Method for growing plants

Abstract

The present invention relates to a method of growing a plant in an adhesive growth substrate article, the method comprising:-providing at least one adhesive growth substrate article comprising artificial vitreous fibres (MMVF) adhered with a cured aqueous adhesive composition; contacting one or more seeds, seedlings, cuttings or plants with the growth substrate article; -irrigating the growth substrate article; wherein, prior to curing, the aqueous adhesive composition comprises:-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 application is a divisional application of a patent application with application number 2020801014132, application date April 3, 2020, and invention name “Method for Growing Plants”. Technical Field

[0002] The present invention relates to a method of growing plants in an adhesive growth substrate, an adhesive growth substrate product and a use of the adhesive growth substrate. Background Art

[0003] For many years, it has been known to grow plants in an adherent growth matrix formed from man-made vitreous fibers (MMVF). MMVF products used for this purpose are usually provided in the form of adherent plugs, blocks or slabs, and usually contain a binder to provide structural integrity to the product.

[0004] Historically, the main binders of choice have been phenol-formaldehyde resins and phenol-formaldehyde urea resins, such as those disclosed in WO2009 / 090053, WO2008 / 009467, WO2008 / 009462, WO2008 / 009461, WO2008 / 009460 and WO2008 / 009465. These binders are economical to produce and provide excellent mechanical handling properties, which is very important for plant growth substrates because automated equipment is used in handling and large amounts of water are retained in the substrate. It is undesirable for the substrate to be damaged during handling or for the substrate to lose its rigidity and shape while holding water.

[0005] However, existing and proposed legislation aimed at reducing or eliminating formaldehyde emissions has led to the development of formaldehyde-free adhesives, such as those described in WO2017 / 114723, WO2017 / 114724, WO2012 / 028650.

[0006] At least most previously known adhesive compositions for plant growth substrates have starting materials derived from fossil fuels. Consumers prefer articles produced wholly or at least partially from renewable materials, and there is a need to provide adhesives for plant growth substrates produced at least partially from renewable materials.

[0007] Adhesive compositions based on renewable materials have been proposed before, such as in WO2017 / 114723 and WO2017 / 114724. However, MMVF articles made with these adhesives still have some disadvantages in terms of mechanical properties compared to MMVF articles made with phenol-formaldehyde resins. In addition, such adhesives are usually made from expensive starting materials.

[0008] In addition, there is a continuing desire to improve the water holding properties of plant growth substrates, such as water retention or water distribution over height. There is also a continuing desire to reduce the phytotoxicity of adhesives used in plant growth substrates.

[0009] It is desirable to use water and nutrients as efficiently as possible during the growing process. This is for both cost reasons and environmental reasons. In particular, wastewater containing nutrients is difficult to dispose of due to environmental regulations. It is therefore desirable to improve water retention in order to reduce the amount of wastewater (also called drainage).

[0010] In addition, there is a desire to reduce the amount and number of ingredients required to produce plant growth substrates. Typically, additives such as wetting agents are added to plant growth substrates to increase hydrophilicity. However, for environmental and cost-effective purposes, it would be desirable to provide an adhesive that does not require the further addition of a wetting agent.

[0011] It is also desirable to produce such an adhesive that can be used at lower levels than other adhesives without sacrificing mechanical properties. Thus, it is desirable to produce such an adhesive for plant growth substrates that does not contain formaldehyde but has mechanical handling properties (such as compressive strength) that are equal to or better than phenol-formaldehyde adhesives. It is desirable that such an adhesive has improved water holding properties (such as water retention and distribution of water over height) thereby reducing water waste and reducing phytotoxicity. Furthermore, it is desirable that the production of such an adhesive is economical and based primarily on renewable sources. Finally, it is desirable that such an adhesive has reduced usage and does not require the further addition of a wetting agent. Summary of the invention

[0012] The plant growth substrate used in the present invention solves the above problems.

[0013] In a first aspect of the present invention, there is provided a method for growing plants in an adherent growth matrix article, the method comprising:

[0014] - providing at least one adherent growth substrate article comprising man-made vitreous fibers (MMVF) bonded with a cured aqueous binder composition;

[0015] - contacting one or more seeds, seedlings, cuttings or plants with the growth matrix preparation;

[0016] - irrigating said growth substrate preparation;

[0017] Wherein, the aqueous adhesive composition before curing comprises:

[0018] - component (i) in the form of one or more oxidized lignins;

[0019] - component (ii) in the form of one or more crosslinking agents;

[0020] - component (iii) in the form of one or more plasticizers.

[0021] In a second aspect of the present invention, there is provided an adherent growth substrate article comprising a man-made vitreous fiber (MMVF) bonded to a cured aqueous binder composition, wherein the aqueous binder composition prior to curing comprises:

[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 a third aspect of the present invention, there is provided an array of two or more adherent growth substrate articles, wherein the adherent growth substrate articles comprise man-made vitreous fibers (MMVF) bonded to a cured aqueous binder composition, wherein the aqueous binder composition prior to curing comprises:

[0026] - component (i) in the form of one or more oxidized lignins;

[0027] - component (ii) in the form of one or more crosslinking agents;

[0028] - component (iii) in the form of one or more plasticizers.

[0029] In a fourth aspect of the present invention there is provided a use of an adherent growth matrix product for growing plants, wherein the adherent growth matrix product comprises man-made vitreous fibers (MMVF) bonded to a cured aqueous binder composition, wherein the aqueous binder composition before curing comprises:

[0030] - component (i) in the form of one or more oxidized lignins;

[0031] - component (ii) in the form of one or more crosslinking agents;

[0032] - component (iii) in the form of one or more plasticizers.

[0033] In a fifth aspect of the present invention there is provided a method for manufacturing a growth substrate product, comprising the steps of:

[0034] (i) provide MMVF;

[0035] (ii) spraying the MMVF with an aqueous adhesive composition;

[0036] (iii) collecting and consolidating the MMVF; and

[0037] (iv) curing the aqueous adhesive composition;

[0038] Wherein, the aqueous adhesive composition before curing comprises:

[0039] - component (i) in the form of one or more oxidized lignins;

[0040] - component (ii) in the form of one or more crosslinking agents;

[0041] - component (iii) in the form of one or more plasticizers.

[0042] The inventors of the present invention have unexpectedly discovered that it is possible to produce a formaldehyde-free adhesive that provides a growth substrate with mechanical handling properties (e.g., compressive strength) that are equal to or even superior to those of a phenol-formaldehyde adhesive. The inventors have also produced such an adhesive that provides a growth substrate with improved water holding properties (e.g., moisture retention) and lower levels of phytotoxicity, which is highly desirable for plant growth and development. This can reduce water waste (i.e., drainage). The inventors have produced such an adhesive that is economical and based primarily on renewable sources. Finally, such an adhesive can be used in lower amounts and does not require the addition of a wetting agent to the growth substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figures 1A to 1E The results of the compressive strength test are shown.

[0044] Figure 2 The results of the water retention test are shown.

[0045] Figure 3 The results of the water distribution test in height are shown.

[0046] Figure 4 A section of a possible lignin structure is shown.

[0047] Figure 5 Lignin precursors and common interunit linkages are shown.

[0048] Figure 6 Four groups of industrial lignins available on the market are shown.

[0049] Figure 7 A summary of the properties of industrial lignin is shown. DETAILED DESCRIPTION

[0050] The present invention relates to a method for growing plants in an adherent growth matrix article, the method comprising:

[0051] - providing at least one adherent growth substrate article comprising man-made vitreous fibers (MMVF) bonded with a cured aqueous binder composition;

[0052] - contacting one or more seeds, seedlings, cuttings or plants with the growth matrix preparation;

[0053] - irrigating said growth substrate preparation;

[0054] Wherein, the aqueous adhesive composition before curing comprises:

[0055] - component (i) in the form of one or more oxidized lignins;

[0056] - component (ii) in the form of one or more crosslinking agents;

[0057] - component (iii) in the form of one or more plasticizers.

[0058] The method of the present invention comprises an adhered growth matrix article containing man-made vitreous fibers (MMVF). The man-made vitreous fibers (MMVF) can have any suitable oxide composition. The fibers can be glass 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.

[0059] Stone fibers usually contain the following oxides, expressed in weight percentage:

[0060] SiO 2 : 30 to 51

[0061] CaO: 8 to 30

[0062] MgO: 2 to 25

[0063] FeO (including Fe 2 O 3 ): 2 to 15

[0064] Na 2 O+K 2 O: No more than 10

[0065] CaO+MgO: 10 to 30

[0066] In a preferred embodiment, the MMVF comprises the following elements in amounts calculated as % by weight of the oxides:

[0067] SiO 2 : At least 30, 32, 35 or 37; not more than 51, 48, 45 or 43

[0068] Al2 O 3 : At least 12, 16 or 17; not more than 30, 27 or 25

[0069] CaO: at least 8 or 10; not more than 30, 25 or 20

[0070] MgO: at least 2 or 5; not more than 25, 20 or 15

[0071] FeO (including Fe 2 O 3 ): At least 4 or 5; not more than 15, 12 or 10

[0072] FeO+MgO: at least 10, 12 or 15; not more than 30, 25 or 20

[0073] Na 2 O+K 2 O: 0 or at least 1; not more than 10

[0074] CaO+MgO: at least 10 or 15; not more than 30 or 25

[0075] TiO 2 : 0 or at least 1; not more than 6, 4 or 2

[0076] TiO 2 +FeO: at least 4 or 6; not more than 18 or 12

[0077] B 2 O 3 : 0 or at least 1; not more than 5 or 3

[0078] P 2 O 5 : 0 or at least 1; not more than 8 or 5

[0079] Others: 0 or at least 1; not more than 8 or 5.

[0080] The MMVF prepared by the process of the present invention preferably has the following composition in wt %:

[0081] SiO 2 35 to 50

[0082] Al 2 O 3 12 to 30

[0083] TiO 2 Up to 2

[0084] Fe 2 O 3 3 to 12

[0085] CaO 5 to 30

[0086] MgO up to 15

[0087] Na 2 O 0 to 15

[0088] K 2 O 0 to 15

[0089] P 2 O 5 Up to 3

[0090] MnO up to 3

[0091] B 2 O 3 Up to 3

[0092] Another preferred composition of the MMVF has the following weight %:

[0093] SiO 2 39% to 55% Preferred 39% to 52%

[0094] Al 2 O 3 16% to 27% preferably 16 to 26%

[0095] CaO 6% to 20% preferably 8% to 18%

[0096] MgO 1% to 5% preferably 1% to 4.9%

[0097] Na 2 O 0% to 15% preferably 2% to 12%

[0098] K 2 O 0% to 15% preferably 2% to 12%

[0099] R 2 O(Na 2 O+K 2 O) 10% to 14.7% preferably 10% to 13.5%

[0100] P 2 O 5 0% to 3% preferably 0% to 2%

[0101] Fe 2 O 3 (Total iron) 3% to 15% preferably 3.2% to 8%

[0102] B 2 O 3 0% to 2% preferably 0 to 1%

[0103] TiO 20% to 2% preferably 0.4% to 1%

[0104] Others 0% to 2.0%.

