WO 01 / 96460, WO 02 / 06178, WO 2004 / 007615 and WO 2006 / 061249. These adhesive compositions are water-soluble and exhibit excellent adhesive properties in terms of cure speed and cure density.

[0009] WO 2008 / 023032 discloses urea-modified binders of this type which provide mineral wool products with reduced hygroscopicity.

[0010] These substances can in principle be used as adhesives for facings on acoustic components. However, since some of the starting materials used to produce these adhesives are relatively expensive chemicals, there is currently a need to provide adhesives that can be produced economically and do not contain formaldehyde.

[0011] A further impact associated with previously known aqueous binder compositions for mineral fibers is that at least most of the starting materials used to produce these binders come from fossil fuels. Consumers increasingly prefer products that are produced completely or at least partially from renewable materials, and there is a need to provide binders for mineral wool that are produced at least partially from renewable materials.

[0012] Another problem associated with previously known aqueous binder compositions for mineral fibers is that they include ingredients that are corrosive and / or harmful. This requires protective measures to be taken on the machinery involved in the production of mineral wool products to prevent corrosion, and also requires safety measures for the personnel operating the machinery. This leads to increased costs and health issues, and therefore there is a need to provide binder compositions with reduced content of corrosive and / or harmful substances.

[0013] At the same time, many binders for mineral fibers have been provided, which are based to a large extent on renewable starting materials. In many cases, these binders based to a large extent on renewable resources are also formaldehyde-free.

[0014] However, many of these adhesives are still relatively expensive because they are based on relatively expensive base materials, so their use as adhesives to bond facings to acoustic elements would be uneconomical. Summary of the invention

[0015] It is therefore an object of the present invention to provide an adhesive composition which is particularly suitable for bonding facings to acoustic elements, uses renewable materials as starting materials, reduces or eliminates corrosive and / or hazardous materials, and is relatively inexpensive to produce.

[0016] It is a further object of the present invention to provide an acoustic product formed from an acoustic element having a facing bonded thereto wherein the bonding properties are good, particularly as good as those provided by phenolic adhesives, but which minimize the disadvantages of phenolic adhesives.

[0017] According to a first aspect of the present invention, we provide a method for manufacturing an acoustic product, the method comprising:

[0018] providing an acoustic element comprising a first major surface and a second major surface;

[0019] providing a first finish;

[0020] fixing the first facing to the first major surface of the acoustic element by using an adhesive; and

[0021] curing the adhesive, wherein the adhesive is an aqueous composition comprising:

[0022] - component (i) in the form of one or more oxidized lignins;

[0023] - component (ii) in the form of one or more crosslinking agents;

[0024] - component (iii) in the form of one or more plasticizers.

[0025] In the present invention we use as adhesive a composition as defined above. The advantage of this is that it has commercially acceptable bonding properties and indeed performs as well as phenolic resins but without the disadvantages associated with phenolic resins.

[0026] According to a second aspect of the invention we provide an acoustic product obtainable by the method of the first aspect of the invention.

[0027] According to a third aspect of the present invention, we provide an acoustic product, comprising an acoustic element, wherein the acoustic element comprises a first main surface, a second main surface and a first facing, wherein the first facing is fixed to the first main surface of the acoustic element by an adhesive, wherein the adhesive before curing is an aqueous adhesive composition, which comprises:

[0028] - component (i) in the form of one or more oxidized lignins;

[0029] - component (ii) in the form of one or more crosslinking agents;

[0030] - component (iii) in the form of one or more plasticizers.

[0031] A preferred method of making the acoustic product comprises applying a second facing to the second major surface of the acoustic element prior to curing and, after curing, cutting the acoustic element in half in a plane parallel to the major faces. Each half has a cut face which becomes the front face of the acoustic product. Each acoustic element has a front major face and a rear major face extending in an XY plane and side edges extending in a Z direction between the front and rear faces. The front face is the face facing the room or other space which will benefit from the sound absorbing properties.

[0032] Each front face is abraded to make it as flat as possible and then an additional facing is usually bonded to it. Thus, a first facing and a second facing are located on the back of the two acoustic products that have been manufactured.

[0033] Acoustic products formed according to the method of the first aspect of the invention or acoustic products formed according to the second and third aspects of the invention may form a ceiling system comprising a plurality of acoustic products suspended in a grid. It is also useful to provide a wall system comprising a plurality of acoustic products as defined in the second or third aspects of the invention suspended on a wall.

[0034] The method of the present invention comprises providing an acoustic element. The acoustic element may be a sound insulating element, but more commonly a sound absorbing element. Therefore, more commonly, it is capable of absorbing sound waves reaching its surface.

[0035] The acoustic elements may be formed from any material known for providing acoustic elements, but are preferably formed from MMVF. The acoustic elements may be made by casting a wet or fluid material (e.g. they may be made from wet laid mineral fibres), but are preferably formed from air laid mineral fibres, typically bound with a binder in a matrix.

[0036] The adhesive may be any adhesive known for bonding MMVF.

[0037] Preferably, the binder is an organic binder, such as a phenolic binder, a urea-formaldehyde binder, a phenol-urea-formaldehyde binder or a melamine-formaldehyde binder. Conventionally used phenolic or phenol-urea-formaldehyde (PUF) resol binders optionally contain a sugar component. For these binders without sugar components, for example, reference is made to EP 0148050 and EP 0996653. For these binders containing sugar components, reference is made to WO 2012 / 076462.

[0038] The adhesive may be formaldehyde-free, for example an adhesive composition based on polycarboxyl polymers and polyols or polyamines, such as those disclosed in EP-A-583086, EP-A-990727, EP-A-1741726, US-A-5,318,990 and US-A-2007 / 0173588.

[0039] Another group of non-phenolic binders that can be used for MMVF matrices are addition / elimination reaction products of aliphatic and / or aromatic anhydrides with alkanolamines, for example, as disclosed in WO 99 / 36368, WO 01 / 05725, WO 01 / 96460, WO 02 / 06178, WO 2004 / 007615 and WO 2006 / 061249. These binder compositions are water-soluble and exhibit excellent adhesive properties in terms of cure speed and cure density. WO 2008 / 023032 discloses urea-modified binders of this type that provide mineral wool products with reduced hygroscopicity.

[0040] The preferred adhesive for MMVF is an aqueous adhesive composition comprising:

[0041] - component (i) in the form of one or more oxidized lignins;

[0042] - component (ii) in the form of one or more crosslinking agents;

[0043] - component (iii) in the form of one or more plasticizers.

[0044] Other preferred features of the adhesive are described below in the context of materials used as adhesives. When such materials are used as adhesives for MMVFs in acoustic elements, all of the same preferred features apply regardless of the characteristics of the adhesive.

[0045] The density of the acoustic element is preferably 40 kg / m 3 Up to 180kg / m 3 In the range of 80kg / m 3 Up to 160kg / m 3 , preferably 100kg / m 3 Up to 140kg / m 3 More preferably at least 100 kg / m 3 In particular, it usually does not exceed 150kg / m 3 .

[0046] When the acoustic element is formed of MMVF, the loss on ignition (LOI) of the man-made vitreous fiber batt bonded by the binder is usually in the range of 0.5 wt % to 8 wt %, preferably 2 wt % to 5 wt %. By convention, the LOI is taken as the binder content. In addition to the main binder component, the binder usually also includes a small amount of oil and other organic binder additives.

[0047] When acoustic elements are formed from MMVF, their average fiber diameter is typically between 3 microns and 8 microns.

[0048] The man-made vitreous fibers (MMVF) used in the present invention may have any suitable oxide composition. The fibers may be vitreous fibers, ceramic fibers, basalt fibers, slag fibers or rock or stone fibers. The fibers are preferably of the type commonly referred to as rock, stone or slag fibers, most preferably stone fibers.

[0049] Stone fibers usually contain the following oxides, expressed in weight percentage:

[0050] SiO 2 : 30 to 51

[0051] CaO: 8 to 30

[0052] MgO: 2 to 25

[0053] FeO (including Fe 2 O 3 ): 2 to 15

[0054] Na 2 O+K 2 O: No more than 10

[0055] CaO+MgO: 10 to 30.

[0056] In a preferred embodiment, the MMVF comprises the following elements in amounts calculated as % by weight of the oxides:

[0057] SiO 2 : At least 30, 32, 35 or 37; not more than 51, 48, 45 or 43Al 2 O 3 : at least 12, 16 or 17; not more than 30, 27 or 25CaO: at least 8 or 10; not more than 30, 25 or 20MgO: at least 2 or 5; not more than 25, 20 or 15FeO (including Fe 2 O 3 ): at least 4 or 5; not more than 15, 12 or 10FeO+MgO: at least 10, 12 or 15; not more than 30, 25 or 20Na 2 O+K 2 O: 0 or at least 1; not more than 10CaO+MgO: at least 10 or 15; not more than 30 or 25

[0058] TiO 2 : 0 or at least 1; not more than 6, 4 or 2TiO 2 +FeO: at least 4 or 6; not more than 18 or 12

[0059] B 2 O 3 : 0 or at least 1; not more than 5 or 3P 2 O 5 : 0 or at least 1; not more than 8 or 5

[0060] Others: 0 or at least 1; not more than 8 or 5.

[0061] The MMVF used in the present invention preferably has the following composition in wt %: SiO 2 35 to 50

[0062] Al 2 O 3 12 to 30

[0063] TiO 2 Up to 2

[0064] Fe 2 O3 3 to 12

[0065] CaO 5 to 30

[0066] MgO up to 15

[0067] Na 2 O 0 to 15

[0068] K 2 O 0 to 15

[0069] P 2 O 5 Up to 3

[0070] MnO up to 3

[0071] B 2 O 3 At most 3.

[0072] Another preferred composition of MMVF has the following weight %: SiO 2 39% to 55%, preferably 39% to 52%

[0073] Al 2 O 3 16% to 27%, preferably 16% to 26%

[0074] CaO 6% to 20%, preferably 8% to 18%

[0075] MgO 1% to 5%, preferably 1% to 4.9%

[0076] Na 2 O 0% to 15%, preferably 2% to 12%

[0077] K 2 O 0% to 15%, preferably 2% to 12%

[0078] R 2 O(Na 2 O+K 2 O) 10% to 14.7%, preferably 10% to 13.5%

[0079] P 2 O 5 0% to 3%, preferably 0% to 2%

[0080] Fe 2 O 3 (Total Iron) 3% to 15%, preferably 3.2% to 8%

[0081] B 2 O 3 0% to 2%, preferably 0 to 1%

[0082] TiO 2 0% to 2%, preferably 0.4% to 1%

[0083] Others 0% to 2.0%.

[0084] Glassy fibers usually contain the following oxides, in percentage by weight:

[0085] SiO 2 : 50 to 70

[0086] Al 2 O 3 : 10 to 30

[0087] CaO: not more than 27

[0088] MgO: not more than 12.

[0089] The glassy fibers may also contain the following oxides, expressed in percentage by weight:

[0090] Na 2 O+K 2 O: 8 to 18, especially Na 2 O+K 2 O is greater than CaO+MgO

[0091] B 2 O 3 : 3 to 12.

[0092] Al 2 O 3 : Less than 2%.

[0093] The acoustic element is usually in the form of a panel. The element has a first main face and a second main face that are substantially parallel (and extend in the XY direction). They are connected by a secondary face that is usually perpendicular to the main faces (and therefore extends in the Z direction).

[0094] When formed from MMVF, the acoustic elements are formed by standard processes for producing MMVF panels.

[0095] The MMV fibers can be made from a mineral melt. The mineral melt is provided in a conventional manner by providing mineral materials and melting them in a furnace. The furnace can be any furnace type known for producing MMVF mineral melts, such as a vertical furnace, such as a cupola, a pot furnace or a cyclone furnace.

[0096] The MMVF can be formed from the mineral melt by fiberization by any suitable method. Fiberization can be carried out by a spinning cup process, in which the melt is centrifugally extruded through orifices in the wall of a rotor (spinning cup, also called internal centrifugal). Alternatively, fiberization can be by centrifugal fiberization, by ejecting the melt onto the outer surface of a fiberizing rotor and stripping it, or stripping it from a cascade of multiple fiberizing rotors, which rotate about a substantially horizontal axis (cascade spinnerets).

[0097] The binder of the fibers is applied while being formed and entrained in the air.The fibers may initially be collected on a collector as a primary web which is then cross-lapped in a conventional manner to form a secondary web.

[0098] Preferably, the first facing is applied to the first main face before the step of curing the MMVF adhesive. The same is true if a second facing is used. This means that the adhesive used for the facing can also be cured in the same curing step as the adhesive. However, it is also possible to apply the facing after the adhesive of the MMVF substrate has cured and then to carry out the step of curing the adhesive.

[0099] When a second facing is applied, it is preferred that the adhesive of the second facing is of the same chemical type as the adhesive of the first facing.

[0100] Curing of the adhesive is preferably carried out at a temperature of 100 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.