[0105] Glass fibers usually contain the following oxides, in percentage by weight:

[0106] SiO 2 : 50 to 70

[0107] Al 2 O 3 : 10 to 30

[0108] CaO: not more than 27

[0109] MgO: not more than 12.

[0110] Glass fibers may also contain the following oxides, expressed in percentage by weight:

[0111] Na 2 O+K 2 O: 8 to 18, especially Na 2 O+K 2 O is greater than CaO+MgO

[0112] B 2 O 3 : 3 to 12.

[0113] Some glass fiber compositions may contain Al 2 O 3 : Less than 2%.

[0114] The geometric mean fiber diameter is typically in the range of 1.5 μm to 10 μm, in particular 2 μm to 8 μm, preferably 2 μm to 5 μm. The inventors have found that this geometric fiber diameter range has a positive effect on capillarity, thereby improving the distribution of water in height and the water absorption rate in the growth substrate.

[0115] Prior to curing, the growth substrate according to the present invention comprises an aqueous binder composition comprising:

[0116] - component (i) in the form of one or more oxidized lignins;

[0117] - component (ii) in the form of one or more crosslinking agents;

[0118] - component (iii) in the form of one or more plasticizers.

[0119] In a preferred embodiment, the adhesive is formaldehyde-free.

[0120] For the purposes of this application, the term "formaldehyde-free" is defined as a mineral wool product characterized by a formaldehyde emission level of less than 5 μg / m 2 / h of mineral wool products, preferably less than 3μg / m 2 / h. Preferably, the test is carried out according to ISO 16000 to test the aldehyde emission.

[0121] Component (i)

[0122] Component (i) is in the form of one or more oxidized lignins.

[0123] 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.

[0124] Figure 4 A slice of a possible lignin structure is shown.

[0125] There are at least four groups of industrial lignins available on the market. Figure 6 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. biorefinery, 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 consists primarily of coniferyl alcohol units, see Figure 5 , thus, they are more homogeneous than hardwood lignins, which have a higher syringol content, see Figure 5 The appearance and consistency of lignin is quite variable and depends largely on the process.

[0126] Figure 7 A summary of the properties of these industrial lignins is shown.

[0127] 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 washing, leaching and filtering to remove ash and other contaminants. These three processes are at various stages of commercialization around the world.

[0128] 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.

[0129] Commercial kraft lignin is usually purer than lignin sulfonate. The molecular weight is 1000 g / mol to 3000 g / mol.

[0130] 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 or higher.

[0131] 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.

[0132] Another type of lignin is that 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.

[0133] 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.

[0134] Previous attempts to use lignin as a basic compound for binder compositions for mineral fibers have failed because it has proven difficult to find suitable crosslinkers 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 phenol in binder applications or phenolic resins in asphalt. It is also used as a cement and concrete additive and in some applications as a dispersant.

[0135] Crosslinking of polymers should generally provide better properties, such as mechanical, chemical and thermal resistance. Lignin is particularly rich in phenolic and aliphatic hydroxyl groups, which can react to result in 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 largely on the way in which lignin is separated from cellulose and hemicellulose (thiols in kraft lignin, sulfonates in lignin sulfonates, etc.).

[0136] It has been found that by using oxidized lignin, binder compositions for mineral fibers can be prepared, resulting in mineral fiber products having excellent properties.

[0137] In one embodiment, component (i) is in the form of one or more oxidized kraft lignins.

[0138] In one embodiment, component (i) is in the form of one or more oxidized alkali lignins.

[0139] 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 mean lignin that has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia-oxidized lignin" is abbreviated as AOL.

[0140] In an alternative embodiment, the ammonia is partially or completely replaced by an alkali metal hydroxide, in particular sodium hydroxide and / or potassium hydroxide.

[0141] A typical oxidizing agent used to prepare oxidized lignin is hydrogen peroxide.

[0142] In one embodiment, the ammoxidized lignin comprises one or more compounds selected from ammonia, amines, hydroxides or any salts thereof.

[0143] In one embodiment, component (i) has a carboxylic acid group content of 0.05 mmol / g to 10 mmol / g, such as 0.1 mmol / g to 5 mmol / g, such as 0.20 mmol / g to 1.5 mmol / g, such as 0.40 mmol / g to 1.2 mmol / g, such as 0.45 mmol / g to 1.0 mmol / g, based on the dry weight of component (i).

[0144] In one embodiment component (i) is a macromolecule having an average carboxylic acid group content of more than 1.5 groups per component (i), such as more than 2 groups, such as more than 2.5 groups.

[0145] The carboxylic acid group content of the oxidized lignin is believed to play an important role in the unexpected advantages of the mineral fibers in the aqueous binder composition of the present invention. In particular, it is believed that the carboxylic acid groups of the oxidized lignin improve the crosslinking properties and thus provide the cured mineral fiber product with better mechanical properties.

[0146] Component (ii)

[0147] Component (ii) is in the form of one or more cross-linking agents.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] In one embodiment, component (ii) is an epoxidized oil based on fatty acid triglycerides.

[0152] It is important to note that epoxidized oils based on fatty acid triglycerides are not considered hazardous, and therefore the use of these compounds in the adhesive compositions of the present invention does not render the handling of these compositions unsafe.

[0153] In one embodiment, component (ii) is a molecule having 3 or more epoxy groups.

[0154] 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.

[0155] 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.

[0156] Without intending to be bound by any particular theory, the inventors believe that the very advantageous properties of the aqueous binder composition are due to the interaction of the oxidized lignin used as component (i) with the above crosslinking agent. It is believed that the presence of carboxylic acid groups in the oxidized lignin enables the oxidized lignin to crosslink very effectively.

[0157] In one embodiment, component (ii) is one or more crosslinking agents selected from multifunctional organic amines such as alkanolamines, diamines such as hexamethyldiamine, triamines.

[0158] In one embodiment, component (ii) is one or more crosslinking agents selected from polyethyleneimine, polyvinylamine, fatty amine.

[0159] In one embodiment, component (ii) is one or more fatty amides.

[0160] In one embodiment, component (ii) is one or more crosslinking agents selected from dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid.

[0161] In one embodiment, component (ii) is one or more crosslinking agents selected from polyester polyols such as polycaprolactone.

[0162] In one embodiment, component (ii) is one or more crosslinking agents selected from starch, modified starch, CMC.

[0163] In one embodiment, component (ii) is one or more cross-linking agents in the form of aliphatic multifunctional carbodiimides.

[0164] 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.

[0165] 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.).

[0166] Component (ii) may also be any mixture of the abovementioned compounds.

[0167] In one embodiment, the adhesive 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).

[0168] Component (iii)

[0169] Component (iii) is in the form of one or more plasticizers.

[0170] In one embodiment, component (iii) is one or more plasticizers selected from: polyols such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids such as adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, 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.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] In one embodiment, component (iii) comprises one or more plasticizers selected from polyethylene glycol and polyethylene glycol ether.

[0176] 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, due to their boiling point, these plasticizers are likely to at least partially evaporate during the curing of the aqueous binder in contact with the mineral fibers.

[0177] 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.

[0178] The effectiveness of these plasticizers in aqueous adhesive compositions is believed to be related to the effect of increasing the fluidity of the oxidized lignin during the curing process. The increased fluidity of the lignin or oxidized lignin during the curing process is believed to facilitate effective crosslinking.

[0179] 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.

[0180] 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.

[0181] In one embodiment, component (iii) is capable of forming covalent bonds with component (i) and / or component (ii) during the curing process. Such a component does not evaporate and remains as part of the composition, but is effectively altered so as not to introduce unwanted side effects, such as water absorption in the cured article. Non-limiting examples of such components are caprolactones and acrylic polymers having free carboxyl groups.

[0182] In one embodiment, component (iii) is selected from fatty alcohols, monohydric alcohols such as amyl alcohol, stearyl alcohol.

[0183] 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.

[0184] In one embodiment, component (iii) is selected from one or more propylene glycols.

[0185] In one embodiment, component (iii) is selected from one or more ethylene glycol esters.

[0186] 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.

[0187] In one embodiment, component (iii) is selected from one or more plasticizers selected from: phenol derivatives such as alkyl or aryl substituted phenols.

[0188] In one embodiment, component (iii) is selected from one or more plasticizers selected from: silanols, siloxanes.

[0189] 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.

[0190] In one embodiment, component (iii) is selected from one or more hydroxy acids.

[0191] 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.

[0192] In one embodiment, component (iii) is selected from one or more plasticizers selected from: quaternary ammonium compounds such as trimethylglycine, distearyldimethylammonium chloride.

[0193] 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.

[0194] In one embodiment, component (iii) is selected from one or more plasticizers selected from: hydrogenated oils, acetylated oils.

[0195] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0196] In one embodiment, component (iii) is selected from one or more plasticizers selected from: alkyl polyglycosides, glucosamides, aminoglucosamides, sucrose esters, sorbitan esters.

[0197] It has been surprisingly found that the addition of a plasticizer to the aqueous binder composition substantially improves the mechanical properties of the growth substrate according to the invention.

[0198] 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.

[0199] Component (iii) may also be any mixture of the abovementioned compounds.

[0200] 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).

[0201] The aqueous binder composition for mineral fibers comprises components (i) and (iia).

[0202] In one embodiment the present invention relates to an aqueous binder composition for mineral fibers, comprising:

[0203] - component (i) in the form of one or more oxidized lignins;

[0204] - component (iia) in the form of one or more modifiers.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] In one embodiment, component (iia) is one or more modifiers selected from polyethyleneimine, polyvinylamine, fatty amine.

[0210] In one embodiment, component (iia) is one or more modifiers selected from aliphatic multifunctional carbodiimides.

[0211] Component (iia) may also be any mixture of the abovementioned compounds.

[0212] Without intending to be bound by any particular theory, the inventors believe that the excellent adhesive properties achieved by the binder composition comprising mineral fibers of 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 cross-linking agent.

[0213] In one embodiment, the aqueous adhesive composition comprises component (iia) in an amount of 1 to 40 wt%, such as 4 to 20 wt%, such as 6 to 12 wt%, based on the dry weight of component (i).

[0214] Other components

[0215] In some embodiments, the aqueous adhesive composition comprises additional components.

[0216] In one embodiment, the aqueous adhesive composition comprises a catalyst selected from an inorganic acid, 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 an ammonium salt, such as an ammonium salt 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 composition.

[0217] In one embodiment, the aqueous adhesive composition includes a catalyst selected from Lewis acids that can accept an electron pair from a donor compound to form a Lewis adduct, such as ZnCl 2 Mg(ClO 4 ) 2 Sn[N(SO 2 -n-C8F17) 2 ] 4 .

[0218] In one embodiment, the aqueous adhesive composition comprises a catalyst selected from metal chlorides, such as KCl, MgCl 2 、ZnCl 2 、FeCl 3 and SnCl 2 .

[0219] In one embodiment, the aqueous adhesive composition includes a catalyst selected from organometallic compounds, such as titanate-based catalysts and tin-based catalysts.

[0220] In one embodiment, the aqueous adhesive composition comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, copper ions.

[0221] In one embodiment, the aqueous adhesive composition further comprises an additional component (iv) in the form of one or more silanes.

[0222] In one embodiment, the aqueous adhesive composition comprises a further component (iv) in the form of one or more coupling agents, such as an organofunctional silane.

[0223] 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.

[0224] In one embodiment, the aqueous adhesive composition further comprises component (v) in the form of one or more components selected from ammonia, amines or any salts thereof.

[0225] The present inventors have found that the addition of ammonia, an amine or any salt thereof as a further component is particularly useful when oxidised lignin is used in component (i), wherein the oxidised lignin is not oxidised in the presence of ammonia.

[0226] In one embodiment, the aqueous binder composition further comprises other components in the form of urea, particularly 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).

[0227] In one embodiment, the aqueous adhesive composition 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 dextrose 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.

[0228] In one embodiment, the aqueous adhesive composition further comprises other components in the form of one or more carbohydrates selected from sucrose and reducing sugars, 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 %, based on the dry weight of component (i).

[0229] In the context of the present invention, an adhesive composition having a sugar content of 50 wt% or more based on the total dry weight of the adhesive components is considered to be a sugar-based adhesive. In the context of the present invention, an adhesive composition having a sugar content of less than 50 wt% based on the total dry weight of the adhesive components is considered to be a non-sugar-based adhesive.

[0230] In one embodiment, the aqueous adhesive further comprises one or more additional components in the form of surfactants in the form of nonionic and / or ionic emulsifiers, such as polyoxyethylene (4) lauryl ether, such as soy lecithin, such as sodium lauryl sulfate.

[0231] In one embodiment, the aqueous adhesive composition comprises:

[0232] - 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);

[0233] - 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;

[0234] - 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 preferably 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; l, in particular 4000 g / mol to 15000 g / mol, more specifically 8000 g / mol to 12000 g / mol; wherein based on the dry weight of component (i), the aqueous adhesive composition preferably comprises component (ii) in an amount of 1 wt % to 40 wt %, such as 4 wt % to 20 wt %, 6 wt % to 12 wt %, and based on the dry weight of component (i), the content of (iii) is 0.5 wt % to 50 wt %, preferably 2.5 wt % to 25 wt %, more preferably 3 wt % to 15 wt %.

[0235] In one embodiment, the aqueous adhesive composition comprises:

[0236] - 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);

[0237] - component (iia) in the form of one or more modifiers selected from epoxidized oils based on fatty acid triglycerides.

[0238] In one embodiment, the aqueous adhesive composition comprises:

[0239] - 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;

[0240] - 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;

[0241] - 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 preferably 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; l, in particular 4000 g / mol to 15000 g / mol, more specifically 8000 g / mol to 12000 g / mol; wherein based on the dry weight of component (i), the aqueous adhesive composition preferably comprises component (ii) in an amount of 1 wt % to 40 wt %, such as 4 wt % to 20 wt %, 6 wt % to 12 wt %, and based on the dry weight of component (i), the content of (iii) is 0.5 wt % to 50 wt %, preferably 2.5 wt % to 25 wt %, more preferably 3 wt % to 15 wt %.

[0242] In one embodiment, the aqueous adhesive composition comprises:

[0243] - 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;

[0244] - component (iia) in the form of one or more modifiers selected from epoxidized oils based on fatty acid triglycerides.

[0245] In one embodiment, the aqueous adhesive composition consists essentially of:

[0246] - component (i) in the form of one or more oxidized lignins;

[0247] - component (ii) in the form of one or more crosslinking agents;

[0248] - component (iii) in the form of one or more plasticizers.

[0249] - component (iv) in the form of one or more coupling agents, such as organofunctional silanes;

[0250] - an optional component in the form of one or more compounds selected from ammonia, amines or any salt thereof;

[0251] - an optional component in the form of urea;

[0252] - optional components in the form of more reactive or non-reactive polysiloxanes;

[0253] - optionally a hydrocarbon oil;

[0254] - optionally one or more surfactants;

[0255] -water.

[0256] In one embodiment, the aqueous adhesive composition consists essentially of:

[0257] - component (i) in the form of one or more oxidized lignins;

[0258] - component (iia) in the form of one or more modifiers selected from epoxidized oils based on fatty acid triglycerides.

[0259] - component (iv) in the form of one or more coupling agents, such as organofunctional silanes;

[0260] - an optional component in the form of one or more compounds selected from ammonia, amines or any salt thereof;

[0261] - an optional component in the form of urea;

[0262] - optional components in the form of more reactive or non-reactive polysiloxanes;

[0263] - optionally a hydrocarbon oil;

[0264] - optionally one or more surfactants;

[0265] -water.

[0266] Preferably the growth substrate comprises 1.0 wt% to 6.0 wt% of the cured binder composition, preferably 2.0 wt% to 4.5 wt%, most preferably 2.5 wt% to 3.5 wt%, based on the weight of the growth substrate. The determination of the binder content is carried out according to DS / EN 13820:2003. The binder content is taken as the loss on ignition. The binder content includes any binder additives.

[0267] The above-mentioned oxidized lignin in the aqueous binder composition is prepared as follows.

[0268] Method I Preparation of Oxidized Lignin

[0269] Oxidized lignin, which can be used as a component of the adhesive used in the present invention, can be prepared by the following method, which comprises contacting:

[0270] - component (a) comprising one or more lignins;

[0271] - component (b) comprising ammonia, one or more amine components and / or any salt thereof;

[0272] - component (c) comprising one or more oxidizing agents.

[0273] Component (a)

[0274] Component (a) includes one or more lignins.

[0275] In one embodiment, component (a) comprises 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.

[0276] In one embodiment, component (a) comprises one or more kraft lignins.

[0277] Component (b)

[0278] In one embodiment, component (b) includes ammonia, one or more amino components and / or any salt thereof. Without intending to be bound by any particular theory, the inventors believe that replacing the alkali hydroxide used in the previously known lignin oxidation process with ammonia, one or more amino components and / or any salt thereof plays an important role in improving the properties of the oxidized lignin prepared according to the method of the present invention.

[0279] The inventors have unexpectedly discovered that oxidized lignin in the presence of ammonia or amines by an oxidant contains a significant amount of nitrogen as part of the oxidized lignin structure. Without intending to be bound by any particular theory, the inventors believe that the improved fire resistance of the oxidized lignin when used in articles in which they are included in adhesive compositions is at least partially due to the nitrogen content of the oxidized lignin structure.

[0280] In one embodiment, component (b) comprises ammonia and / or any salt thereof.

[0281] Without wishing to be bound by any particular theory, the inventors believe that the improved stability of the derivatized lignin prepared according to the present invention is at least in part due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused. In contrast, it has proven difficult to remove residual amounts of alkali hydroxide used in previously known oxidation processes.

[0282] However, in this process 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.

[0283] 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.

[0284] Component (c)

[0285] In the methods described herein, component (c) includes one or more oxidizing agents.

[0286] 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.

[0287] 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%.

[0288] In one embodiment, component (c) comprises hydrogen peroxide.

[0289] 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:

[0290]

[0291] The inventors have found that the derivatized lignin prepared by the methods described herein contains an increased amount of carboxylic acid groups due to the oxidation process. Without intending to be bound by any particular theory, the inventors believe that the carboxylic acid group content of the oxidized lignin prepared by the method plays an important role in the desirable reaction properties of the derivatized lignin prepared by the methods described herein.

[0292] 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.

[0293] Other components

[0294] In one embodiment, the method for preparing oxidized lignin preferably includes 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.

[0295] This oxidation catalyst can increase the reaction rate and thus improve the performance of oxidized lignin.

[0296] Mass ratio of components

[0297] One skilled in the art will use the relative amounts of components (a), (b) and (c) to achieve the desired degree of lignin oxidation.

[0298] In one embodiment,

[0299] - component (a), comprising one or more lignins

[0300] - component (b) comprising ammonia

[0301] - component (c) comprising one or more oxidizing agents in the form of hydrogen peroxide,

[0302] 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.

[0303] Technology

[0304] There is more than one possibility for contacting components (a), (b) and (c) to achieve the desired oxidation reaction.

[0305] In one embodiment, the method comprises the following steps:

[0306] - 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;

[0307] - a step of adjusting the pH by adding component (b) comprising an aqueous solution of ammonia, one or more amine components and / or any salt thereof;

[0308] - an oxidation step by adding component (c) comprising an oxidizing agent.

[0309] 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.

[0310] 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.

[0311] 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.

[0312] 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.

[0313] 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.

[0314] Method II for preparing oxidized lignin

[0315] The oxidized lignin used as the binder component used in the present invention can be prepared by the following method, which comprises contacting the following substances:

[0316] - component (a) comprising one or more lignins;

[0317] - component (b) comprising ammonia, and / or one or more amine components, and / or any salt thereof and / or alkali and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide;

[0318] - component (c) comprising one or more oxidizing agents.

[0319] - component (d) in the form of one or more plasticizers.

[0320] Component (a)

[0321] Component (a) includes one or more lignins.

[0322] In one embodiment of the method for preparing oxidized lignin, component (a) includes one or more sulfate lignins, one or more alkali lignins, one or more lignin sulfonate lignins, one or more organosolv lignins, one or more lignins obtained from a biorefining process of a lignocellulosic raw material, or any mixture thereof.

[0323] In one embodiment, component (a) comprises one or more kraft lignins.

[0324] Component (b)

[0325] In one embodiment of preparing oxidized lignin, component (b) includes 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.

[0326] "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.

[0327] In one embodiment, component (b) comprises ammonia and / or any salt thereof.

[0328] Without intending to be bound by any particular theory, the inventors believe 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.

[0329] However, in the method for preparing oxidized lignin in this embodiment, it is advantageous that component (b) includes, in addition to ammonia, one or more amino components and / or any salts thereof, a relatively small amount of alkali and / or alkaline earth metal hydroxide, such as sodium hydroxide and / or potassium hydroxide.

[0330] 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.

[0331] Component (c)

[0332] In the method for preparing oxidized lignin, component (c) includes one or more oxidizing agents.