[0101] In a preferred embodiment curing of the binder is carried out in a conventional curing oven used for mineral wool production, preferably at a temperature of 150 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.

[0102] In one embodiment, curing is performed for 30 seconds to 20 minutes, such as 1 minute to 15 minutes, such as 2 minutes to 10 minutes.

[0103] In a typical embodiment, curing is performed at a temperature of 150°C to 250°C for 30 seconds to 20 minutes.

[0104] If the acoustic product is a bonded web of MMVF, the web also includes an adhesive. This must also be cured. The curing process of the adhesive can begin immediately after the adhesive is applied to the fibers.

[0105] Curing of the adhesive and / or binder is defined as a process whereby the adhesive / binder composition undergoes a physical and / or chemical reaction, which in the case of a chemical reaction generally increases the molecular weight of the compounds in the adhesive / binder composition, thereby increasing the viscosity of the adhesive / binder composition, generally until the adhesive / binder composition reaches a solid state. The cured adhesive composition bonds the fibers to form a structurally coherent fiber matrix. The cured adhesive composition bonds the facing to the acoustic element.

[0106] In one embodiment, curing of the binder / adhesive is carried out in a hot press. Curing the binder in contact with the mineral fibers in a hot press has the particular advantage of allowing the production of a high density product.

[0107] In one embodiment, the curing process comprises drying by pressure.The pressure may be applied by blowing air or gas through / onto the product to be cured.

[0108] Two products are made by forming a cured fiber batt, bonding a first facing and a second facing to a first major face and a second major face, respectively, and then cutting the batt in half in a plane parallel to the major faces. Each half has a cut face that becomes the front face of the acoustic product. Each front face is abraded to make it as flat as possible.

[0109] In the process described, it is also possible to apply an additional facing on the front side. This is preferably applied using a dry adhesive rather than the adhesive of the invention.

[0110] The method of the present invention is preferably according to WO 2005 / 095727. According to this method, the acoustic product is manufactured by the following method, the method comprising:

[0111] - collecting the MMVF entrained in air on a moving collector and selectively compressing the collected fibers vertically after cross-lapping to form a web,

[0112] - Reorient the fibers to provide a density of 70kg / m 3 Up to 200kg / m 3 unbonded batts and improve fiber orientation in the Z direction,

[0113] - curing the binder to form a cured batt,

[0114] - cutting the solidified wadding in the XY plane into two cut waddings at a certain position in the Z dimension, wherein the fibers have an increased orientation in the Z direction,

[0115] - and smoothes each cut surface by abrasion to produce a flat, smooth surface.

[0116] Preferably, the first facing and preferably the second facing are applied to the first and second major faces of the batt prior to the curing step.

[0117] The method may further comprise the conventional step of forming the element with the desired XY dimensions by subdividing the cured batt before cutting it into two cut batts and / or by subdividing the cut batt before or after abrasion.

[0118] The cutting of the bonded batt can be carried out in a conventional manner, for example using a band saw or a rotary saw with a suitably small tooth size, for example similar to a conventional joinery saw. The abrasion or grinding can be carried out by a sanding belt or any other abrasive or grinding element. The abrasive particles on the belt may be relatively coarse, so the abrasion may be similar to a conventional coarse wood grinder or grinder.

[0119] Further details of the preferred production method are given in WO 2005 / 095727.

[0120] The thickness of an acoustic product is the vertical distance between the main faces of the product. This is typically in the range of 12mm to 100mm, for example 15mm to 50mm.

[0121] The length of the acoustic product is preferably in the range of 550 mm to 650 mm or 1100 mm to 1300 mm. Preferred lengths are about 600 mm and about 1200 mm. For special products, the length may be as high as 3000 mm, but this may cause practical problems in handling and installation and may therefore be less preferred.

[0122] The width of acoustic products ranges from 550mm to 650mm. The preferred width is approximately 600mm. For special products the length may be as low as 150mm, this will increase installation time but may be preferred for design reasons or to utilise a portion of the product that would otherwise be scrapped.

[0123] The first, second and further facings may independently be any known material used as facings for acoustic products. Preferably the facing or each facing is a fibre muslin, in particular a glass fibre muslin. The glass fibre muslin itself may be bonded with a binder, such as any conventional binder known for bonding MMVF substrates. The binder content of the muslin may be in the range of 10% to 25%, for example 12% to 23%.

[0124] An example of such a glass muslin cloth is Owens Corning I50U. Another example is Evalith Glass Fibre Veil DH50 / 20. Another suitable glass muslin cloth is Saint-Gobain Adfors GlassVeil U 50D75.

[0125] For example, the surface of glass fiber gauze cloth can have an area weight of 20g / m 2 Up to 80g / m 2 In the range of 40g / m 2 Up to 60g / m 2 within the range.

[0126] In the method, the adhesive is typically applied to the first facing, or if a second facing is used, the second facing, before the facing is brought into contact with the respective major face of the acoustic element. However, the adhesive may be applied directly to the facing to be adhered on the major face of the element.

[0127] The applied weight is preferably 5g / m 2 Up to 12g / m 2 range, preferably 7g / m 2 Up to 10g / m 2 The applied weight is per m 2 of dry solids content.

[0128] Preferably, the adhesive is applied by passing the facing through a coating bath containing the adhesive.Another method of application is spraying.

[0129] Any of the facings may be provided with a lacquer layer. The lacquer may be applied to the facing before the facing is adhered to the acoustic element or after application.

[0130] The product is an acoustic product and therefore preferably has good sound absorption properties. For example, the sound absorption coefficient αw is preferably at least 0.7, more preferably at least 0.8, more preferably at least 0.85, even more preferably at least 0.9 or 0.95. The sound absorption coefficient αw is determined on the front side.

[0131] The acoustic product made according to the method of the present invention, as well as the acoustic product of the third aspect of the present invention, can be used in any known acoustic product application.

[0132] For example, it may be a ceiling tile or form part of a suspended ceiling, or used as a wall tile or baffle. Acoustic products can be bonded directly to a wall or ceiling, but often they are mounted on a grid, particularly where it is desirable to provide ceiling tiles suspended from a grid.

[0133] The adhesive used in the present invention is in the form of an aqueous composition. Preferred features are discussed below. When the acoustic product is formed from MMVF bonded to an adhesive, the adhesive may also be of the type discussed below, and all of the same preferred features apply.

[0134] Water-based adhesives and / or binders include:

[0135] - component (i) in the form of one or more oxidized lignins;

[0136] - component (ii) in the form of one or more crosslinking agents;

[0137] - component (iii) in the form of one or more plasticizers.

[0138] In a preferred embodiment, the adhesives and / or binders used according to the invention are formaldehyde-free.

[0139] For the purposes of this application, the term "formaldehyde-free" is defined as a mineral wool product wherein the formaldehyde emission from the mineral wool product is below 5 μg / m2 / h, preferably below 3 μg / m2 / h. Preferably, the test is performed according to ISO 16000 to test for aldehyde emission.

[0140] Component (i)

[0141] Component (i) is in the form of one or more oxidized lignins.

[0142] Lignin, cellulose, and hemicellulose are the three main organic compounds in plant cell walls. Lignin can be thought of as the glue that holds cellulose fibers together. Lignin contains both hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, after cellulose, and is estimated to account for as much as 20% to 30% of the total carbon contained in biomass, which totals more than 1 billion tons worldwide.

[0143] Figure 1 Part of a possible lignin structure is shown.

[0144] There are at least four groups of industrial lignins available on the market. Figure 3 . A possible fifth group, biorefinery lignin, is a bit different in that it is not described by extraction process but by process source, i.e. biorefining, and therefore it may be similar or different to any of the other groups listed above. Each group is distinct from the others and each is suitable for different applications. Lignin is a complex, heterogeneous material consisting of up to three different phenylpropane monomers, depending on the source. Softwood lignin is made primarily of coniferyl alcohol units, see Figure 2 , thus, they are more homogeneous than hardwood lignins, which have a higher syringol content, see Figure 2 The appearance and consistency of lignin is quite variable and depends largely on the process.

[0145] Figure 4 A summary of the properties of these industrial lignins is shown.

[0146] Lignosulfonates from the sulfite pulping process remain the largest source of commercially available lignin, with a capacity of 1.4 million tonnes. But leaving these aside, the Kraft process is currently the most used pulping process and is gradually replacing the sulfite process. It is estimated that 78 million tonnes of lignin are produced annually from Kraft pulp production worldwide, but most of this is burned to obtain steam and energy. The current recovery capacity of Kraft is estimated to be 160,000 tonnes, but some sources indicate that the current recovery volume is only about 75,000 tonnes. Kraft lignin is developed from black liquor, which is the waste liquor from the kraft or Kraft process. Currently, there are 3 well-known processes used to produce kraft lignin: LignoBoost, LignoForce and SLRP. The similarity between these 3 processes is that they all involve the addition of CO 2 The process involves reducing the pH to 9 to 10, followed by acidification to further reduce the pH to about 2. The final step involves some combination of washing, leaching and filtering to remove ash and other contaminants. All three processes are at various stages of commercialization around the world.

[0147] The kraft process introduces thiol groups and stilbenes while retaining some carbohydrates. Sodium sulfate is also present as an impurity due to the precipitation of the lignin from the liquor with sulfuric acid, but it is possible to avoid this problem by changing the way the lignin is isolated. The kraft process results in the production of a large number of phenolic hydroxyl groups, and when these groups are ionized (above pH ~10), this lignin is soluble in water.

[0148] Commercial kraft lignin is usually purer than lignin sulfonate. The molecular weight is 1000 g / mol to 3000 g / mol.

[0149] Alkali lignin is derived from the sodium hydroxide pulping process and is mainly used in wheat straw, sugarcane bagasse and flax. The properties of alkali lignin vary in solubility and T g Similar in nature to kraft lignin. No sulfur is used in this process and there is no covalently bound sulfur. Ash levels are very low. Alkali lignin has low solubility in neutral and acidic media but is completely soluble at pH 12 and above.

[0150] The lignin sulfonate process introduces a large number of sulfonate groups, making the lignin soluble in water and also soluble in acidic aqueous solutions. The sulfur content of lignin sulfonate is up to 8%, which is a sulfonate, while the kraft lignin contains 1% to 2% sulfur, which is mainly combined with lignin. The molecular weight of lignin sulfonate is 15.000g / mol to 50.000g / mol. Compared with other types of lignin, this lignin contains more residual carbohydrates and has a higher average molecular weight. The typical hydrophobic core of lignin and the large number of ionized sulfonate groups make this lignin attractive as a surfactant, which is often used in dispersed cement, etc.

[0151] Another class of lignin that can be used is lignin produced in a biorefinery process, where carbohydrates are separated from the lignin by chemical or biochemical processes to produce a carbohydrate-rich fraction. This remaining lignin is called biorefinery lignin. The focus of biorefineries is to produce energy and to produce alternatives to products obtained from fossil fuels and petrochemicals as well as lignin. The lignin produced in this process is generally considered a low-value product or even a waste product, and is mainly used for thermal combustion or used as a low-grade feed or disposed of in other ways.

[0152] The availability of organosolv lignin is still being considered at pilot scale. This process involves the extraction of lignin using water and various organic solvents (most commonly ethanol) and some organic acids. The advantage of this process is that the lignin obtained is of higher purity, but the cost is much higher compared to other industrial lignins, and the lignin obtained is dissolved in an organic solvent instead of water.

[0153] Previous attempts to use lignin as a base compound for binder and / or adhesive compositions for mineral fibers have failed because it has proven difficult to find suitable crosslinking agents to achieve the desired mechanical properties of the cured mineral wool product while avoiding harmful and / or corrosive components. Currently, lignin is used to replace petroleum-derived chemicals such as phenols in binder and / or adhesive applications or phenolic resins in asphalt. It is also used as a cement and concrete additive and in some applications as a dispersant.

[0154] Crosslinking of polymers should generally provide improved properties, such as mechanical, chemical and thermal resistance. Lignin is particularly rich in phenolic and aliphatic hydroxyl groups, which can react to form a crosslinked structure of lignin. Different lignins will also have other available functional groups. Depending on the specific source, the presence of these other groups depends to a large extent on the way in which lignin is separated from cellulose and hemicellulose (thiols in kraft lignin, sulfonates in lignin sulfonates, etc.).

[0155] It has been found that by using oxidized lignin, adhesives and / or binder compositions can be prepared, resulting in mineral fiber products having superior properties.

[0156] In one embodiment, component (i) is in the form of one or more oxidized kraft lignins.

[0157] In one embodiment, component (i) is in the form of one or more oxidized alkali lignins.

[0158] In one embodiment, component (i) is in the form of one or more ammonia-oxidized lignins. For the purposes of the present invention, the term "ammonia-oxidized lignin" is understood to be lignin that has been oxidized by an oxidant in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.