[0333] 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.

[0334] 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%.

[0335] In one embodiment, component (c) comprises hydrogen peroxide.

[0336] 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:

[0337]

[0338] The inventors have discovered that the derivatized lignin prepared by the methods described herein contains an increased amount of carboxylic acid groups due to the oxidation process. Without intending to be bound by any particular theory, the inventors believe that the carboxylic acid group content of the oxidized lignin prepared by the methods of the present invention plays an important role in the desirable reaction properties of the derivatized lignin prepared by the methods described herein.

[0339] 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.

[0340] Component (d)

[0341] Component (d) includes one or more plasticizers.

[0342] 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.

[0343] The present inventors have 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.

[0344] In one embodiment according to the present invention, component (d) comprises one or more plasticizers in the form of polyols, such as carbohydrates, hydrogenated sugars such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyvinyl alcohol, acrylic polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides (such as urea / urea) or any mixture thereof.

[0345] In one embodiment of the present invention, component (d) comprises one or more plasticizers selected from polyethylene glycol, polyvinyl alcohol, urea or any mixture thereof.

[0346] Other components

[0347] In one embodiment, the method for preparing oxidized lignin preferably includes further components, in particular component (v), which is 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.

[0348] This oxidation catalyst can increase the reaction rate, thereby improving the properties of the oxidized lignin prepared by the method.

[0349] Mass ratio of components

[0350] 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.

[0351] In one embodiment, the method is carried out such that the method comprises:

[0352] - component (a) comprises one or more lignins;

[0353] - component (b) comprises ammonia;

[0354] - component (c) comprises one or more oxidizing agents in the form of hydrogen peroxide;

[0355] - component (d) comprises one or more plasticizers selected from polyethylene glycol,

[0356] 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.

[0357] For the purposes of the present invention, "dry weight of lignin" is preferably defined as the weight of lignin in the form provided.

[0358] method

[0359] There is more than one possibility for contacting components (a), (b), (c) and (d) to achieve the desired oxidation reaction.

[0360] In one embodiment, the method comprises the following steps:

[0361] - 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;

[0362] - a step of adjusting the pH by adding component (b);

[0363] - a step of adding component (d);

[0364] - an oxidation step by adding component (c) comprising an oxidizing agent.

[0365] 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.

[0366] 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.

[0367] 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≥.

[0368] 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.

[0369] 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.

[0370] The inventors have found that the method as described herein allows to produce a reaction mixture with a high dry matter content, thus a high yield can be achieved in the process of the invention, which allows the reaction product in the form of oxidized lignin to be used as a component for industrial large-scale production of articles such as mineral fibre articles.

[0371] 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%.

[0372] 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.

[0373] 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-slab-well Brookfield viscometer.

[0374] In one embodiment, the method is carried out such that the method comprises a rotor-stator arrangement.

[0375] In one embodiment, the method is performed such that the method is carried out as a continuous or semi-continuous process.

[0376] Device for carrying out the method

[0377] The present invention also relates to a device for implementing the above method.

[0378] In one embodiment, an apparatus for performing the method comprises:

[0379] - rotor-stator arrangement,

[0380] - a premixing device for components (a), (b), (d),

[0381] - one or more inlets for water, components (a), (b), (c) and (d),

[0382] - One or more outlets for oxidized lignin.

[0383] 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,

[0384] The chamber has an inlet for component (c), and

[0385] The chamber has an outlet for oxidized lignin.

[0386] 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.

[0387] In one embodiment, the rotor-stator device used in 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.

[0388] 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.

[0389] 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.

[0390] 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.

[0391] The method can be divided into two steps:

[0392] 1. Prepare lignin material (a) + (b) + (d);

[0393] 2. Oxidation of lignin

[0394] Typically, two different types of rotor / stator machines are used:

[0395] 1. Open rotor / stator machine, 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.

[0396] 2. Inline rotor / stator machines 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.

[0397] 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.

[0398] 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.

[0399] 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.

[0400] Reaction products

[0401] The present inventors have unexpectedly discovered that oxidized lignins are prepared that have highly desirable reactivity properties while exhibiting improved fire resistance when used in articles in which they are included in adhesive compositions, and have improved long term stability over previously known oxidized lignins.

[0402] Oxidized lignin also showed improved hydrophilicity.

[0403] An important parameter for the reactivity of the prepared oxidized lignin is the carboxylic acid group content of the oxidized lignin.

[0404] 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).

[0405] 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:

[0406]

[0407] 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.

[0408] Method III for preparing oxidized lignin

[0409] The oxidized lignin used as the binder component used in the present invention can be prepared by the following method, which comprises contacting the following substances:

[0410] - component (a) comprising one or more lignins;

[0411] - 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;

[0412] - component (c) comprising one or more oxidizing agents,

[0413] - optional component (d) in the form of one or more plasticizers,

[0414] 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.

[0415] Components (a), (b), (c) and (d) are as defined above in process II for preparing oxidized lignin.

[0416] In one embodiment, the method comprises a premixing step of contacting the components with each other.

[0417] During the premixing step, the following components may be brought into contact with each other:

[0418] - component (a) and component (b), or

[0419] - component (a) and component (b) and component (c), or

[0420] - component (a) and component (b) and component (d), or

[0421] - component (a) and component (b) and component (c) and component (d).

[0422] In an embodiment, 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.

[0423] In one embodiment, 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 as the equipment used to perform the mixing / oxidation step. If component (c) is air, this embodiment of the invention is particularly advantageous.

[0424] The inventors have found that by having a mixing / oxidation step followed by an oxidation step, wherein the reaction mixture is preferably not further mixed, the oxidation rate can be controlled in a very effective manner. At the same time, the cost of carrying out the process is reduced because the oxidation step following the mixing / oxidation step requires less complex equipment.

[0425] Another advantage is that the oxidized lignin produced is particularly stable. Another unexpected advantage is that the oxidized lignin produced can be very well adjusted with respect to viscosity. Another unexpected advantage is that the concentration of the oxidized lignin can be very high.

[0426] In one embodiment, the residence time is selected so that the oxidation reaction proceeds to a desired degree of completion, preferably to complete completion.

[0427] System I for carrying out method III

[0428] In one embodiment, a system for performing the method comprises:

[0429] - at least one rotor-stator arrangement,

[0430] - one or more inlets for water and components (a) and (b),

[0431] - one or more outlets of the rotor-stator arrangement,

[0432] 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.

[0433] In one embodiment, the system comprises one or more inlets for component (c) and / or component (d).

[0434] In one embodiment, the system includes a premixing device.

[0435] 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).

[0436] In one embodiment of the invention, the premixing device comprises inlets for water and components (a) and (b).

[0437] 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).

[0438] In one embodiment, the system is constructed in such a way that:

[0439] The inlet for components (a), (b) and (d) is the inlet of a premixing device, in particular an open rotor-stator device,

[0440] The system thus also comprises an additional rotor-stator arrangement,

[0441] The additional rotor-stator device has an inlet for component (c) and the additional rotor-stator device has an outlet for oxidized lignin.

[0442] 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.

[0443] 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.

[0444] System II for carrying out method III

[0445] In one embodiment, a system for performing the method comprises:

[0446] - one or more inlets for water, components (a) and (b),

[0447] - at least one mixing and oxidation device having one or more outlets, and

[0448] - At least one mixer / heat exchanger arranged downstream of at least one or more outlets in the process flow direction, whereby said mixer / heat exchanger comprises temperature control means.

[0449] In one embodiment, the system comprises an additional one or more inlets for component (c) and / or component (d).

[0450] In one embodiment, the system includes a premixing device.

[0451] 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).

[0452] In one embodiment, the premixing device comprises inlets for water and components (a) and (b).

[0453] 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).

[0454] 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.

[0455] 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.

[0456] 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.

[0457] 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.

[0458] 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 slab mixer, and another common device type consists of a mixer element contained in a cylindrical (tube) or square housing.

[0459] 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.

[0460] Preferably, the growth matrix product according to the present invention comprises at least 90% by weight of man-made vitreous fibers, based on the weight of the total solid content of the growth matrix. The advantage of such an amount of fibers in the growth matrix product is that sufficient pores are formed between the fibers so that the growth matrix product can retain moisture and nutrients for cuttings while maintaining the ability of plant roots to penetrate the growth matrix product. The remaining solid content may consist mainly of binder.

[0461] The growth matrix product is in the form of a coherent mass. That is, the growth matrix is ​​usually a coherent matrix of man-made vitreous fibers, which has been produced as such, but can also be formed by granulation of mineral wool masses and consolidation of particulate material. The coherent matrix is ​​a single, integrated matrix.

[0462] Growth substrate preparations according to the present invention may optionally comprise a wetting agent.

[0463] The wetting agent has the usual meaning in the art and may be a cationic, anionic or nonionic surfactant.

[0464] The growth substrate preparation may include a nonionic wetting agent such as

[0465] The growth substrate preparation may include an ionic surfactant, more preferably an alkyl ether sulfate surfactant wetting agent. The wetting agent may be an alkali metal alkyl ether sulfate or an ammonium alkyl ether sulfate. The preferred wetting agent is sodium alkyl ether sulfate. Alkyl ether sulfate surfactant wetting agents are commercially available. The wetting agent may also be a linear alkyl benzene sulfonate anionic surfactant.

[0466] Some of the nonionic wetting agent may be washed out of the MMVF matrix over time. It is therefore preferred to use an ionic wetting agent, particularly an anionic wetting agent such as linear alkylbenzene sulfonate.

[0467] Preferably the growth substrate preparation comprises 0.01 wt% to 1 wt% wetting agent, preferably 0.05 wt% to 0.5 wt% wetting agent, more preferably 0.1 wt% to 0.3 wt% wetting agent.

[0468] However, the inventors have found that a wetting agent is not necessary for the growth substrate article according to the present invention. It is believed that this is due to the nature of the adhesive composition. Therefore, it is preferred that the growth substrate does not contain any wetting agent. By this, it is meant that the growth substrate preferably does not contain a wetting agent, i.e., contains 0 wt% of a wetting agent.

[0469] This has several advantages. First, it reduces the number of additives in the growth substrate preparation, which is good for the environment while also saving costs. Wetting agents are typically made from non-renewable sources, so avoiding the use of wetting agents is beneficial. Additionally, wetting agents can be washed out of the growth substrate preparation. This is problematic because wetting agents can contaminate the water supply and must be properly disposed of in accordance with environmental regulations. When wetting agents are washed off, this also changes the properties of the growth substrate preparation, which can lead to inconsistencies in the growth process. Additionally, a disadvantage of wetting agents is that they can cause foam to be released from the preparation during use. Avoiding the use of wetting agents can avoid these problems.