[0159] In an alternative embodiment, the ammonia is partially or completely replaced by an alkali metal hydroxide, in particular sodium hydroxide and / or potassium hydroxide.

[0160] A typical oxidizing agent used to prepare oxidized lignin is hydrogen peroxide.

[0161] In one embodiment, the ammonia-oxidized lignin comprises one or more compounds selected from ammonia, amines, hydroxides or any salts thereof.

[0162] In one embodiment, the carboxylic acid group content of component (i) 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 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).

[0163] In one embodiment, the average carboxylic acid group content of component (i) exceeds 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups.

[0164] It is believed that the carboxylic acid group content of the oxidized lignin plays an important role in the unexpected advantages of the mineral fibers in the aqueous binder and / or adhesive composition of the present invention. In particular, it is believed that the carboxylic acid groups of the oxidized lignin improve the crosslinking properties, thereby giving the cured mineral fiber product better mechanical properties.

[0165] Component (ii)

[0166] Component (ii) is in the form of one or more cross-linking agents.

[0167] In one embodiment, component (ii) in one embodiment comprises one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

[0168] β-Hydroxyalkylamide crosslinkers are curing agents for acid-functional macromolecules. They provide a hard, durable, corrosion-resistant and solvent-resistant crosslinked polymer network. It is believed that β-Hydroxyalkylamide crosslinkers cure by esterification to form multiple ester bonds. The hydroxyl functionality of the β-Hydroxyalkylamide crosslinker should average at least 2, preferably greater than 2, and more preferably 2 to 4, in order to obtain the best curing response.

[0169] The cross-linking agent containing an oxazoline group is a polymer containing one or more oxazoline groups in each molecule, and generally, the cross-linking agent containing an oxazoline group can be easily obtained by polymerizing an oxazoline derivative. Patent US6818699 B2 discloses such a process.

[0170] In one embodiment, component (ii) is an epoxidized oil based on fatty acid triglycerides.

[0171] It is to be noted that epoxidized oils based on fatty acid triglycerides are not considered hazardous, and therefore the use of these compounds in adhesives and / or binder compositions according to the present invention does not render the handling of these compositions unsafe.

[0172] In one embodiment, component (ii) is a molecule having 3 or more epoxy groups.

[0173] In one embodiment, component (ii) is one or more flexible oligomers or polymers, such as low Tg acrylic polymers, such as low Tg vinyl polymers, such as low Tg polyethers, which contain reactive functional groups, such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

[0174] In one embodiment, component (ii) is selected from crosslinking agents that participate in the curing reaction, such as hydroxyalkylamides, alkanolamines, and reaction products of alkanolamines and polycarboxylic acids. The reaction products of alkanolamines and polycarboxylic acids can be found in US Pat. No. 6,706,853 B1.

[0175] Without intending to be bound by any particular theory, it is believed that the very advantageous properties of the aqueous adhesives and binder compositions according to the invention are due to the interaction of the oxidized lignin used as component (i) with the above-mentioned crosslinking agent. It is believed that the presence of carboxylic acid groups in the oxidized lignin enables the oxidized lignin to crosslink very effectively.

[0176] In one embodiment, component (ii) is one or more crosslinking agents selected from multifunctional organic amines such as alkanolamines, diamines such as hexamethyldiamine, triamines.

[0177] In one embodiment, component (ii) is one or more crosslinking agents selected from polyethyleneimine, polyvinylamine, fatty amine.

[0178] In one embodiment, component (ii) is one or more fatty amides.

[0179] In one embodiment, component (ii) is one or more crosslinking agents selected from dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid.

[0180] In one embodiment, component (ii) is one or more crosslinking agents selected from polyester polyols, such as polycaprolactone.

[0181] In one embodiment, component (ii) is one or more crosslinking agents selected from starch, modified starch, CMC.

[0182] In one embodiment, component (ii) is one or more cross-linking agents in the form of aliphatic multifunctional carbodiimides.

[0183] In one embodiment, component (ii) is one or more crosslinking agents selected from melamine-based crosslinking agents, such as hexa(methylmethoxy)melamine (HMMM)-based crosslinking agents.

[0184] Examples of such compounds are Picassian XL 701, 702, 725 (Stahl Polymers), such as XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).

[0185] Component (ii) may also be any mixture of the abovementioned compounds.

[0186] In one embodiment, the adhesive and / or binder composition according to the invention comprises component (ii) in an amount of 1 wt % to 40 wt %, such as 4 wt % to 20 wt %, such as 6 wt % to 12 wt %, based on the dry weight of component (i).

[0187] Component (iii)

[0188] Component (iii) is in the form of one or more plasticizers.

[0189] In one embodiment, component (iii) is in the form of one or more plasticizers selected from: polyols such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids such as adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides (such as urea / urea) or any mixtures thereof.

[0190] In one embodiment, component (iii) is in the form of one or more plasticizers selected from: carbonates such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with a structure similar to lignin such as vanillin, acetosyringone, solvents used as coalescing agents such as alcohol ethers, polyvinyl alcohol.

[0191] In one embodiment, component (iii) is in the form of one or more non-reactive plasticizers selected from: polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or other esters, solvents used as coalescing agents such as alcohol ethers, acrylic polymers, polyvinyl alcohol.

[0192] In one embodiment, component (iii) is one or more reactive plasticizers selected from: carbonates such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, dicarboxylic acids or tricarboxylic acids such as adipic acid, or lactic acid, and / or vanillic acid and / or ferulic acid, polyurethane dispersions, acrylic polymers with free carboxyl groups, compounds with a structure similar to lignin such as vanillin, acetosyringone.

[0193] In one embodiment, component (iii) is in the form of one or more plasticizers selected from fatty alcohols, monohydric alcohols such as amyl alcohol, stearyl alcohol.

[0194] In one embodiment, component (iii) comprises one or more plasticizers selected from polyethylene glycol, polyethylene glycol ethers.

[0195] Another particularly surprising aspect of the present invention is that the use of plasticizers with a boiling point above 100°C, in particular from 140°C to 250°C, substantially improves the mechanical properties of the mineral fiber products according to the invention, even though, given their boiling point, these plasticizers are likely to at least partially evaporate during the curing of the aqueous binder and / or adhesive in contact with the mineral fibers.

[0196] In one embodiment, component (iii) comprises one or more plasticizers having a boiling point exceeding 100°C, such as 110°C to 280°C, more preferably 120°C to 260°C, more preferably 140°C to 250°C.

[0197] It is believed that the effectiveness of these plasticizers in the aqueous adhesive and / or binder composition according to the invention is related to the effect of increasing the fluidity of the oxidized lignin during the curing process. It is believed that the increased fluidity of the lignin or oxidized lignin during the curing process contributes to effective crosslinking.

[0198] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 g / mol to 50000 g / mol, in particular 150 g / mol to 4000 g / mol, more particularly 150 g / mol to 1000 g / mol, preferably 150 g / mol to 500 g / mol, more preferably 200 g / mol to 400 g / mol.

[0199] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4000 g / mol to 25000 g / mol, particularly 4000 g / mol to 15000 g / mol, more particularly 8000 g / mol to 12000 g / mol.

[0200] In one embodiment, component (iii) is capable of forming covalent bonds with component (i) and / or component (ii) during the curing process. Such components do not evaporate and remain as part of the composition, but are effectively altered so as not to introduce undesirable side effects, such as water absorption in the cured product. Non-limiting examples of such components are caprolactones and acrylic polymers having free carboxyl groups.

[0201] In one embodiment, component (iii) is selected from fatty alcohols, monohydric alcohols such as amyl alcohol, stearyl alcohol.

[0202] In one embodiment, component (iii) is selected from one or more plasticizers selected from alkoxylates such as ethoxylates, such as butanol ethoxylates, such as butoxytriglycol.

[0203] In one embodiment, component (iii) is selected from one or more propylene glycols.

[0204] In one embodiment, component (iii) is selected from one or more ethylene glycol esters.

[0205] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, caprates, azelates, butyrates, valerates.

[0206] In one embodiment, component (iii) is selected from one or more plasticizers selected from: phenol derivatives such as alkyl or aryl substituted phenols.

[0207] In one embodiment, component (iii) is selected from one or more plasticizers selected from: silanols, siloxanes.

[0208] In one embodiment, component (iii) is selected from one or more plasticizers selected from sulfates such as alkyl sulfates, sulfonates such as alkylaryl sulfonates such as alkyl sulfonates, phosphates such as tripolyphosphates, such as tributyl phosphate.

[0209] In one embodiment, component (iii) is selected from one or more hydroxy acids.

[0210] In one embodiment, component (iii) is selected from one or more plasticizers selected from: monomeric amides such as acetamide, benzamide, fatty acid amides such as tall oil amide.

[0211] In one embodiment, component (iii) is selected from one or more plasticizers selected from: quaternary ammonium compounds such as trimethylglycine, distearyldimethylammonium chloride.

[0212] In one embodiment, component (iii) is selected from one or more plasticizers selected from: vegetable oils such as castor oil, palm oil, linseed oil, tall oil, soybean oil.

[0213] In one embodiment, component (iii) is selected from one or more plasticizers selected from: hydrogenated oils, acetylated oils.

[0214] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0215] In one embodiment, component (iii) is selected from one or more plasticizers selected from: alkyl polyglycosides, glucosamides, aminoglucosamides, sucrose esters, sorbitan esters.

[0216] It has surprisingly been found that the addition of a plasticizer to the aqueous binder and / or adhesive composition according to the invention substantially improves the mechanical properties of the mineral fiber product according to the invention.

[0217] 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.

[0218] Component (iii) may also be any mixture of the abovementioned compounds.

[0219] In one embodiment, the content of component (iii) is 0.5 to 50 wt%, preferably 2.5 to 25 wt%, more preferably 3 to 15 wt%, based on the dry weight of component (i).

[0220] The aqueous binder and / or adhesive composition for mineral fibers comprises components (i) and (iia).

[0221] In one embodiment of the present invention, the aqueous binder and / or adhesive composition for mineral fibers comprises:

[0222] - component (i) in the form of one or more oxidized lignins;

[0223] - component (iia) in the form of one or more modifiers.

[0224] The present inventors have found that excellent adhesive properties can also be achieved by a two-component system comprising one or more components (i) in the form of oxidized lignin and one or more components (iia) in the form of modifiers, and optionally any other components mentioned above and below.

[0225] In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from epoxidized oils based on fatty acid triglycerides.

[0226] In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from molecules having 3 or more epoxy groups.

[0227] In one embodiment, component (iia) is a modifier in the form of one or more flexible oligomers or polymers, such as low Tg acrylic polymers, such as low Tg vinyl polymers, such as low Tg polyethers, which contain reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

[0228] In one embodiment, component (iia) is one or more modifiers selected from polyethyleneimine, polyvinylamine, fatty amine.

[0229] In one embodiment, component (iia) is one or more modifiers selected from aliphatic multifunctional carbodiimides.

[0230] Component (iia) may also be any mixture of the abovementioned compounds.

[0231] Without intending to be bound by any particular theory, it is believed that the excellent adhesive properties achieved by the binder and / or binder composition for mineral fibers comprising components (i) and (iia) and optionally other components are at least partly due to the effect of the modifier used as component (iia) serving at least partly the functions of a plasticizer and a crosslinker.

[0232] In one embodiment, the aqueous adhesive and / or binder composition comprises component (iia) in an amount of 1 to 40 wt%, such as 4 to 20 wt%, such as 6 to 12 wt%, based on the dry weight of component (i).

[0233] Other components

[0234] In some embodiments, the aqueous adhesive and / or binder composition used in the present invention comprises other components.

[0235] In one embodiment, the aqueous adhesive and / or adhesive composition used in the present invention comprises a catalyst selected from inorganic acids, such as sulfuric acid, aminosulfonic acid, nitric acid, boric acid, hypophosphorous 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, hypophosphorous acid and / or phosphoric acid. The presence of such a catalyst can improve the curing properties of the aqueous adhesive and / or adhesive composition according to the present invention.

[0236] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention includes a catalyst selected from Lewis acids, which can accept an electron pair from a donor compound to form a Lewis adduct, such as ZnCl 2 Mg(ClO 4 ) 2 Sn[N(SO 2 -n-C8F17) 2 ] 4 .

[0237] In one embodiment, the aqueous adhesive and / or adhesive composition used in the present invention includes a catalyst selected from metal chlorides, such as KCl, MgCl 2 、ZnCl 2 、FeCl 3 and SnCl 2 .

[0238] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention includes a catalyst selected from organometallic compounds, such as titanate-based catalysts and tin-based catalysts.

[0239] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, copper ions.

[0240] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention further comprises an additional component (iv) in the form of one or more silanes.

[0241] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention comprises a further component (iv) in the form of one or more coupling agents, such as organofunctional silanes.

[0242] In one embodiment, component (iv) is selected from organofunctional silanes, such as primary or secondary amino-functional silanes, epoxy-functional silanes, such as polymeric or oligomeric epoxy-functional silanes, methacrylate-functional silanes, alkyl- and aryl-functional silanes, urea-functional silanes or vinyl-functional silanes.

[0243] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention further comprises component (v), which is in the form of one or more components selected from ammonia, amines or any salts thereof.

[0244] It has been found that the addition of ammonia, an amine or any salt thereof as a further component is particularly useful when oxidized lignin is used in component (i), wherein the oxidized lignin is not oxidized in the presence of ammonia.

[0245] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention further comprises other components in the form of urea, in particular in an amount of 5 to 40 wt %, such as 10 to 30 wt %, 15 to 25 wt %, based on the dry weight of component (i).

[0246] In one embodiment, the aqueous adhesive and / or binder composition used in the present invention further comprises one or more other components in the form of carbohydrates, wherein the carbohydrates are selected from sucrose, reducing sugars, in particular glucose, polycarbohydrates and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, more preferably glucose syrup having 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.

[0247] In one embodiment, the aqueous binder and / or adhesive composition used in the present invention further comprises other components in the form of one or more carbohydrates selected from sucrose and reducing sugars, based on the dry weight of component (i), in an amount of 5 wt % to 50 wt %, such as 5 wt % to less than 50 wt %, such as 10 wt % to 40 wt %, such as 15 wt % to 30 wt %.

[0248] In the context of the present invention, an adhesive or adhesive composition having a sugar content of 50% by weight or more, based on the total dry weight of the adhesive or adhesive component, is considered to be a sugar-based adhesive or adhesive. In the context of the present invention, an adhesive or adhesive composition having a sugar content of less than 50% by weight, based on the total dry weight of the adhesive or adhesive component, is considered to be a non-sugar-based adhesive or adhesive.

[0249] In one embodiment, the aqueous adhesive and / or adhesive composition used in the present invention further comprises one or more other components in the form of surfactants, wherein the surfactant is in the form of a nonionic and / or ionic emulsifier, such as polyoxyethylene (4) lauryl ether, such as soy lecithin, and such as sodium lauryl sulfate.

[0250] In one embodiment, the aqueous adhesive and / or adhesive composition used in the present invention comprises:

[0251] - component (i) in the form of one or more ammonia-oxidized lignins, having 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);

[0252] - component (ii) 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, triamines;

[0253] - component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 g / mol to 50,000 g / mol, in particular 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, more particularly 150 g / mol to 300 g / mol, or in the form of one or more polyethylene glycols having an average molecular weight of 4,000 g / mol to 25,000 g / mol, in particular % to 40 wt %, such as 4 wt % to 20 wt %, 6 wt % to 12 wt %, based on the dry weight of component (i), and the content of component (iii) is 0.5 wt % to 50 wt %, preferably 2.5 wt % to 25 wt %, more preferably 3 wt % to 15 wt %, based on the dry weight of component (i).

[0254] In one embodiment, the aqueous adhesive and / or adhesive composition used in the present invention comprises:

[0255] - component (i) in the form of one or more ammonia-oxidized lignins, having 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);

[0256] - component (iia) in the form of one or more modifiers selected from epoxidized oils based on fatty acid triglycerides.

[0257] In one embodiment, the aqueous adhesive and / or adhesive composition used in the present invention comprises:

[0258] - component (i) in the form of one or more ammonia-oxidized lignins, the average carboxylic acid group content per macromolecule of component (i) exceeding 1.5 groups, such as more than 2 groups, such as more than 2.5 groups;

[0259] - component (ii) 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, triamines;

[0260] - component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 g / mol to 50,000 g / mol, in particular 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, more particularly 150 g / mol to 300 g / mol, or in the form of one or more polyethylene glycols having an average molecular weight of 4,000 g / mol to 25,000 g / mol, in particular % to 40 wt %, such as 4 wt % to 20 wt %, 6 wt % to 12 wt %, based on the dry weight of component (i), and the content of component (iii) is 0.5 wt % to 50 wt %, preferably 2.5 wt % to 25 wt %, more preferably 3 wt % to 15 wt %, based on the dry weight of component (i).

[0261] In one embodiment, the aqueous adhesive and / or adhesive composition used in the present invention comprises:

[0262] - component (i) in the form of one or more ammonia-oxidized lignins, the average carboxylic acid group content per macromolecule of component (i) exceeding 1.5 groups, such as more than 2 groups, such as more than 2.5 groups;

[0263] - component (iia) in the form of one or more modifiers selected from epoxidized oils based on fatty acid triglycerides.

[0264] In one embodiment, the aqueous adhesive and / or adhesive composition used in the present invention consists essentially of the following substances:

[0265] - component (i) in the form of one or more oxidized lignins;

[0266] - component (ii) in the form of one or more crosslinking agents;

[0267] - component (iii) in the form of one or more plasticizers.

[0268] - component (iv) in the form of one or more coupling agents, such as organofunctional silanes;

[0269] - an optional component in the form of one or more compounds selected from ammonia, amines or any salt thereof;

[0270] - an optional component in the form of urea;

[0271] - optional components in the form of more reactive or non-reactive polysiloxanes;

[0272] - optionally a hydrocarbon oil;

[0273] - optionally one or more surfactants;

[0274] -water.

[0275] In one embodiment, the aqueous adhesive and / or adhesive composition used in the present invention consists essentially of the following:

[0276] - component (i) in the form of one or more oxidized lignins;

[0277] - component (iia) in the form of one or more modifiers selected from epoxidized oils based on fatty acid triglycerides.

[0278] - component (iv) in the form of one or more coupling agents, such as organofunctional silanes;

[0279] - an optional component in the form of one or more compounds selected from ammonia, amines or any salt thereof;

[0280] - an optional component in the form of urea;

[0281] - optional components in the form of more reactive or non-reactive polysiloxanes;

[0282] - optionally a hydrocarbon oil;

[0283] - optionally one or more surfactants;

[0284] -water.

[0285] Oxidized lignin which can be used as a component of an aqueous binder and / or adhesive composition for mineral fibers according to the invention and a method for preparing such an oxidized lignin

[0286] In the following, we describe oxidized lignin and its preparation that can be used as a component of binders and / or adhesive compositions.

[0287] Method for preparing oxidized lignin I

[0288] Oxidized lignin useful as a component for the adhesive of the present invention can be prepared by the following method, the method comprising contacting:

[0289] - component (a) comprising one or more lignins;

[0290] - component (b) comprising ammonia, one or more amine components and / or any salts thereof;

[0291] - component (c) comprising one or more oxidizing agents.

[0292] Component (a)

[0293] Component (a) includes one or more lignins.

[0294] In one embodiment of the method, component (a) includes one or more kraft lignins, one or more alkali lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins obtained from a biorefining process of a lignocellulosic feedstock, or any mixture thereof.

[0295] In one embodiment, component (a) comprises one or more kraft lignins.

[0296] Component (b)

[0297] In one embodiment according to the present invention, component (b) comprises ammonia, one or more amino components and / or any salts thereof. Without intending to be bound by any particular theory, it is believed that replacing the alkali hydroxide used in the previously known lignin oxidation process with ammonia, one or more amino components and / or any salts thereof plays an important role in improving the properties of the oxidized lignin prepared according to the method of the present invention.

[0298] It has been unexpectedly found that lignin oxidized by an oxidizing agent in the presence of ammonia or an amine contains a large amount of nitrogen as part of the oxidized lignin structure. Without intending to be bound by any particular theory, it is believed that when oxidized lignin (which is prepared according to the present invention) is used in products in which they are included in adhesives and / or adhesive compositions, the improved fire resistance of the oxidized lignin is at least partly due to the nitrogen content of the oxidized lignin structure.

[0299] In one embodiment, component (b) comprises ammonia and / or any salts thereof.

[0300] Without wishing to be bound by any particular theory, it is believed that the improved stability of the derivatized lignin prepared according to the present invention is at least in part due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused. In contrast, it has proven difficult to remove residual amounts of alkali hydroxide used in previously known oxidation processes.

[0301] However, in the present invention, it may be advantageous if component (b) comprises, in addition to ammonia, one or more amino components and / or any salts thereof, relatively small amounts of alkali and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0302] In embodiments where component (b) comprises 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 alkali and / or alkaline earth metal hydroxide is typically small, such as 5 to 70 parts by weight, such as 10 to 20 parts by weight, of alkali and / or alkaline earth metal hydroxide, based on ammonia.

[0303] Component (c)

[0304] In the present invention, component (c) includes one or more oxidizing agents.

[0305] In one embodiment, component (c) includes one or more oxidants in the form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen-containing oxidants, or any mixture thereof.

[0306] In the initial steps of oxidation, the reactive free radicals from the oxidant will typically abstract a proton from the phenolic group, since this bond has the lowest dissociation energy in lignin. Since lignin has the potential to stabilize the free radicals through mesoisomerization, there are multiple pathways to continue (but also terminate) the reaction and obtain a variety of intermediates and final products. Due to this complexity (and the conditions chosen), the average molecular weight can increase and decrease, and in their experiments, the inventors generally saw a modest increase in average molecular weight of about 30%.

[0307] In one embodiment, component (c) comprises hydrogen peroxide.

[0308] Hydrogen peroxide is probably the most commonly used oxidant due to its combination of low price, high efficiency, and relatively low environmental impact. When hydrogen peroxide is used in the absence of a catalyst, alkaline conditions and temperature are important because the following reactions lead to free radical formation:

[0309]

[0310] It has been found that the derivatized lignin prepared by the method according to the invention contains an increased amount of carboxylic acid groups due to the oxidation process. Without intending to be bound by any particular theory, it is believed that the carboxylic acid group content of the oxidized lignin prepared by the method according to the invention plays an important role in the desired reaction properties of the derivatized lignin prepared by the method according to the invention.

[0311] 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 substrates such as mineral fibers.

[0312] Other components

[0313] In one embodiment, the process according to the invention comprises a binder and / or adhesive comprising further components, in particular component (d) in the form of an oxidation catalyst, such as one or more transition metal catalysts, such as iron sulfate, such as catalysts containing manganese, palladium, selenium, tungsten.

[0314] Such an oxidation catalyst can increase the reaction rate, thereby improving the properties of the oxidized lignin prepared by the method according to the present invention.

[0315] Mass ratio of components

[0316] One skilled in the art will use the relative amounts of components (a), (b) and (c) to achieve the desired degree of lignin oxidation.

[0317] In one embodiment,

[0318] - component (a), comprising one or more lignins

[0319] - component (b) comprising ammonia

[0320] - component (c) comprising one or more oxidizing agents in the form of hydrogen peroxide,

[0321] The mass ratio of lignin, ammonia and hydrogen peroxide is such that the amount of ammonia is 0.01 to 0.5 parts by weight, such as 0.1 to 0.3 parts by weight, such as 0.15 to 0.25 parts by weight of ammonia, based on the dry weight of lignin, and the amount of hydrogen peroxide is 0.025 to 1.0 parts by weight, such as 0.05 to 0.2 parts by weight, such as 0.075 to 0.125 parts by weight of hydrogen peroxide, based on the dry weight of lignin.

[0322] method

[0323] There is more than one possibility for contacting components (a), (b) and (c) to achieve the desired oxidation reaction.

[0324] In one embodiment, the method comprises the following steps:

[0325] - a step of providing a dispersion of component (a) and / or one or more lignins in the form of an aqueous solution, the aqueous solution having a lignin content of 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;

[0326] - a step of adjusting the pH by adding component (b) comprising an aqueous solution of ammonia, one or more amine components and / or any salts thereof;

[0327] - an oxidation step by adding component (c) comprising an oxidizing agent.

[0328] In one embodiment, the pH adjustment step is performed such that the pH of the resulting aqueous solution and / or dispersion is ≥ 9, such as ≥ 10, such as ≥ 10.5.

[0329] In one embodiment, the 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.

[0330] In one embodiment, the pH adjustment step is performed such that the temperature is allowed to rise to ≥ 25°C and then controlled in the range of 25°C to 50°C, such as 30°C to 45°C, such as 35°C to 40°C.

[0331] In one embodiment, during the oxidation step, the temperature is allowed to rise to ≥ 35°C and then controlled in the range of 35°C to 150°C, such as 40°C to 90°C, such as 45°C to 80°C.

[0332] In one embodiment, the oxidation step is performed for a period of time ranging from 1 second to 48 hours, such as from 10 seconds to 36 hours, such as from 1 minute to 24 hours, such as from 2 hours to 5 hours.

[0333] Method II for preparing oxidized lignin

[0334] Oxidized lignin useful as a binder and / or adhesive component for use in the present invention can be prepared by a method comprising contacting:

[0335] - component (a) comprising one or more lignins;

[0336] - component (b) comprising ammonia, and / or one or more amine components, and / or any salts thereof and / or alkali and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide;

[0337] - component (c) comprising one or more oxidizing agents.

[0338] - component (d) in the form of one or more plasticizers.