[0470] The hydrophilicity of an MMVF matrix sample can be measured by determining the sinking time of the sample. An MMVF matrix sample of dimensions 100x100x65 mm is required to determine the sinking time. A container of minimum dimensions 200x200x200mm is filled with water. The sinking time is the time from the first contact of the sample with the water surface to the complete immersion of the sample. The sample is contacted with the water so that a cross section of 100x100mm contacts the water first. The sample then needs to sink a distance of more than 65mm to be completely immersed. The faster the sample sinks, the more hydrophilic the sample is. If the sinking time is less than 120 seconds, the MMVF matrix is ​​considered hydrophilic. Preferably, the sinking time is less than 60 seconds. In practice, the sinking time of the MMVF matrix may be a few seconds, such as less than 10 seconds.

[0471] The hydrophilicity of the growth matrix product can be defined according to the contact angle with water. Preferably, the contact angle of the MMVF of the growth matrix product with water is less than 90 °. The contact angle is measured by the sessile drop measurement method. Any sessile drop method can be used, such as using a contact angle goniometer. In practice, the droplet is placed on a solid surface and the image of the droplet is recorded in time. The static contact angle is then defined by fitting the Young-Laplace equation around the droplet. The contact angle is given by the angle between the calculated drop shape function and the sample surface, and its projection in the droplet image is called the baseline. The equilibrium contact angle is used to further evaluate and calculate the surface free energy using the Owens-Wendt-Rabel-Kaeble method. The method for calculating the contact angle of the material with water is well known to those skilled in the art.

[0472] In the method of the present invention, the density of the growth matrix product is 40 kg / m 3 Up to 100kg / m 3 In the range of 45kg / m 3 Up to 80kg / m 3 This density range was found to be optimal for root growth and product handling, allowing root penetration and ensuring that the product is not damaged during handling.

[0473] In the method of the present invention, the growth substrate article preferably has a volume in the range of 0.003 liters to 87 liters, such as 0.005 liters to 30 liters, preferably 0.008 liters to 20 liters. The growth substrate article may be in the form of an article commonly known as a plug, or in the form of an article traditionally known as a block, or in the form of an article commonly known as a slab.

[0474] Preferably, the growth substrate article has a height in the range of 10 mm to 200 mm.

[0475] The growth substrate article may have conventional dimensions for the type of article commonly referred to as a plunger. Thus, its height may be between 20 mm and 35 mm, typically 25 mm to 28 mm, and its length and width between 15 mm and 25 mm, typically around 20 mm. In this case, the substrate is typically substantially cylindrical, with the end faces of the cylinder forming the top and bottom surfaces of the growth substrate.

[0476] The volume of the growth substrate article in plug form preferably does not exceed 150 cm 3 Generally speaking, the volume of the growth matrix product in the form of a plug is 3 cm 3 Up to 150cm 3 range and preferably not more than 100cm 3 , preferably not more than 80cm 3 , especially not more than 75cm 3 , preferably no more than 70cm 3 The minimum distance between the top surface and the bottom surface of the plunger is preferably less than 60 mm, more preferably less than 50 mm, especially less than 40 mm or less.

[0477] Another embodiment of the plunger has a height of 30 mm to 50 mm, typically about 40 mm, and a length and width in the range of 20 mm to 40 mm, typically about 30 mm. In this case, the growth substrate is typically in the form of a cuboid. In the first case, the volume of the growth substrate is typically no more than 50 cm 3 , preferably no more than 40cm 3 .

[0478] The growth substrate may be of the type described as the first plug-type adhered MMVF growth substrate in the applicant's WO2010 / 003677 publication. In this case, the volume of the growth substrate article is most preferably 10 cm 3 Up to 40cm 3 within the range.

[0479] The growth substrate product may have conventional dimensions commonly known for block-like products of this type. Thus, its height may be between 5 cm and 20 cm, typically between 6 cm and 15 cm, and its length and width between 4 cm and 30 cm, typically between 10 cm and 20 cm. In this case, the substrate is typically substantially rectangular. The volume of the block-like growth substrate product is preferably between 64 cm and 15 cm. 3 Up to 8000cm 3 within the range.

[0480] The growth substrate article may have conventional dimensions for the type of article commonly referred to as a slab. Thus, it may have a height of 5 cm to 15 cm, typically 7.5 cm to 12.5 cm, a width in the range of 5 cm to 30 cm, typically 12 cm to 24 cm, and a length in the range of 30 cm to 240 cm, typically 40 cm to 200 cm. In this case, the substrate is typically substantially rectangular. The volume of the growth substrate article in slab form is preferably 750 cm 3 to 86,400cm 3 within the range.

[0481] The volume of the growth matrix product can be 3cm 3 Up to 300cm 3 The growth substrate article may be within a range of 4 cm x 4 cm x 4 cm. It may be a cube with a size of 4 cm x 4 cm x 4 cm. The growth substrate article may also be cylindrical. Preferably, it has a length of 50 mm and a diameter of 46 mm, or a length of 40 mm and a diameter of 36 mm, or a length of 27 mm and a diameter of 22 mm.

[0482] Generally, the growth substrate article may be of any suitable shape, including cylinders, cuboids, and cubes. Typically the top and bottom surfaces are substantially planar.

[0483] In the present invention, the term "height" refers to the distance from the bottom surface to the top surface when the substrate is used. The top surface refers to the surface facing upward when the article is placed for intended use, and the bottom surface refers to the surface facing downward (the article is supported on it) when the article is placed for intended use. The term "length" refers to the longest distance between the two sides, that is, the distance from one end to the other end when the substrate is used. The term "width" is the distance between the two sides perpendicular to the length. These terms have their usual meanings in the art.

[0484] The growth substrate article according to the present invention may have a seed hole. Alternatively, it may not have a seed hole. The term seed hole has its ordinary meaning in the art and may also be referred to as a plant hole or cavity. A seed hole is an indentation on the top surface of the growth substrate into which a seed, seedling, cutting or plant is placed.

[0485] Preferably, the growth substrate article comprises a liquid impermeable cover surrounding at least the side surfaces of the substrate. The liquid impermeable cover is preferably plastic. The growth substrate article may comprise a liquid impermeable cover surrounding the entire substrate, wherein the cover has at least one opening for a drainage hole and at least one opening on the upper surface to allow contact between the growth substrate and other growth substrates.

[0486] The terms seeds, seedlings, cuttings and plants have their usual meanings in the art. The seeds, seedlings, cuttings and plants may be cucumbers, tomatoes, eggplants, bell peppers, strawberries, lettuce, perennials such as roses; gerbera.

[0487] In the method of the present invention, the growth substrate preparation is irrigated. Preferably, it is irrigated with water and nutrients. This can be done using any method known to those skilled in the art.

[0488] In the present invention, the seed, seedling, cutting or plant is placed in contact with the growth matrix product. This means that the seed, seedling, cutting or plant can be placed directly into the matrix, such as in a seed hole. Alternatively, it can be placed so that it grows into the matrix, such as from another growth matrix. Any part of the seed, seedling, cutting or plant can be in contact with any part of the growth matrix product.

[0489] The present invention also relates to an adhered growth matrix article comprising a man-made vitreous fiber (MMVF) bonded to a cured adhesive composition, wherein the adhesive composition before curing comprises:

[0490] - component (i) in the form of one or more oxidized lignins;

[0491] - component (ii) in the form of one or more crosslinking agents;

[0492] - component (iii) in the form of one or more plasticizers.

[0493] The adhered growth substrate article is as described above. This embodiment may have any of the preferred features described above for the method of the invention.

[0494] The present invention also relates to an array of two or more adhered growth substrate articles, wherein the adhered growth substrate article comprises man-made vitreous fibers (MMVF) bonded to a cured adhesive composition, wherein the adhesive composition before curing comprises:

[0495] - component (i) in the form of one or more oxidized lignins;

[0496] - component (ii) in the form of one or more crosslinking agents;

[0497] - component (iii) in the form of one or more plasticizers.

[0498] In this embodiment, the one or more adherent growth substrate articles may have any of the preferred features described above for the methods of the present invention.

[0499] In an array according to the present invention, at least two of the adhesive growth substrate articles may be identical. For example, two identical adhesive growth substrate articles may be placed adjacent to each other. Alternatively, at least two of the growth substrate articles may be different.

[0500] Preferably, the array includes a growth substrate article placed in contact with a second growth substrate article. Preferably, a growth substrate is located on the top surface of the second growth substrate, such as in the arrangement of plunger / block, block / slab, block / block, plunger / block / slab or plunger / block / block. In the plunger / block arrangement, the placement is such that the substrate described above as a plunger contacts the substrate described above as a block. For example, the plunger can be inserted into a cavity in the block. In the block / slab arrangement, the substrate described above as a block contacts the substrate described above as a slab. For example, the block is located on the top surface of the slab. In the block, the block is arranged so that the block is placed in contact with another block, such as, it can be placed on the top surface of another block. In the plunger, block, slab arrangement, the plunger contacts the block, and the block contacts the slab. This is similar to the plunger / block / block arrangement: the plunger contacts another block, and the other block is placed in contact with the block.

[0501] The present invention also relates to the use of an adherent growth substrate product for growing plants, wherein the adherent growth substrate product comprises man-made vitreous fibers (MMVF) bonded to a cured aqueous binder composition, wherein the aqueous binder composition before curing comprises:

[0502] - component (i) in the form of one or more oxidized lignins;

[0503] - component (ii) in the form of one or more crosslinking agents;

[0504] - component (iii) in the form of one or more plasticizers.

[0505] This embodiment of the invention may have any of the additional features described above for the method of the invention.

[0506] The present invention also relates to a method for manufacturing a growth matrix product, comprising the following steps:

[0507] (i) provide MMVF;

[0508] (ii) spraying the MMVF with an aqueous adhesive composition;

[0509] (iii) collecting and consolidating the MMVF; and

[0510] (iv) curing the aqueous adhesive composition;

[0511] Wherein, the aqueous adhesive composition before curing comprises:

[0512] - component (i) in the form of one or more oxidized lignins;

[0513] - component (ii) in the form of one or more crosslinking agents;

[0514] - component (iii) in the form of one or more plasticizers.

[0515] This embodiment of the invention may have any of the additional features described above for the method of the invention or the growth substrate of the invention.

[0516] Man-made vitreous 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.

[0517] 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).

[0518] The melt is thus formed into a cloud of fibers entrained in the air, which are collected as a web on a conveyor belt and carried away from the fiberizing device. The fiber web is then consolidated, which may involve cross-lapping and / or longitudinal compression and / or vertical compression and / or winding around a mandrel to produce a cylindrical article for pipe insulation. Other consolidation processes may also be performed.

[0519] The adhesive composition is preferably applied to the fibers while they are a cloud entrained in the air. Alternatively, it can be applied after being collected on a conveyor belt, but this is less preferred.