[0339] Component (a)

[0340] Component (a) includes one or more lignins.

[0341] In one embodiment of the method, component (a) includes one or more kraft lignins, one or more alkali lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins obtained from a biorefining process of a lignocellulosic feedstock, or any mixture thereof.

[0342] In one embodiment, component (a) comprises one or more kraft lignins.

[0343] Component (b)

[0344] In one embodiment, component (b) comprises ammonia, one or more amino components and / or any salts thereof and / or alkali and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0345] "Ammonia oxidized lignin" is understood to be lignin oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia oxidized lignin" is abbreviated as AOL.

[0346] In one embodiment, component (b) comprises ammonia and / or any salts thereof.

[0347] Without intending to be bound by any particular theory, it is believed that the improved stability of the derivatized lignin prepared according to the present invention wherein component (b) is ammonia and / or any salt thereof is at least partly due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused.

[0348] However, in this embodiment of the process, it is advantageous that component (b) comprises, in addition to ammonia, one or more amino components and / or any salts thereof, relatively small amounts of alkali and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0349] In some embodiments, where 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 alkali and / or alkaline earth metal hydroxide is generally small, such as 5 to 70 parts by weight, such as 10 to 20 parts by weight, of alkali and / or alkaline earth metal hydroxide, based on ammonia.

[0350] Component (c)

[0351] In the method according to the invention, component (c) comprises one or more oxidizing agents.

[0352] In one embodiment, component (c) includes one or more oxidizing agents in the form of hydrogen peroxide, an organic or inorganic peroxide, molecular oxygen, ozone, air, a halogen-containing oxidizing agent, or any mixture thereof.

[0353] In the initial steps of oxidation, the reactive free radical from the oxidant will typically abstract a proton from the phenolic group, since this bond has the lowest dissociation energy in lignin. Since lignin has the potential to stabilize the free radical via mesoisomerization, there are multiple pathways to continue (but also terminate) the reaction and obtain a variety of intermediates and final products. Due to this complexity (and the conditions chosen), the average molecular weight can increase and decrease, and in their experiments we typically see a modest increase in average molecular weight of about 30%.

[0354] In one embodiment, component (c) comprises hydrogen peroxide.

[0355] Hydrogen peroxide is probably the most commonly used oxidant due to its combination of low price, high efficiency, and relatively low environmental impact. When hydrogen peroxide is used in the absence of a catalyst, alkaline conditions and temperature are important because the following reactions lead to free radical formation:

[0356]

[0357] It has been found that the derivatized lignin prepared by the method according to the present invention contains an increased amount of carboxylic acid groups due to the oxidation process. Without intending to be bound by any particular theory, it is believed that the carboxylic acid group content of the oxidized lignin prepared in the method plays an important role in the desired reaction properties of the derivatized lignin prepared by the method.

[0358] 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 substrates such as mineral fibers.

[0359] Component (d)

[0360] Component (d) includes one or more plasticizers.

[0361] In one embodiment, component (d) includes one or more plasticizers in the form of polyols, such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids such as adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides (such as urea / urea) or any mixtures thereof.

[0362] It has been found 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 the production of oxidized lignin in a very efficient process.

[0363] In one embodiment, component (d) includes 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 with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides (such as urea / urea) or any mixture thereof.

[0364] In one embodiment, component (d) comprises one or more plasticizers selected from polyethylene glycol, polyvinyl alcohol, urea or any mixture thereof.

[0365] Other components

[0366] In one embodiment, the process includes further components, particularly component (v), in the form of an oxidation catalyst, such as one or more transition metal catalysts, such as iron sulfate, such as catalysts containing manganese, palladium, selenium, tungsten.

[0367] This oxidation catalyst can increase the reaction rate, thereby improving the properties of the oxidized lignin prepared by the method.

[0368] Mass ratio of components

[0369] One skilled in the art will use the relative amounts of components (a), (b), (c) and (d) to achieve the desired degree of lignin oxidation.

[0370] In one embodiment, the method is carried out such that the method comprises:

[0371] - component (a) comprises one or more lignins;

[0372] - component (b) comprises ammonia;

[0373] - component (c) comprises one or more oxidizing agents in the form of hydrogen peroxide;

[0374] - component (d) comprises one or more plasticizers selected from polyethylene glycol,

[0375] The mass ratio of lignin, ammonia, hydrogen peroxide and polyethylene glycol is such that, based on the dry weight of lignin, the amount of ammonia is 0.01 to 0.5 parts by weight, for example, 0.1 to 0.3 parts by weight, for example, 0.15 to 0.25 parts by weight of ammonia (25 wt% aqueous solution), and based on the dry weight of lignin, the amount of hydrogen peroxide (30 wt% aqueous solution) is 0.025 to 1.0 parts by weight, for example, 0.07 to 0.50 parts by weight, for example, 0.15 to 0.30 parts by weight of hydrogen peroxide, and the amount of polyethylene glycol is 0.03 to 0.60 parts by weight, for example, 0.07 to 0.50 parts by weight, for example, 0.10 to 0.40 parts by weight of polyethylene glycol.

[0376] For the purposes of the present invention, "dry weight of lignin" is preferably defined as the weight of lignin in the form provided.

[0377] method

[0378] There is more than one possibility for contacting components (a), (b), (c) and (d) to achieve the desired oxidation reaction.

[0379] In one embodiment, the method comprises the following steps:

[0380] - a step of providing component (a) in the form of an aqueous solution and / or a dispersion of one or more lignins, the aqueous solution having a lignin content of 5 to 90 wt.-%, such as 10 to 85 wt.-%, such as 15 to 70 wt.-%, based on the total weight of the aqueous solution;

[0381] - a step of adjusting the pH by adding component (b);

[0382] - a step of adding component (d);

[0383] - an oxidation step by adding component (c) comprising an oxidizing agent.

[0384] In one embodiment, the pH adjustment step is performed such that the pH of the resulting aqueous solution and / or dispersion is ≥ 9, such as ≥ 10, such as ≥ 10.5.

[0385] In one embodiment, the 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.

[0386] In one embodiment, the pH adjustment step is performed such that the temperature is allowed to rise to ≥ 25°C and then controlled in the range of 25°C to 50°C, such as 30°C to 45°C, such as 35°C to 40°C.

[0387] In one embodiment, during the oxidation step, the temperature is allowed to rise to ≥ 35°C and then controlled in the range of 35°C to 150°C, such as 40°C to 90°C, such as 45°C to 80°C.

[0388] In one embodiment, the oxidation step is performed for a period of from 1 second to 24 hours, such as from 1 minute to 12 hours, such as from 10 minutes to 8 hours, such as from 5 minutes to 1 hour.

[0389] It has been found that the process allows the production of a reaction mixture with a high dry matter content, so that a high yield can be achieved in the process, which allows the reaction product in the form of oxidized lignin to be used as a component for industrial large-scale production of products such as mineral fiber products.

[0390] In one embodiment, the process is carried out such that the dry matter content of the reaction mixture is from 20 wt% to 80 wt%, such as from 40 wt% to 70 wt%.

[0391] In one embodiment, the method is performed such that the viscosity of the oxidized lignin has a value of 100 cP to 100.000 cP, such as a value of 500 cP to 50.000 cP, such as a value of 1.000 cP to 25.000 cP.

[0392] For the purposes of the present invention, viscosity is dynamic viscosity, defined as the resistance of a liquid / paste to change of shape, or the resistance of adjacent parts to movement relative to each other. Viscosity is measured in centipoise (cP), equivalent to 1 mPa s (million Pascal seconds). Viscosity is measured at 20°C using a viscometer. For the purposes of the present invention, dynamic viscosity can be measured at 20°C by a cone-plate-well Brookfield viscometer.

[0393] In one embodiment, the method is carried out such that the method comprises a rotor-stator arrangement.

[0394] In one embodiment, the method is performed such that the method is carried out as a continuous or semi-continuous process.

[0395] Equipment for carrying out the method

[0396] The present disclosure also includes an apparatus for performing the above method.

[0397] In one embodiment, an apparatus for performing the method comprises:

[0398] - rotor-stator arrangement,

[0399] - a premixing device for components (a), (b), (d),

[0400] - one or more inlets for water, components (a), (b), (c) and (d),

[0401] - One or more outlets for oxidized lignin.

[0402] In one embodiment, the device is constructed in such a way that the inlet for premixing components (a), (b) and (d) is connected to the rotor-stator device, and the device also includes a chamber,

[0403] The chamber has an inlet for component (c), and

[0404] The chamber has an outlet for oxidized lignin.

[0405] A rotor-stator device is a device for processing materials, comprising a stator configured as an inner cone with a toothed ring. The stator cooperates with a rotor having arms extending from a hub. Each of these arms has teeth that mesh with the teeth of the toothed ring of the stator. With each revolution of the rotor, the material to be processed is conveyed a certain distance outwards, while being subjected to strong shearing effects, mixing and redistribution. The rotor arms of the upright device and the adjacent container chambers allow permanent rearrangement of the material from the inside to the outside and provide multiple processing of dry and / or highly viscous substances, so that the device has good utility for intensive mixing, kneading, fiberizing, disintegrating and similar processes that are important in industrial production. The upright arrangement of the shell facilitates the fall of the material from the periphery to the center of the device.

[0406] In one embodiment, the rotor-stator device used in the method comprises a stator with a toothed ring and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotor-stator device has the following features: a guide funnel protrudes between the arms of the rotor to focus the material flow coming from above to the central area 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 the working area of ​​the device. The guide funnel retains the product in the working area of ​​the device, while the feed screw generates an increased material pressure in the central area.

[0407] For more details on the rotor-stator arrangement used in one embodiment of the method, reference is made to US 2003 / 0042344 A1, which is incorporated herein by reference.

[0408] In one embodiment, the method is carried out so that the method uses a rotor-stator device. In this embodiment, the mixing of the components and the reaction of the components are carried out in the same rotor-stator device.

[0409] In one embodiment, the method is carried out such that the method uses two or more rotor-stator devices, wherein at least one rotor-stator device is used for mixing of the components and at least one rotor-stator device is used for reacting the components.

[0410] The method can be divided into two steps:

[0411] 1. Prepare lignin material (a) + (b) + (d);

[0412] 2. Oxidation of lignin

[0413] Typically, two different types of rotor / stator machines are used:

[0414] 1. Open rotor / stator machine, which is suitable for incorporating lignin powder into water at very high concentrations (30 to 50 wt. %). The mixing intensity is low, but special auxiliary equipment (inlet funnel, screw, etc.) is used to handle high viscosity materials. Low peripheral speed (up to 15 m / s). The machine can be used as a batch system or a continuous system.

[0415] 2. Inline rotor / stator machines, which have higher shear forces - peripheral speeds up to 55 m / s) - and create favorable conditions for very fast chemical reactions. The machines should be used continuously.

[0416] In an open rotor / stator system, a high concentration (45 to 50 wt%) lignin / water mass is prepared. The lignin powder is slowly added to warm water (30°C to 60°C) to which the correct amount of aqueous ammonia and / or alkalibase has been added. This can be done in batch mode, or by adding the material intermittently / continuously, creating a continuous flow of mass to the next step.

[0417] The resulting mass should be maintained at a temperature of approximately 60 degrees to keep the viscosity as low as possible so that the material is pumpable. The hot mass of lignin / water at 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.

[0418] In one embodiment, the oxidation is accomplished as a continuous on-line reaction in a closed rotor / stator system. An aqueous solution of ammonia and / or alkali is injected into the rotor / stator chamber at the point of highest turbulence / shear with a metering pump. This ensures a rapid oxidation reaction. The oxidized material (AOL) leaves the on-line reactor and is collected in a suitable tank.

[0419] Reaction products

[0420] It has surprisingly been found that the oxidized lignins prepared have highly desirable reactivity properties while showing improved fire resistance when used in products comprising them in adhesive and / or binder compositions and having improved long term stability over previously known oxidized lignins.

[0421] Oxidized lignin also showed improved hydrophilicity.

[0422] An important parameter for the reactivity of the prepared oxidized lignin is the carboxylic acid group content of the oxidized lignin.

[0423] In one embodiment, the carboxylic acid 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).

[0424] Another way to describe the carboxylic acid group content is to use the average carboxylic acid group content per lignin macromolecule according to the following formula:

[0425]

[0426] In one embodiment, the oxidized lignin prepared has an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (a), such as more than 2 groups, such as more than 2.5 groups.

[0427] Method III for preparing oxidized lignin

[0428] The oxidized lignin used as a component of the binder and / or adhesive used in the present invention can be prepared by a method comprising contacting:

[0429] - component (a) comprising one or more lignins;

[0430] - component (b) comprising ammonia, and / or one or more amine components, and / or any salts thereof, and / or alkali and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide;

[0431] - component (c) comprising one or more oxidizing agents,

[0432] - optional component (d) in the form of one or more plasticizers,

[0433] and performing a mixing / oxidation step in which an oxidation mixture is produced, followed by an oxidation step in which the oxidized mixture is allowed to continue reacting for a residence time of 1 second to 10 hours, such as 10 seconds to 6 hours, such as 30 seconds to 2 hours.