[0520] After consolidation, the consolidated fiber web is sent to a curing device to cure the adhesive.

[0521] In one embodiment, curing is carried out at a temperature of 100°C to 300°C, such as 170°C to 270°C, such as 180°C to 250°C, such as 190°C to 230°C.

[0522] In a preferred embodiment, curing is carried out in a conventional curing oven used for mineral wool production, preferably operating at a temperature of 150 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.

[0523] In one embodiment, curing occurs over a period of time from 30 seconds to 20 minutes, such as from 1 minute to 15 minutes, such as from 2 minutes to 10 minutes.

[0524] In a typical embodiment, curing is performed at a temperature of 150°C to 250°C for 30 seconds to 20 minutes.

[0525] The curing process may begin immediately after the adhesive is applied to the fibers. Curing is defined as a process in which the adhesive 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 composition, thereby increasing the viscosity of the adhesive composition, generally until the adhesive composition reaches a solid state. The cured adhesive composition bonds the fibers to form a structurally adhered fiber matrix.

[0526] In one embodiment, curing of the binder in contact with the mineral fibers is performed in a hot press.

[0527] Curing the binder in contact with the mineral fibers in a hot press offers the particular advantage of producing high-density articles.

[0528] In one embodiment, the curing process comprises drying by pressure.The pressure may be applied by blowing air or gas through / onto the mixture of mineral fibres and binder.

[0529] Example

[0530] Example 1 - Phytotoxicity

[0531] The phytotoxicity of the adhesive according to the present invention was compared with that of the PUF adhesive. Each adhesive was diluted to different concentrations in a nutrient solution. These solutions were then used to grow cucumber plants. The results are shown in Table 1.

[0532] In this test, the length of the first two leaves of cucumber seedlings is measured. The length of this pair of leaves is called the cotyledon leaf length. The control without the addition of adhesive is measured and set to 100%. If the added adhesive causes the plant growth to decrease, the length of this pair of leaves will decrease, and then the reduction rate of length is calculated (see column growth inhibition rate).

[0533] The adhesive of the present invention is prepared as follows:

[0534] -AOL (ammonia oxidized lignin): 1000kg (284kg lignin UPM BioPiva 100, 57kg H 2 O 2 (35%), 53kgNH 4 OH (24.7%), 506 kg water)

[0535] -Plasticizer (PEG200): 44kg

[0536] - Cross-linking agent (Primid XL552-β-hydroxyalkyl-amide (HAA) cross-linking agent supplied by EMS-Chemie AG): 22 kg.

[0537] The preparation method of PUF adhesive is as follows:

[0538] - Phenol urea formaldehyde resin: 329 liters

[0539] - Water: 1337 litres

[0540] - Ammonia: 13 liters

[0541] -Ammonium sulfate: 30.5 liters

[0542] Aminosilane VS-142 from Momentive: 1.6 liters.

[0543] Primid XL552 has the following structure:

[0544]

[0545] Table 1

[0546]

[0547] From the results it can be seen that for both adhesive types tested the pH of all used dilutions was similar and therefore there was no pH effect. Therefore, the results can be directly compared.

[0548] Regarding phytotoxicity, all tested dilutions of the present invention showed better growth effects than the PUF adhesive.

[0549] The higher the value, the greater the growth inhibition. For example, when 4% PUF was added, the growth inhibition was 100%, so the plants did not germinate. When 4% of the new adhesive was added, the growth inhibition was 31.7%, which means that the length of the leaves of the pair was 68.3% of the length of the leaves of the control plants; so this is a significant improvement compared to PUF.

[0550] The phytotoxicity of the adhesive of the invention at higher concentrations was lower. At 6% and 4% dilutions, growth was observed. However, the PUF adhesive showed no growth at all at these dilutions.

[0551] For lower concentrations, the adhesive of the present invention performs slightly better than the PUF adhesive.

[0552] Example 2 - Compressive Strength

[0553] Six different matrices were prepared and analyzed for their compressive strength.

[0554] Article 1: MMVF growth substrate containing 2.1 wt. % of the formaldehyde-free binder according to the invention; density 76 kg / m 3 ; 3.5 liters / ton (0.15 weight %) of wetting agent The adhesive in this product was prepared as described in Example 1 above.

[0555] Article 2: MMVF growth substrate, containing 2.1 wt. % of the formaldehyde-free binder according to the invention; density 76 kg / m 3 ; No wetting agent. The adhesive in this product is the same as the adhesive in product 1 above.

[0556] Comparative product 1: MMVF growth matrix containing 2.6 wt% PUF binder; density 77 kg / m 3 ; 5.7 liters / ton of wetting agent (linear alkyl sulfonate). The adhesive in this product was prepared as described in Example 1 above.

[0557] Comparative product 2: MMVF growth matrix containing 2.6 wt% PUF binder; density 77 kg / m 3 ; 3.5 liters / ton of wetting agent The adhesive in this product is the same as the adhesive in the comparative product 1 described above.

[0558] Comparative Product 3: MMVF growth substrate containing 2.8 wt% formaldehyde-free binder; density 78 kg / m 3 ; 6.7 liters / ton of wetting agent (linear alkyl sulfonate). The adhesive in this product is made by reacting the following substances together:

[0559] 185 kg AAA resin: 239 kg glucose: 575 kg water: 1.1 kg silane.

[0560] The preparation method of AAA resin is as follows:

[0561] 90 kg of diethanolamine (DEA) was charged into a 400 L reactor and heated to 60°C. Then, 75 kg of tetrahydrophthalic anhydride (THPA) was added. After heating and maintaining at 130°C for 1 hour, 50 kg of trimellitic anhydride (TMA) was added. The reaction mixture was cooled to 95°C, water was added and the mixture was stirred for 1 hour.

[0562] Comparative Product 4: MMVF growth substrate containing 2.8 wt% formaldehyde-free binder; density 78 kg / m 3 ; 3.5 liters / ton of wetting agent The adhesive in this product is the same as the adhesive in the comparative product 3 described above.

[0563] The results are as follows Figures 1A to 1E As shown, wet and dry compression is measured on insulating materials according to the 1996 standard EN826, and the deviations are as follows:

[0564] -In EN 826, the initial deformation X is not calculated 0 and critical compressive strength σ c and σ e .

[0565] - The EN standard for insulating materials requires that the specimens must be stored and measured at (23 ± 5) ° C. In case of dispute, the storage and measurement should be carried out at (23 ± 2) ° C and (50 ± 5)% relative humidity, as this is not considered to have any effect on the mineral wool.

[0566] The amount of adhesive used in the inventive articles 1 and 2 is significantly lower than the amount used in the comparative articles 1 to 4. However, despite this, comparable compression results can be seen compared to the PUF adhesive and another formaldehyde-free adhesive. Thus, using a lower amount of the inventive adhesive, equivalent compressive strength can be achieved. It is expected that increasing the amount of the inventive adhesive to 2.8 wt% will result in an increase in compressive strength. However, having comparable compression results at lower amounts provides the additional advantage of reducing the total amount of adhesive in the article.

[0567] Example 3 - Water Retention

[0568] The water retention test was performed on the six products defined in Example 2 above: Product 1, Product 2, Comparative Product 1, Comparative Product 2, Comparative Product 3 and Comparative Product 4.

[0569] Water retention was determined according to the following test method.

[0570] definition :

[0571] Water content, WC: water content (volume %)

[0572] (Initial) saturation, WC -1 / 2h : Water content (volume %) of a fully saturated sample after leakage for 2 hours at the same negative pressure as a “half-thick water column”.

[0573] WC -10 : Water content (volume %) of a fully saturated sample after stabilization under the same negative pressure as a 10 cm water column.

[0574] Resaturation: The water content (volume %) after 50% by volume of the sample has been resaturated in 0.5 cm of water for 24 hours.

[0575] Water Column: The height of the water column starting from half the thickness of the specimen or block.

[0576] equipment:

[0577] -Sandbox for pF determination (range pF 0-2.0 (0-100cm), accuracy: zeroing 2mm / flatness 6mm / scale 1mm)

[0578] The sand molds used are usually sandblasting quality (FEPA grade F100)

[0579] -Digital altimeter (height) (accuracy 0.1mm, range 0mm to 200mm)

[0580] - Balance (accuracy A: 0.5g to 600g ± 0.01g, B: 600g to 3000g ± 0.01g)

[0581] -Band saw

[0582] - Bucket 25 litres or larger

[0583] -Plastic containers

[0584] - Drainage grilles

[0585] - Wet rock wool column 1000mm high, 200mm wide

[0586] method:

[0587] Determine the weight immediately after immersion (m 湿 ) and height (h 湿 ).

[0588] Place the sample on the sandbox in the direction of the user, with the pressure at 0 (100 on the level controller). The water level in the water column should be the same height as the sand surface. Determine the weight of the sample after 2 hours.

[0589] Place the sample back into the sandbox as directed by the user and apply a negative pressure equivalent to 10 cm of water column for 24 ± 2 hours. The application of negative pressure must be done in 3 (approximately equal) steps, with a stabilization time of 5 minutes after each step. The height of the level controller depends on the height of the sample.

[0590] The results are as follows Figure 2 shown.

[0591] The results for Formulation 1 and Formulation 2 were comparable, so the addition of a wetting agent did not appear to have a significant effect on water retention.

[0592] Compared with the products containing PUF (comparative products 1 and 2), until WC -10 , product 1 and product 2 according to the invention are significantly wetter.

[0593] The water properties of Formulations 1 and 2 are comparable to other formaldehyde-free binders in Comparative Formulations 3 and 4.

[0594] The resaturation degree was almost equal for all tested articles.

[0595] Thus, the articles of the present invention exhibit improved water retention compared to a PUF adhesive and comparable water retention compared to another formaldehyde-free adhesive.

[0596] Example 4 - Distribution of water in height

[0597] The six products defined in Example 1 above were tested for water distribution in height. The results are as follows: Figure 3 The distribution of water is measured as follows.

[0598] Immerse the sample in a container filled with tap water (20°C ± 1°C). Then use a rock wool column and a balance to bring the water content of the sample to 50% (v / v). The weight of 50% (v / v) is calculated based on the sample volume, using the weight and height of the wet sample.

[0599] The moisture content was measured using a moisture sensor and a handheld reader at a 1.5 cm step above the sample height.

[0600] As can be seen from the figure, the distribution of water in height for the products of the present invention is comparable to those containing PUF binders or other formaldehyde-free binders.

[0601] Example 5

[0602] The adhesive used in the growth substrate of the present invention is prepared as follows:

[0603] 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 was done by checking the solution on a glass plate or Hegman gauge. The insoluble lignin was visible as small particles in the brown adhesive. During the dissolution step, the color of the lignin solution will change from brown to shiny black.