[0434] Components (a), (b), (c) and (d) are as defined above in process II for preparing oxidized lignin.

[0435] In one embodiment of the invention, the process comprises a premixing step of bringing the components into contact with each other.

[0436] During the premixing step, the following components may be brought into contact with each other:

[0437] - component (a) and component (b), or

[0438] - component (a) and component (b) and component (c), or

[0439] - component (a) and component (b) and component (d), or

[0440] - component (a) and component (b) and component (c) and component (d).

[0441] In an embodiment of the invention, the premixing step can be carried out as a separate step and the mixing / oxidation step is carried out after the premixing step. In this embodiment of the invention, it is particularly advantageous to contact component (a) and component (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.

[0442] In another embodiment of the invention, the premixing step may correspond to the mixing / oxidation step. In this embodiment of the invention, components such as component (a), component (b) and component (c) are mixed and the oxidation process is started simultaneously. The subsequent residence time may be carried out in the same equipment used to perform the mixing / oxidation step. If component (c) is air, this embodiment of the invention is particularly advantageous.

[0443] It has been found that the oxidation rate can be controlled in a very effective manner by having a mixing / oxidation step followed by an oxidation step, wherein the reaction mixture is preferably not further mixed. At the same time, the cost of carrying out the process is reduced, since the oxidation step after the mixing / oxidation step requires less complex equipment.

[0444] Another advantage is that the oxidized lignin produced is particularly stable. Another unexpected advantage is that the oxidized lignin produced can be well adjusted with respect to viscosity. Another unexpected advantage is that the concentration of the oxidized lignin can be very high.

[0445] In one embodiment, the residence time is selected so that the oxidation reaction proceeds to a desired degree of completion, preferably to complete completion.

[0446] System I for carrying out method III

[0447] In one embodiment, a system for performing the method comprises:

[0448] - at least one rotor-stator arrangement,

[0449] - one or more inlets for water and components (a) and (b),

[0450] - one or more outlets of the rotor-stator arrangement,

[0451] At least one reaction device, in particular at least one reaction tube, which is arranged downstream of the at least one or more outlets in the process flow direction.

[0452] In one embodiment, the system comprises one or more inlets for component (c) and / or component (d).

[0453] In one embodiment, the system includes a premixing device.

[0454] The premixing device may comprise one or more inlets for water and / or component (a) and / or component (b) and / or component (c) and / or component (d).

[0455] In one embodiment, the premixing device comprises inlets for water and components (a) and (b).

[0456] In the premixing step, component (c) may also be mixed with the three ingredients mentioned (water, component (a) and component (b)). The premixing device may then have a further inlet for component (c). If component (c) is air, the premixing device may be formed by an open mixing container, so that in this case component (c) is already in contact with the other components (water, component (a) and component (b)) through the opening of the container. Also in this embodiment of the invention, the premixing device may optionally include an inlet for component (d).

[0457] In one embodiment, the system is constructed in such a way that:

[0458] The inlet for components (a), (b) and (d) is the inlet of a premixing device, in particular an open rotor-stator device,

[0459] The system thus also comprises an additional rotor-stator arrangement,

[0460] The additional rotor-stator device has an inlet for component (c) and the additional rotor-stator device has an outlet for oxidized lignin.

[0461] The premixing step and the mixing / oxidation step can be performed simultaneously. In this case, the premixing device and the mixing / oxidation device are a single device, i.e. a rotor-stator device.

[0462] In one embodiment, a rotor-stator device for the method according to the invention comprises a stator with a toothed ring and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotor-stator device has the following features: a guide funnel protrudes between the arms of the rotor to focus the material flow coming from above into the central area of ​​the container. The outer surface of the guide funnel defines an annular gap that throttles the material flow. A feed screw is provided on the rotor to feed the working area of ​​the device. The guide funnel retains the product in the working area of ​​the device, while the feed screw generates an increased material pressure in the central area.

[0463] System II for carrying out method III

[0464] In one embodiment, a system for performing the method comprises:

[0465] - one or more inlets for water, components (a) and (b),

[0466] - at least one mixing and oxidation device having one or more outlets, and

[0467] - At least one mixer / heat exchanger arranged downstream of at least one or more outlets in the process flow direction, whereby the mixer / heat exchanger comprises a temperature control device.

[0468] In one embodiment, the system comprises an additional one or more inlets for component (c) and / or component (d).

[0469] In one embodiment, the system includes a premixing device.

[0470] The premixing device may comprise one or more inlets for water and / or component (a) and / or component (b) and / or component (c) and / or component (d).

[0471] In one embodiment, the premixing device comprises inlets for water and components (a) and (b).

[0472] In the premixing step, component (c) may also be mixed with the three ingredients mentioned (water, component (a) and component (b)). The premixing device may then have a further inlet for component (c). If component (c) is air, the premixing device may be formed by an open mixing container, so that in this case component (c) is already in contact with the other components (water, component (a) and component (b)) through the opening of the container. Also in this embodiment of the invention, the premixing device may optionally include an inlet for component (d).

[0473] In one embodiment, the system is constructed in such a way that the inlets for components (a), (b) and (d) are inlets of an open rotor-stator device, whereby the system also comprises a mixer / heat exchanger having an inlet for component (c) and an outlet for oxidized lignin.

[0474] The premixing step and the mixing / oxidation step can be carried out simultaneously. In this case, the premixing device and the mixing / oxidation device are a single device.

[0475] In one embodiment, a rotor-stator device for use in the process of the present invention comprises a stator having a toothed ring and a rotor having teeth that mesh with the teeth of the stator. In this embodiment, the rotor-stator device has the following features: A guide funnel protrudes between the arms of the rotor to focus the material flow coming from above into the central area of ​​the container. The outer surface of the guide funnel defines an annular gap that throttles the material flow. A feed screw is provided on the rotor to feed the working area of ​​the device. The guide funnel retains the product in the working area of ​​the device, while the feed screw generates an increased material pressure in the central area.

[0476] Of course, other devices can also be used as premixing devices. In addition, the premixing step can be carried out in a mixing and oxidation device.

[0477] In one embodiment, the mixing and oxidation device is a static mixer. A static mixer is a device for continuous mixing of fluid materials without moving the components. One design of a static mixer is a plate mixer, and another common device type consists of a mixer element contained in a cylindrical (tube) or square housing.

[0478] In one embodiment, the mixer / heat exchanger is configured as a multi-tube heat exchanger with mixing elements. The mixing elements are preferably fixed devices through which the mixture must flow, whereby mixing occurs as a result of the flow. The mixer / heat exchanger can be configured as a plug flow reactor.

[0479] Embodiment 1

[0480] Example IA – Lignin oxidation by hydrogen peroxide in aqueous ammonia solution:

[0481] The amounts of ingredients used according to Example IA are provided in Tables IA 1.1 and IA 1.2.

[0482] Although kraft lignin is soluble in water at relatively high pH values, it is known that at a certain weight percent, the viscosity of the solution increases dramatically. It is generally believed that the increase in viscosity is due to the combined effects of strong hydrogen bonding and π-electron interactions of the many aromatic rings present in lignin. For kraft lignin, a sudden increase in viscosity of about 21 to 22 weight percent in water was observed, and 19 weight percent kraft lignin was used in this example.

[0483] In the pH adjustment step, aqueous ammonia solution was used as base. The amount was fixed at 4 wt % based on the total reaction weight. The pH value after the pH adjustment step and at the start of oxidation was 10.7.

[0484] Table IA2 shows the CHNS elemental analysis results of kraft lignin before and after oxidation. Prior to analysis, the samples were heat treated at 160°C to remove adsorbed ammonia. The analysis showed that during the oxidation process, a certain amount of nitrogen became part of the oxidized lignin structure.

[0485] In batch test experiments, it was determined that adding the entire amount of hydrogen peroxide in small time intervals facilitated oxidation rather than adding peroxide in small amounts over a long period of time. In this example, 2.0 wt % H based on the total reaction weight was used. 2 O 2 .

[0486] Oxidation is an exothermic reaction and a temperature increase will be noted after the addition of peroxide. In this example, the temperature was maintained at 60°C during the three hours of the reaction.

[0487] After oxidation, the amount of lignin functional groups per gram of sample increases, as measured by 31 P NMR and water titration method. 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) was used as phosphorylation reagent and cholesterol was used as internal standard to prepare 31 P NMR samples. The NMR spectra of kraft lignin before and after oxidation were analyzed and the results are summarized in Table IA3.

[0488] The change in COOH groups was determined by water titration and using the following formula:

[0489]

[0490] Where V 2s and V 1s is the endpoint volume of the sample, and V 2b and V 1b is the volume of the blank. In this case, C 酸 is 0.1M HCI, m s is the weight of the sample. The values ​​obtained by water titration before and after oxidation are shown in Table IA4.

[0491] The average COOH functionality can also be quantified by the saponification value, which expresses the number of milligrams of KOH required to saponify 1 g of lignin. This method can be found in AOCS Official Method Cd 3-25.

[0492] 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 enabled the calculation of the average carboxylic acid group content per lignin macromolecule, and these results are shown in Table IA5.

[0493] Example IB – Scale-up of lignin oxidation in ammonia by hydrogen peroxide to pilot scale

[0494] The oxidation of lignin with hydrogen peroxide is an exothermic process and even at laboratory scale, a significant temperature increase was observed after the addition of peroxide. This is a natural consideration when scaling up chemical processes, since the heat generated is related to the cubic dimension (volume), while cooling generally only increases with the square dimension (area). Furthermore, due to the high viscosity of the adhesive intermediates, the process equipment must be carefully selected or designed. Therefore, the scale-up is carefully designed and carried out in several steps.

[0495] The first scale-up step was from 1 L (laboratory scale) to 9 L using a stainless steel professional mixer with very efficient mechanical mixing. The final temperature after scale-up was only slightly higher than that at the lab scale, which was attributed to the efficient air cooling of the reactor and the slow addition of hydrogen peroxide.

[0496] The next scale-up step was done in a closed 200 L reactor with an efficient water jacket and an efficient propeller stirrer. This time the scale was 180 L and the hydrogen peroxide was added in two steps. The separation was about 30 minutes. This scale-up went relatively smoothly, although considerable foaming was a problem, partly due to the high reactor filling. To control the foaming, a small amount of food-grade defoamer was sprayed on the foam. Most importantly, external water cooling was used to obtain a temperature controllable and final temperature below 70 °C.

[0497] The pilot scale reaction was carried out in an 800 L reactor with a water-cooled jacket and a two-blade propeller. 158 kg of lignin (UPM LignoBoost™ BioPiva 100) with a dry matter content of 67% by weight was crushed and suspended in 224 kg of water and stirred to form a uniform suspension. While stirring, 103 kg of 25% ammonia water was pumped into the reactor and stirred for another 2 hours until a dark viscous lignin solution was formed.

[0498] To the stirred lignin solution was added 140 kg of 7.5 wt% hydrogen peroxide over 15 minutes at 20° C. to 25° C. The temperature and foam level were carefully monitored during and after the addition of hydrogen peroxide and cooling water to the cooling jacket to maintain an acceptable foam level and a temperature rise of less than 4° C. per minute and a final temperature of less than 70° C. After the temperature rise stopped, the cooling was turned off and the product mixture was stirred for an additional 2 hours before being transferred to a shipping container.

[0499] Based on the scale-up runs, it can be concluded that even though the reaction is exothermic, in fact most of the heat of reaction is balanced out by the heat capacity of water from room temperature to about 60 °C, and only the last part must be removed by cooling. It should be noted that due to this and due to the short reaction time, the process is very suitable for scale-up and process intensification using continuous reactors such as in-line mixers, tubular reactors or CSTR type reactors. This will ensure good temperature control and a more defined reaction course.

[0500] Testing of scale-up batches showed that the oxidized lignin produced had properties consistent with laboratory-produced batches.

[0501] Table IA 1.1

[0502] Quantity of material to be used in the form provided:

[0503]

[0504] Table IA 1.2

[0505] Active material dosage:

[0506]

[0507] Table IA 2

[0508] Elemental analysis of kraft lignin before and after oxidation:

[0509]

[0510] Table IA 3

[0511] pass 31 P-NMR obtains the functional group distribution of kraft lignin before and after oxidation:

[0512]

[0513] Table 1A4

[0514] COOH group content determined by water titration (mmol / g):

[0515]

[0516] Table IA5

[0517] Table IA5. Number average molar mass (Mn) and weight average molar mass (Mw) determined by size exclusion chromatography, expressed in g / mol, and the average carboxylic acid group content per lignin macromolecule before and after oxidation.

[0518]

[0519] Example II

[0520] In the following examples, several oxidized lignins were prepared.

[0521] The following properties of oxidized lignin were determined:

[0522] Solid content of components:

[0523] The amount of each component in a given oxidized lignin solution is based on the water-free mass of the component or as described below.

[0524] Kraft lignin from UPM as BioPiva100 TM Supplied as dry powder. NH supplied by Sigma-Aldrich 4 OH25% and used in the supplied form. 2 O 2, 30% (Cas no 7722-84-1) was provided by Sigma-Aldrich and used as supplied or diluted with water. PEG 200 was provided by Sigma-Aldrich and was assumed to be anhydrous for simplicity and used as is. PVA (Mw 89.000-98.000, Mw 85.000-124.000, Mw 130.000, Mw 146.000-186.000) (Cas no 9002-89-5) was provided by Sigma-Aldrich and was assumed to be anhydrous for simplicity and used as is. Urea (Cas no57-13-6) was provided by Sigma-Aldrich and was used as supplied or diluted with water. Glycerol (Cas no 56-81-5) was provided by Sigma-Aldrich and was assumed to be anhydrous for simplicity and used as is.

[0525] Oxidized lignin solids

[0526] The content of oxidized lignin after heating to 200°C for 1 hour is called "dry solids" and is expressed as a percentage of the weight remaining after heating.

[0527] Disc-shaped rock wool samples (diameter: 5 cm; height 1 cm) were cut out of the rock wool and heat treated at 580°C for at least 30 minutes to remove all organic matter. The solids of the binder mixture were measured by distributing a sample of the binder mixture (about 2 g) onto the heat-treated rock wool disc in a tinfoil container. The weight of the tinfoil container containing the rock wool disc was weighed directly before and after the addition of the binder mixture. Two such binder mixture-loaded rock wool discs were produced in a tinfoil container 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 solid matter was calculated as the average of the two results.

[0528] COOH group content

[0529] The change in the COOH group content was also determined by water titration using the following formula:

[0530]

[0531] Where V 2s and V 1s is the endpoint volume of the sample, and V 2b and V 1b is the volume of the blank sample. In this case, C 酸 is 0.1M HCI, m s,g is the weight of the sample.

[0532] Method for producing oxidized lignin:

[0533] 1) Mix water and lignin in a 3-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) with stirring. Stir for 1 hour.

[0534] 2) Add ammonia in portions during stirring.

[0535] 3) If the slightly exothermic reaction with ammonia does not raise the temperature, heat to raise the temperature to 35°C.

[0536] 4) Measure pH.

[0537] 5) Add plasticizer PEG200 and stir for 10 minutes.

[0538] 6) After the lignin is completely dissolved for about 1 hour, slowly add 30% H 2 O 2 .

[0539] 7) Add H 2 O 2 The exothermic reaction increases the temperature in the glass bottom flask. If the reaction temperature is below 60°C, the temperature is raised to 60°C and the sample is placed at 60°C for 1 hour.

[0540] 8) The round bottom flask was then removed from the water bath and cooled to room temperature.

[0541] 9) Take samples to determine dry solids, COOH, viscosity, density and pH.

[0542] Oxidized lignin composition

[0543] In the following, the entry numbers of the oxidized lignin examples correspond to the entry numbers used in Table II.

[0544] Example IIA

[0545] 71.0 g of lignin UPM Biopiva 100 was dissolved in 149.0 g of water at 20 °C and 13.3 g of 25% NH 4 OH and stirred for 1 hour with a magnetic stirrer, after which 16.8 g of 30% H 2 O 2 The temperature was raised to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solids, pH, viscosity and density.

[0546] Example IIE

[0547] 71.0 g of lignin UPM Biopiva 100 was dissolved in 88.8 g of water at 20 °C and 13.3 g of 25% NH4 OH and stirred for 1 hour with a magnetic stirrer. 22.8 g PEG 200 was added and stirred for 10 minutes, after which 16.7 g 30% H 2 O 2 The temperature was raised to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solids, pH, viscosity and density.

[0548] Example IIC

[0549] 71.0 g lignin UPM Biopiva 100 was dissolved in 57.1 g water at 20 °C and 13.3 g 25% NH 4 OH and stirred for 1 hour by a mechanical stirrer, wherein 16.6 g of 30% H 2 O 2 The temperature was raised to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solids, pH, viscosity and density.

[0550] Example II F

[0551] 71.0 g lignin UPM Biopiva 100 was dissolved in 57.1 g water at 20 °C and 13.3 g 25% NH 4 OH and stirred for 1 hour by a mechanical stirrer. 19.0 g PEG200 was added and stirred for 10 minutes, after which 16.6 g 30% H 2 O 2 The temperature was raised to 60°C in a water bath. After 1 hour of oxidation, the water bath was cooled to stop the reaction. The resulting material was analyzed for COOH, dry solids, pH, viscosity and density.

[0552]

[0553]

[0554]

[0555]

[0556] Example III:

[0557] 8.5L hot water (50℃) and 1.9L NH 4OH (24.7%) was mixed, to which 9.0 kg lignin (UPM biopiva 100) was slowly added within 10 minutes under high stirring (660 rpm, 44 Hz).

[0558] The temperature increased due to the high shear forces. After 30 minutes, 4 L of hot water were added and the material was stirred for another 15 minutes before the remaining portion of hot water (5 L) was added. A sample was taken and analyzed for undissolved lignin by using a Hegman gauge and pH measurement.

[0559] The premix is ​​then transferred to the rotor-stator apparatus and the reaction apparatus, where the premix is ​​heated by using H 2 O 2 (17.5 volume %) was oxidized. The reaction apparatus used in this case at least partially comprises a reaction tube and a reaction vessel. The feed rate of the premix is ​​150 L / h, H 2 O 2 The feed rate is 18L / h.

[0560] In this example, a Cavitron CD1000 rotor-stator device was used for the mixing / oxidation step. The rotor-stator device was operated at 250 Hz (55 m / s peripheral speed) and a back pressure of 2 bar. The residence time in the reaction tube was 3.2 minutes and the residence time in the reaction vessel was 2 hours.

[0561] The premix temperature was 62°C and the oxidation step raised the temperature to 70°C.

[0562] The final product was analyzed for COOH group content, dry solid matter, pH, viscosity and residual H 2 O 2 .

[0563] Table III:

[0564]

[0565] Example IV:

[0566] 484L hot water (70℃) and 47.0L NH 4 OH (24.7%) was mixed, wherein 224.0 kg lignin (UPM biopiva 100) was then slowly added within 15 minutes under high stirring. A sample was taken and analyzed for undissolved lignin by using a Hegman gauge and pH measurement.

[0567] The premix is ​​then transferred to a static mixer and mixer / heat exchanger where it is heated by using H 2 O 2 (35 volume %) was oxidized. The feed rate of the premix was 600 L / h, H 2 O2 The feed rate was 17.2 L / h. The residence time in the mixer / heat exchanger was 20 minutes.

[0568] During the oxidation step, the temperature of the mixture increases to as high as 95°C.

[0569] The final product was analyzed for COOH group content, dry solid matter, pH, viscosity and residual H 2 O 2 .

[0570] An adhesive was prepared based on this AOL: 49.3 g AOL (19.0% solids), 0.8 g primid XL552 (100% solids) and 2.4 g PEG200 (100% solids) were mixed with 0.8 g water to give 19% solids; this was then used for mechanical property testing in bar tests.

[0571] Primid XL552 has the following structure:

[0572]

[0573] Bar testing

[0574] The mechanical strength of the binders was tested in a rod test. For each binder, 16 rods were manufactured from a mixture of the binder and rock wool pellets from a rock wool spinning production.

[0575] A sample of the adhesive solution (16.0 g) comprising 15% dry solids was thoroughly mixed with pellets (80.0 g). The resulting mixture was then filled into four grooves provided in the form of heat-resistant silicone for making small rods (4×5 grooves per shape; groove top dimensions: length = 5.6 cm, width = 2.5 cm; groove bottom dimensions: length = 5.3 cm, width = 2.2 cm; groove height = 1.1 cm). The mixture placed in the groove was then pressed with a flat metal rod of appropriate size to produce a uniform rod surface. 16 rods of each adhesive were made in this way. The resulting rods were then cured at 200°C. The curing time was 1 hour. After cooling to room temperature, the rods were carefully removed from the container. Five of the rods were aged in an 80°C water bath for 3 hours.

[0576] After drying for 1 to 2 days, the aged bars and 5 unaged bars were broken 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) was studied for its mechanical strength on a Bent Tram machine. When the bars were placed in the machine, the "top surface" (i.e. the surface with the dimensions length = 5.6 cm, width = 2.5 cm) was facing upwards.

[0577] BRIEF DESCRIPTION OF THE DRAWINGS

[0578] Figure 1 Parts of possible lignin structures are shown.

[0579] Figure 2 Lignin precursors and common interunit linkages are shown.

[0580] Figure 3 At least four groups of industrial lignins available on the market are shown.

[0581] Figure 4 A summary of some industrial lignin properties is shown.

[0582] Figure 5 is a perspective view of an acoustic product according to the present invention;

[0583] Figure 6 is a schematic diagram of the method of the present invention up to the curing oven stage;

[0584] Figure 7 yes Figure 6 Schematic diagram outside the curing oven continued. DETAILED DESCRIPTION

[0585] Figure 5 The acoustic product 1 in the figure has a smooth, flat, sound-absorbing front face 2 extending in the XY plane, a back face 3, and side edges 4 extending in the Z direction between the front face and the back face. The acoustic product consists of an acoustic element, which is a bonded MMVF substrate, and a facing on the front face 2 and the back face 3. The side edges 4 can be square or have some other contours.

[0586] like Figure 6As shown, a typical apparatus for manufacturing the product comprises a cascade spinneret 6 having a plurality of rotors 7 mounted on the front face for receiving melt from a melt tank 8, whereby the melt falling on the rotors is thrown from said rotors as fibers from one rotor to the next. These fibers are entrained in the air from inside and around the rotors 7, whereby the fibers are conveyed to a collecting chamber 9 having a perforated collector conveyor belt 10 at its base. The air is sucked through the collector and a web 11 is formed on the collector, which is removed from the collecting chamber 9 and sent to another conveyor belt 12. The primary web 11 is guided by the conveyor belt 12 into the top of a cross-lapping pendulum 13, by which the layers of the primary web are cross-lapped with each other, whereupon they are collected as a secondary web 15A below the pendulum on the conveyor belt 14.

[0587] The secondary web 15A is guided by conveyor belt 14 to a pair of conveyor belts 16 for applying vertical compression to the secondary web from its natural depth (point A) to its compressed depth (at point B). The weight per unit area of ​​the secondary web at point A is W.

[0588] The compressed secondary web 15B is transferred from point C to point D by conveyor belt 17. Conveyor belts 16 and 17 typically both travel at substantially the same speed to establish a constant travel speed of the secondary web from the vertical compression section AB to point D.

[0589] The web is then transferred between a pair of conveyor belts 18 extending between points E and F. Conveyor belt 18 travels much slower than conveyor belts 16 and 17, thereby applying longitudinal compression between points D and F.

[0590] Although items 14, 16, 17 and 18 are shown as conveyor belts spaced apart from one another in the X-direction for clarity, in practice they are typically very close to one another in the X-direction.

[0591] Points D and E are preferably close enough to each other or connected to each other by a belt to prevent the secondary web from escaping from the desired path of travel. As a result, a large amount of longitudinal compression has occurred when the web emerges at point F. If necessary, a restraining guide can be provided between points D and E to prevent the web from breaking out when points D and E are not close together.

[0592] The resulting longitudinally compressed wadding 15C is then transported along conveyor belt 19 between points G and H at a higher speed than conveyor belt 18. This applies some longitudinal decompression or extension to the longitudinally compressed web and prevents the web from being interrupted from the desired path of travel, for example, by bending upward due to internal forces within the web. If desired or necessary, conveyor belts or other guides (not shown) can be established between the wadding. [T1] The upper surface (above the conveyor belt 19) is checked to ensure that there is no leakage.

[0593] When vertical compression is to be applied to the longitudinally compressed web, this is accomplished by passing the web after it leaves point H between conveyor belts 20 which meet to vertically compress the web as it travels between the conveyor belts and points I and J.

[0594] The resulting uncured batt 15D has first and second major faces 3A and 3B. Glass fiber muslin cloth 22 from roller 23 is then brought into contact with faces 3A and 3B. Glass muslin cloth 22 has been provided with an adhesive in accordance with the present invention to bond the muslin cloth to the batt. The resulting assembly is then passed through a curing oven 25, where sufficient pressure is applied by a conveyor belt 24 to secure the sandwich of the two layers of muslin cloth 22 and batt 15D together while the adhesive and bonding agent for the MMVF are cured.