[0604] After the lignin was completely dissolved, 1 liter of defoamer (from of 11-10). The temperature of the batch was maintained at 40°C.

[0605] 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.

[0606] 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.

[0607] After reacting at 65° C. for 15 minutes, the reaction mixture was cooled to below 50° C. The COOH value of the resin obtained was 1.2 mmol / g solid.

[0608] From the above AOL resin, an adhesive was formulated by adding 270 kg of polyethylene glycol 200 and 433 kg of a 31% solution of Primid XL-552 in water.

[0609] Analysis of the final adhesive showed the following data:

[0610] Solid content: 18.9%;

[0611] pH: 9.7;

[0612] Viscosity: 25.5mPas.s;

[0613] Density: 1.066kg / l

[0614] Lignin Oxidation Example

[0615] Embodiment 1

[0616] Example IA – Lignin oxidation by hydrogen peroxide in aqueous ammonia solution:

[0617] The amounts of ingredients used according to Example IA are provided in Tables IA 1.1 and IA 1.2.

[0618] Although kraft lignin is soluble in water at relatively high pH values, it is known that at a certain weight percentage, 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 in water was observed at about 21 to 22 weight percent, and 19 weight percent kraft lignin was used in the examples described.

[0619] 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.

[0620] 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.

[0621] 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 .

[0622] 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.

[0623] 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.

[0624] The change in COOH groups was determined by titration with water using the following formula:

[0625]

[0626] Where V 2s and V 1s is the endpoint volume of the sample, and V 2b and V 1bis 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.

[0627] 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.

[0628] 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.

[0629] Example IB – Scale-up of lignin oxidation in ammonia by hydrogen peroxide to pilot scale

[0630] 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 cube of the size (volume), while cooling generally only increases with the square of the size (area). Furthermore, due to the high viscosity of the bonding intermediates, the process equipment must be carefully selected or designed. Therefore, the scale-up is carefully designed and carried out in several steps.

[0631] 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.

[0632] 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.

[0633] 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.

[0634] 140 kg of 7.5 wt% hydrogen peroxide was added to the stirred lignin solution 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.

[0635] 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.

[0636] Testing of scale-up batches showed that the oxidized lignin produced had properties consistent with laboratory-produced batches.

[0637] Table IA 1.1

[0638] Quantity of material to be used in the form provided:

[0639]

[0640] Table IA 1.2

[0641] Active material dosage:

[0642]

[0643]

[0644] Table IA 2

[0645] Elemental analysis of kraft lignin before and after oxidation:

[0646]

[0647] Table IA 3

[0648] pass 31 P-NMR obtains the functional group distribution of kraft lignin before and after oxidation:

[0649]

[0650] Table 1A4

[0651] COOH group content determined by water titration (mmol / g):

[0652]

[0653] Table IA5

[0654] Table IA5. Number average molar mass (Mn) and weight average Molar mass (Mw), expressed in g / mol, and the average carboxylic acid group content per lignin macromolecule before and after oxidation.

[0655]

[0656] Example II

[0657] In the following examples, several oxidized lignins were prepared. The following properties of the oxidized lignins were determined:

[0658] Solid content of components:

[0659] 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.

[0660] 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, for simplicity, was assumed to be anhydrous 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, for simplicity, was assumed to be anhydrous and used as is. Urea (Cas no 57-13-6) was provided by Sigma-Aldrich and used as supplied or diluted with water. Glycerol (Cas no 56-81-5) was provided by Sigma-Aldrich and, for simplicity, was assumed to be anhydrous and used as is.

[0661] Oxidized lignin solids

[0662] The content of oxidized lignin after heating to 200°C for 1 hour is referred to as "dry solids" and is expressed as a percentage of the weight remaining after heating.

[0663] 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.

[0664] COOH group content

[0665] The change in the COOH group content was also determined by water titration using the following formula:

[0666]

[0667] 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.

[0668] Method for producing oxidized lignin:

[0669] 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.

[0670] 2) Add ammonia in portions during stirring.

[0671] 3) If the slightly exothermic reaction with ammonia does not raise the temperature, heat to raise the temperature to 35°C.

[0672] 4) Measure pH.

[0673] 5) Add plasticizer PEG200 and stir for 10 minutes.

[0674] 6) After the lignin is completely dissolved for about 1 hour, slowly add 1 part of 30% H 2 O 2 .

[0675] 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.

[0676] 8) The round bottom flask was then removed from the water bath and cooled to room temperature.

[0677] 9) Take samples to determine dry solids, COOH, viscosity, density and pH.

[0678] Oxidized lignin composition

[0679] In the following, the entry numbers of the oxidized lignin examples correspond to the entry numbers used in Table II.

[0680] Example IIA

[0681] 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.

[0682] Example IIE

[0683] 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. PEG 200, 22.8 g, was added and stirred for 10 minutes, after which 16.7 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.

[0684] Example IIC

[0685] 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.

[0686] Example II F

[0687] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 l of water at 20 °C and 13.3 g of 25% NH 4 19.0 g of PEG 200 was added and stirred for 10 minutes, after which 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.

[0688]

[0689]

[0690] Example III:

[0691] 8.5L hot water (50℃) and 1.9L NH 4 OH (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).

[0692] 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.

[0693] 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.

[0694] 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.

[0695] The premix temperature was 62°C and the oxidation step raised the temperature to 70°C.

[0696] The final product was analyzed for COOH group content, dry solid matter, pH, viscosity and residual H 2 O 2 .

[0697] Table III:

[0698]

[0699] Example IV:

[0700] 484L hot water (70℃) and 47.0L NH 4 OH (24.7%) was mixed to which 224.0 kg lignin (UPM biopiva 100) was 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.

[0701] 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 O 2 The feed rate was 17.2 L / h. The residence time in the mixer / heat exchanger was 20 minutes.

[0702] During the oxidation step, the temperature of the mixture is increased to as high as 95°C.

[0703] The final product was analyzed for COOH group content, dry solids, pH, viscosity and residual H 2 O 2 .

[0704] 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 testing.

[0705] Bar testing

[0706] 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.

[0707] 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 troughs in the form of heat-resistant silica gel for making small rods (4×5 troughs per shape; trough top dimensions: length = 5.6 cm, width = 2.5 cm; trough bottom dimensions: length = 5.3 cm, width = 2.2 cm; trough height = 1.1 cm). The mixture placed in the trough 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 manner. 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.

[0708] 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.

[0709]

[0710]

[0711] Examples of embodiments of the present disclosure may be described in view of the following clauses.

[0712] Clause 1. A method of growing plants in an adherent growth matrix article, the method comprising:

[0713] - providing at least one adherent growth substrate article comprising man-made vitreous fibers (MMVF) bonded with a cured aqueous binder composition;

[0714] - contacting one or more seeds, seedlings, cuttings or plants with the growth matrix preparation;

[0715] - irrigating said growth substrate preparation;

[0716] Wherein, the aqueous adhesive composition before curing comprises:

[0717] - component (i) in the form of one or more oxidized lignins;

[0718] - component (ii) in the form of one or more crosslinking agents;

[0719] - component (iii) in the form of one or more plasticizers.

[0720] Clause 2. The method according to Clause 1, wherein the component (i) is in the form of one or more ammonia oxidized lignins (AOL).

[0721] Item 3. The method according to Item 1 or 2, wherein the component (ii) comprises one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

[0722] Clause 4. A method according to any one of the preceding clauses, wherein the component (ii) comprises:

[0723] - one or more crosslinking agents selected from polyethyleneimine, polyvinylamine, fatty amine; and / or

[0724] - one or more cross-linking agents in the form of fatty amides; and / or

[0725] - one or more cross-linking agents selected from dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid; and / or

[0726] - one or more crosslinking agents selected from polyester polyols such as polycaprolactone; and / or

[0727] - one or more cross-linking agents selected from starch, modified starch, CMC; and / or

[0728] - one or more cross-linking agents in the form of aliphatic multifunctional carbodiimides; and / or

[0729] - One or more cross-linking agents selected from melamine-based cross-linking agents, such as hexa(methylmethoxy)melamine (HMMM)-based cross-linking agents.

[0730] Clause 5. A method according to any of the preceding clauses, comprising 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).

[0731] Item 6. A method according to any of the preceding items, 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 with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups.

[0732] Clause 7. A method according to any one of the preceding clauses, wherein component (iii) comprises:

[0733] - one or more plasticizers selected from fatty alcohols, monohydric alcohols such as amyl alcohol, stearyl alcohol; and / or

[0734] - one or more plasticizers selected from alkoxylates such as ethoxylates, butanol ethoxylates such as butoxytriglycol; and / or

[0735] - one or more plasticizers in the form of propylene glycol; and / or

[0736] - one or more plasticizers in the form of ethylene glycol esters; and / or

[0737] - one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates; and / or

[0738] - one or more plasticizers selected from phenol derivatives such as alkyl or aryl substituted phenols; and / or

[0739] - one or more plasticizers selected from silanols, siloxanes; and / or

[0740] - one or more plasticizers selected from sulfates such as alkyl sulfates, sulfonates such as alkyl aryl sulfonates such as alkyl and / or

[0741] - sulfonates, phosphates such as tripolyphosphates; and / or

[0742] - one or more plasticizers in the form of hydroxy acids; and / or

[0743] - one or more plasticizers selected from monomeric amides such as acetamide, benzamide, fatty acid amides such as tall oil amide; and / or

[0744] - one or more plasticizers selected from quaternary ammonium compounds such as trimethylglycine, distearyldimethylammonium chloride; and / or

[0745] - one or more plasticizers selected from vegetable oils such as castor oil, palm oil, linseed oil, tall oil, soybean oil; and / or

[0746] - one or more plasticizers selected from hydrogenated oils, acetylated oils; and / or

[0747] - one or more plasticizers selected from acidic methyl esters; and / or

[0748] - one or more plasticizers selected from alkyl polyglycosides, glucosamides, aminoglucosamides, sucrose esters, sorbitan esters; and / or

[0749] - One or more plasticizers selected from polyethylene glycol and polyethylene glycol ethers.

[0750] Clause 8. A method according to any one of the preceding clauses, wherein 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).

[0751] Clause 9. The method according to any one of the preceding clauses, wherein the aqueous adhesive composition comprises: an additional component (iv) in the form of one or more coupling agents, such as an organofunctional silane.

[0752] Clause 10. The method according to any one of the preceding clauses, wherein the aqueous adhesive composition comprises: component (v) in the form of one or more components selected from ammonia, amines or any salts thereof.

[0753] Clause 11. A method according to any of the preceding clauses, wherein the aqueous binder composition comprises: an additional component in the form of urea, in particular, in an amount of 5 wt % to 40 wt %, such as 10 wt % to 30 wt %, such as 15 wt % to 25 wt %, based on the dry weight of component (i).