[0595] The bonded batt 15E comes out of the curing oven and is cut from the center by a band saw 26 or other suitable saw into two cut batts 27, each having an outer face 3 with a tissue cloth 22 and an inner cut surface 2. Each cut batt 27 is supported on a conveyor belt 28 and travels under a wear belt 29, where the batt 27 is worn or ground to a flat configuration and an additional facing 22 is applied from a roller 30 and bonded to the wear surface 2. The worn or ground cut batt 27 is then separated by a suitable cutter 31 into individual batts 1, which are transported away on a conveyor belt 32.

[0596] The lacquer may be applied to one or both sides.

[0597] In this specification, conveyor bands or belts are exemplified, but any or all conveyor bands can be replaced by any suitable device that generates relevant transportation in a manner of acceleration, deceleration or vertical compression as required. For example, a roller conveyor can be used instead of a belt.

[0598] Example

[0599] Testing was conducted to determine the peel strength of glass scrim that had been applied to an MMVF acoustic element using the adhesive of claim 1. The acoustic element had the properties defined in Table 1 below:

[0600] Table 1

[0601]

[0602]

[0603] Determination of LOI (binder content) The determination of organic content is carried out according to DS / EN13820:2003, where the binder content is defined as the amount of organic material burned off at a given temperature, here (590 ± 20 ° C) for at least 10 minutes or more, until the mass is constant. The determination of loss on ignition consists of at least 10 g of mineral wool, equivalent to 8 to 20 cuts (at least 8 cuts), evenly distributed on the specimen using a cork borer, ensuring that the entire product thickness is included.

[0604] The peel strength was determined as follows:

[0605] Gauze adhesion measurements [g] were made using a 5 cm wide metal punch and a small manual weight with a hook.

[0606] Measurement method:

[0607] Place the product on a flat surface.

[0608] Using a cutter, cut the surface of the gauze cloth into approximately 50cm lengths.

[0609] Attach the torn end to the grip of the dynamometer and pull.

[0610] The maximum and minimum scale deflections should be read simultaneously.

[0611] result

[0612]

[0613]

[0614] It is generally believed that commercial production requires a peel strength of at least 100 g. It can be seen that the product of the present invention fully meets this standard.

[0615] Details of adhesive composition:

[0616] 3267 kg of water was charged into a 6000 L reactor, followed by 287 kg of ammonia (24.7%). Then 1531 kg of lignin UPM BioPiva 100 was slowly added over 30 to 45 minutes. The mixture was heated to 40°C and kept at this temperature for 1 hour. After 1 hour, the insoluble lignin was checked. This can be achieved by checking the solution on a glass plate or Hegman gauge. The insoluble lignin can be seen as small particles in the brown adhesive. During the dissolution step, the color of the lignin solution will change from brown to shiny black.

[0617] After the lignin was completely dissolved, 1 liter of foam inhibitor (from The temperature of the batch was maintained at 40°C.

[0618] Then the addition of 307.5 kg of 35% hydrogen peroxide was started. Hydrogen peroxide was fed at a rate of 200 to 300 liters / hour. The first half of the hydrogen peroxide was fed at a rate of 200 liters / hour, after which the feed rate was increased to 300 liters / hour.

[0619] During the addition of hydrogen peroxide, the temperature in the reaction mixture was controlled by heating or cooling so that the final reaction temperature reached 65°C.

[0620] After reacting at 65° C. for 15 minutes, the reaction mixture was cooled to a temperature of 50° C. or less. Thus, a resin having a COOH value of 1.2 mmol / g solid was obtained.

[0621] Starting from this ammoxidized lignin (AOL) resin, a binder was formulated by adding 270 kg of polyethylene glycol 200 and 281 kg of a 31% aqueous solution of β-hydroxyalkylamide (Primid XL-552).

Claims

1. A method of manufacturing an acoustic product, the method comprises: providing an acoustic element including a first major surface and a second major surface; providing a first facing; fixing the first facing on the first major surface of the acoustic element by using an adhesive; and curing the adhesive, wherein the adhesive is an aqueous adhesive composition comprising: - component (i), which is in the form of one or more oxidized lignins; - component (iia), which is in the form of one or more modifiers.

2. The method according to claim 1, wherein the second component (iia) comprises one or more modifiers selected from the group consisting of: - epoxy oils based on fatty acid triglycerides; - molecules having 3 or more epoxy groups; - one or more flexible oligomers or polymers containing reactive functional groups, preferably wherein (a) the polymer is selected from: low Tg acrylic polymers; low Tg vinyl polymers; and low Tg polyethers; and / or (b) the reactive functional groups are selected from: carbodiimide groups, acid anhydride groups, oxazoline groups, amino groups, and epoxy groups; - polyethyleneimine, polyvinylamine, or fatty amines; and - aliphatic polyfunctional carbodiimides.

3. The method according to claim 1 or 2, wherein based on the dry weight of component (i), the aqueous adhesive composition comprises component (iia) in an amount of 1 wt% to 40 wt%, preferably 4 wt% to 20 wt%, more preferably 6 wt% to 12 wt%.

4. The method according to any one of the preceding claims, wherein the adhesive composition further comprises: - component (ii), which is in the form of one or more crosslinking agents; and / or - component (iii), which is in the form of one or more plasticizers.

5. The method according to any one of the preceding claims, wherein the acoustic element is a man-made vitreous fiber (MMVF) panel.

6. The method according to claim 5, wherein the man-made vitreous fiber panel is formed of man-made vitreous fibers, and the man-made vitreous fibers are bonded by a cured adhesive, wherein the adhesive before curing is a composition which comprises: component (i), which is in the form of one or more oxidized lignins; component (ii), which is in the form of one or more crosslinking agents; and component (iii), which is in the form of one or more plasticizers.

7. The method according to any one of the preceding claims, wherein the first facing is a fiberglass scrim.

8. The method according to any one of the preceding claims, wherein the first facing has two major surfaces, and the method comprises applying an adhesive to the major surfaces of the first facing, and then applying the major surfaces of the first facing to the first major surface of the acoustic element.

9. The method according to claim 8, comprising applying the adhesive by using a roller.

10. The method according to any one of the preceding claims, wherein the step of curing the adhesive is carried out at a temperature of from 100 °C to 300 °C, preferably from 170 °C to 270 °C, preferably from 180 °C to 250 °C, preferably from 190 °C to 230 °C.

11. The method according to any one of the preceding claims, wherein the density of the acoustic element is in the range of 40 kg / m 3 to 180 kg / m 3 and, for example, in the range of 80 kg / m 3 to 160 kg / m 3 and preferably in the range of 100 kg / m 3 to 140 kg / m 3 .

12. The method according to any one of the preceding claims, wherein the loss on ignition (LOI) of the acoustic element is in the range of from 2% by weight to 8% by weight, preferably in the range of from 3% by weight to 5% by weight.

13. The method according to any one of the preceding claims, comprising fixing a second facing to the second major surface of the acoustic element.

14. The method according to claim 13, comprising cutting the cured element in a plane substantially parallel to the major surface and smoothing each cut surface by abrasion to form two acoustic products.

15. The method according to any one of the preceding claims, wherein the thickness of the acoustic product is in the range of from 12 mm to 100 mm, for example in the range of from 15 mm to 50 mm.

16. The method according to any one of the preceding claims, wherein the width of the acoustic product is in the range of from 550 mm to 650 mm, preferably about 600 mm.

17. The method according to any one of the preceding claims, wherein the length of the acoustic product is in the range of from 550 mm to 650 mm or from 1100 mm to 1300 mm, preferably about 600 mm, preferably about 1200 mm.

18. The method according to any one of the preceding claims, comprising applying the binder at a dry weight of from 5 g / m 2 to 12 g / m 2 .

19. The method according to any one of the preceding claims, wherein the acoustic product is a ceiling.

20. The method according to any one of claims 1 to 18, wherein the acoustic product is a wall panel.

21. The method according to any one of claims 1 to 18, wherein the acoustic product is a baffle.

22. An acoustic product obtained by a method according to any one of claims 1 to 21.

23. An acoustic product comprising an acoustic element having a first major surface and a second major surface and a first facing, wherein the first facing is fixed to the first major surface of the acoustic element by an adhesive, wherein the adhesive before curing is an aqueous adhesive composition, the aqueous adhesive composition comprises: - component (i), which is in the form of one or more oxidized lignins; - component (iia), which is in the form of one or more modifiers.

24. The acoustic product according to claim 23, wherein the adhesive composition further comprises: - component (ii), which is in the form of one or more crosslinking agents; and / or - component (iii), which is in the form of one or more plasticizers.

25. A ceiling system comprising a plurality of acoustic products according to any one of claims 22 to 24 suspended in a grid.

26. A wall system comprising a plurality of acoustic products according to any one of claims 22 to 24 suspended on a wall.

27. The method, product or system according to any one of the preceding claims, wherein component (i) is in the form of one or more ammonia-oxidized lignins (AOL).

28. The method, product or system according to any one of claims 4 to 22 or 24 to 27, wherein the component (ii) comprises one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

29. The method, product or system according to any one of claims 4 to 22 or 24 to 27, wherein the component (ii) comprises: - one or more crosslinking agents selected from polyethyleneimine, polyvinylamine, fatty amines; and / or - one or more crosslinking agents in the form of fatty acid 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 such as polycaprolactone; and / or - one or more crosslinking agents selected from starch, modified starch, CMC; and / or - one or more crosslinking agents in the form of aliphatic polyfunctional carbodiimides; and / or - one or more crosslinking agents selected from melamine-based crosslinking agents such as hexakis(methoxymethyl)melamine (HMMM) crosslinking agents.

30. The method, product or system according to any one of claims 4 to 22 or 24 to 29, wherein based on the dry weight of component (i), the aqueous adhesive composition comprises component (ii) in an amount of 1% to 40% by weight, such as 4% to 20% by weight, such as 6% to 12% by weight.

31. The method, product or system according to any one of claims 4 to 22 or 24 to 30, wherein component (iii) comprises one or more plasticizers selected from polyethylene glycol, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or acids such as adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic polymers having free carboxyl groups and / or polyurethane dispersions having free carboxyl groups.

32. The method, product or system according to any one of claims 4 to 22 or 24 to 30, wherein the component (iii) comprises: - one or more plasticizers selected from fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol; and / or - one or more plasticizers selected from alkoxylates such as ethoxylates, such as butanol ethoxylates such as butoxytriglycol; 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 adipates, acetates, benzoates, cyclohexanecarboxylates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates; and / or - one or more plasticizers selected from phenolic derivatives such as alkyl- or aryl-substituted phenols; and / or -One or more plasticizers selected from silanols, siloxanes; and / or - -One or more plasticizers selected from sulfates such as alkyl sulfates, sulfonates such as alkyl aryl sulfonates such as alkyl and / or -sulfonates, phosphates such as tripolyphosphates; and / or -One or more plasticizers in the form of hydroxy acids; and / or -One or more plasticizers selected from monomeric amides such as acetamide, benzamide, fatty acid amides such as tall oil amide; and / or - -One or more plasticizers selected from quaternary ammonium compounds such as betaine, distearyldimethylammonium chloride; and / or - -One or more plasticizers selected from vegetable oils such as castor oil, palm oil, linseed oil, tall oil, soybean oil; and / or -One or more plasticizers selected from hydrogenated oils, acetylated oils; and / or - -One or more plasticizers selected from acidic methyl esters; and / or - -One or more plasticizers selected from alkyl polyglycosides, glucamides, aminoglucamides, sucrose esters, sorbitan esters; and / or -One or more plasticizers selected from polyethylene glycols, polyethylene glycol ethers.

33. The method, product or system according to any one of claims 4 to 22 or 24 to 32, wherein based on the dry weight of component (i), the content of component (iii) in the aqueous binder composition is 0.5 wt% to 50 wt%, preferably 2.5 wt% to 25 wt%, more preferably 3 wt% to 15 wt%.

34. The method, product or system according to any one of the preceding claims, wherein the aqueous binder composition comprises: Additional component (iv) in the form of one or more coupling agents such as organofunctional silanes.

35. The method, product or system according to any one of the preceding claims, wherein the aqueous binder composition further comprises: Component (v) in the form of one or more components selected from ammonia, amines or any salts thereof.

36. The method, product or system according to any one of the preceding claims, wherein the aqueous binder composition comprises: Additional component in the form of urea, in particular, based on the dry weight of component (i), in an amount of 5 wt% to 40 wt%, such as 10 wt% to 30 wt%, such as 15 wt% to 25 wt%.

37. The method, product or system according to any one of the preceding claims, wherein the aqueous binder composition consists essentially of the following components consisting of: -Component (i) in the form of one or more oxidized lignins; -Component (iia) in the form of one or more modifiers of epoxy oils based on fatty acid triglycerides; -Component (iv) in the form of one or more coupling agents such as organofunctional silanes; -Optional component in the form of one or more compounds selected from ammonia, amines or any salts thereof; -Optional component in the form of urea; -Optional component in the form of more reactive or non-reactive polysiloxanes; -Optional hydrocarbon oil; -Optional one or more surfactants; and -Water.

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