[0754] Clause 12. The method according to any one of the preceding clauses, wherein the adhesive composition consists essentially of the following components:

[0755] - component (i) in the form of one or more oxidized lignins;

[0756] - component (ii) in the form of one or more crosslinking agents;

[0757] - component (iii) in the form of one or more plasticizers.

[0758] - component (iv) in the form of one or more coupling agents, such as organofunctional silanes;

[0759] - an optional component in the form of one or more compounds selected from ammonia, amines or any salt thereof;

[0760] - an optional component in the form of urea;

[0761] - optional components in the form of more reactive or non-reactive polysiloxanes;

[0762] - optionally a hydrocarbon oil;

[0763] - optionally one or more surfactants;

[0764] -water.

[0765] Clause 13. The method of any of the preceding clauses, wherein the adherent growth substrate article comprises man-made vitreous fibers having a contact angle with water of less than 90°.

[0766] Clause 14. The method of any of the preceding clauses, wherein the adherent growth substrate article comprises man-made vitreous fibers having a geometric mean fiber diameter in the range of 1.5 microns to 10 microns, preferably 2 microns to 8 microns, most preferably 2 microns to 5 microns.

[0767] Clause 15. The method of any preceding clause, wherein the volume of the growth substrate preparation ranges from 0.003 liters to 87 liters.

[0768] Clause 16. The method of any of the preceding clauses, wherein the adhesive growth substrate article comprises a liquid-impermeable covering.

[0769] Clause 17. The method of any of the preceding clauses, wherein the adhesive growth substrate article has a height of 10 mm to 150 mm.

[0770] Clause 18. The method of any preceding clause, wherein the adhesive growth substrate article does not include any wetting agent.

[0771] Clause 19. An adhered growth substrate article comprising man-made vitreous fibers (MMVF) bonded to a cured aqueous binder composition, wherein the aqueous binder composition prior to curing comprises:

[0772] - component (i) in the form of one or more oxidized lignins;

[0773] - component (ii) in the form of one or more crosslinking agents;

[0774] - component (iii) in the form of one or more plasticizers.

[0775] Clause 20. The adherent growth substrate article of Clause 19, further comprising the features of any one of Clauses 2 to 18.

[0776] Clause 21. An array of two or more adhered growth substrate articles, wherein the adhered growth substrate articles comprise man-made vitreous fibers (MMVF) bonded to a cured aqueous binder composition, wherein the aqueous binder composition prior to curing comprises:

[0777] - component (i) in the form of one or more oxidized lignins;

[0778] - component (ii) in the form of one or more crosslinking agents;

[0779] - component (iii) in the form of one or more plasticizers.

[0780] Clause 22. Use of an adherent growth substrate article for growing plants, wherein the adherent growth substrate article comprises man-made vitreous fibers (MMVF) bonded to a cured aqueous binder composition, wherein the aqueous binder composition prior to curing comprises:

[0781] - component (i) in the form of one or more oxidized lignins;

[0782] - component (ii) in the form of one or more crosslinking agents;

[0783] - component (iii) in the form of one or more plasticizers.

[0784] Clause 23. The use according to Clause 22, wherein the adhesive growth substrate further comprises the features of any one of Clauses 2 to 18.

[0785] Clause 24. A method of making a growth substrate article, comprising the steps of:

[0786] (i) provide MMVF;

[0787] (ii) spraying the MMVF with an aqueous adhesive composition;

[0788] (iii) collecting and consolidating the MMVF; and

[0789] (iv) curing the aqueous adhesive composition;

[0790] Wherein, the aqueous adhesive composition before curing comprises:

[0791] - component (i) in the form of one or more oxidized lignins;

[0792] - component (ii) in the form of one or more crosslinking agents;

[0793] - component (iii) in the form of one or more plasticizers.

Claims

1. A method for growing plants in an adherent growth matrix product, the method comprising: include: - providing at least one adherent growth substrate article comprising man-made vitreous fibers (MMVF) bonded with a cured aqueous binder composition; - contacting one or more seeds, seedlings, cuttings or plants with the growth matrix preparation; - irrigating said growth substrate preparation; Wherein, the aqueous adhesive composition before curing comprises: - component (i) in the form of one or more oxidized lignins; - component (iia) in the form of one or more modifiers.

2. The method of claim 1, wherein the first component (i) is in the form of one or more ammonia oxidized lignins (AOL).

3. The method according to claim 1, wherein the component (iia) comprises one or more modifiers selected from the group consisting of: - epoxidized oils based on fatty acid triglycerides; - Molecules with 3 or more epoxy groups; - one or more flexible oligomers or polymers containing reactive functional groups, preferably wherein (i) the polymer is selected from: a low Tg acrylic polymer, a low Tg vinyl polymer, and a low Tg polyether; and / or (ii) the reactive functional group is selected from the group consisting of: a carbodiimide group, an anhydride group, an oxazoline group, an amino group, and an epoxy group; -polyethyleneimine, polyvinylamine, or fatty amine; and - Aliphatic polyfunctional carbodiimide.

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

5. The method according to any one of claims 1 to 3, wherein the aqueous adhesive composition before curing is further include: - component (ii) in the form of one or more crosslinking agents; and / or - component (iii) in the form of one or more plasticizers.

6. The method according to claim 5, wherein the component (ii) comprises at least one of: One or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and oxazoline crosslinking agents; - one or more cross-linking agents selected from the group consisting of polyethyleneimine, polyvinylamine and fatty amine; - one or more cross-linking agents in the form of fatty amides; - one or more cross-linking agents selected from the group consisting of dimethoxyacetaldehyde, glycolaldehyde and glyoxylic acid; - one or more crosslinking agents selected from polyester polyols; - one or more cross-linking agents selected from the group consisting of starch, modified starch and carboxymethyl cellulose (CMC); - one or more cross-linking agents in the form of aliphatic multifunctional carbodiimides; and - One or more cross-linking agents selected from melamine-based cross-linking agents.

7. The method of claim 5, wherein component (iii) comprises at least one of: - one or more plasticizers selected from the group consisting of polyethylene glycol, polyethylene glycol ether, polyether, hydrogenated sugar, phthalate, acid, acrylic polymer, polyvinyl alcohol, polyurethane dispersion, ethylene carbonate, propylene carbonate, lactone, lactam, lactide, acrylic polymer with free carboxyl group, and polyurethane dispersion with free carboxyl group; - one or more plasticizers selected from the group consisting of fatty alcohols and monohydric alcohols; and / or - One or more plasticizers selected from the group consisting of alkoxylates; and / or - one or more plasticizers in the form of propylene glycol; and / or - one or more plasticizers in the form of ethylene glycol esters; and / or - one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates and valerates; and / or - One or more plasticizers selected from the group consisting of phenol derivatives; and / or - One or more plasticizers selected from the group consisting of silanols and siloxanes; and / or - One or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates; and / or - sulfonates, phosphates such as tripolyphosphates; and / or - one or more plasticizers in the form of hydroxy acids; and / or - one or more plasticizers selected from the group consisting of monomeric amides, benzamides and fatty acid amides; and / or - One or more plasticizers selected from the group consisting of quaternary ammonium compounds such as trimethylglycine, distearyl dimethyl ammonium chloride; and / or - One or more plasticizers selected from the group consisting of vegetable oils such as castor oil, palm oil, linseed oil, tall oil, soybean oil; and / or - One or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils; and / or - One or more plasticizers selected from acidic methyl esters; and / or - one or more plasticizers selected from the group consisting of alkyl polyglycosides, glucosamides, aminoglucosamides, sucrose esters and sorbitan esters; and / or - One or more plasticizers selected from the group consisting of polyethylene glycol and polyethylene glycol ethers.

8. The method according to claim 5, in: (a) the content of component (ii) is 1 wt% to 40 wt% based on the dry weight of the first component (i); and / or (b) The content of the component (iii) is 0.5 wt% to 50 wt% based on the dry weight of the first component (i).

9. The method according to any one of the preceding claims, wherein the aqueous adhesive composition further comprises one or more of the following: - additional component (iv) in the form of one or more coupling agents; - component (v) in the form of one or more components selected from the group consisting of ammonia, amines or any salts thereof; - a further component in the form of urea in an amount of 5 to 40 wt %, such as 10 to 30 wt %, such as 15 to 25 wt %, based on the dry weight of the first component (i).

10. The method of claim 1, wherein the aqueous adhesive composition consists essentially of the following components: composition: - component (i) in the form of one or more oxidized lignins; - component (iia) in the form of one or more modifiers selected from epoxidized oils based on fatty acid triglycerides; - component (iv) in the form of one or more coupling agents, such as organofunctional silanes; - an optional component in the form of one or more compounds selected from the group consisting of ammonia, amines or any salts thereof; - an optional component in the form of urea; - optional components in the form of more reactive or non-reactive polysiloxanes; - optionally a hydrocarbon oil; - optionally one or more surfactants; and -water.

11. The method of any one of the preceding claims, wherein the adherent growth substrate article comprises man-made vitreous fibers having a contact angle with water of less than 90°.

12. The method of any one of the preceding claims, wherein the adherent growth matrix article comprises man-made vitreous fibers having a geometric mean fiber diameter in the range of 1.5 microns to 10 microns, preferably 2 microns to 9 microns, most preferably 2 microns to 5 microns.

13. The method of any one of the preceding claims, wherein the growth substrate article has: - a volume ranging from 0.003 litres to 87 litres; and / or -Height from 10 mm to 150 mm.

14. The method of any one of the preceding claims, wherein the adherent growth substrate article comprises a liquid-impermeable covering.

15. The method of any one of the preceding claims, wherein the adhesive growth substrate article does not include any wetting agent.

16. An adherent growth substrate article comprising man-made vitreous fibers (MMVF) bonded to a cured aqueous binder composition, wherein the aqueous binder composition prior to curing include: - a first component (i) in the form of one or more oxidized lignins; as well as; - a second component (iia) in the form of one or more modifiers.

17. The adherent growth substrate article of claim 16, wherein the second component (iia) comprises one or more modifiers selected from the group consisting of: - epoxidized oils based on fatty acid triglycerides; - Molecules with 3 or more epoxy groups; - one or more flexible oligomers or polymers containing reactive functional groups, preferably wherein (i) the polymer is selected from: a low Tg acrylic polymer, a low Tg vinyl polymer, and a low Tg polyether; and / or (ii) the reactive functional group is selected from the group consisting of: a carbodiimide group, an anhydride group, an oxazoline group, an amino group, and an epoxy group; -polyethyleneimine, polyvinylamine, or fatty amine; and - Aliphatic polyfunctional carbodiimide.

18. An array of two or more adhered growth substrate articles, wherein the adhered growth substrate articles comprise man-made vitreous fibers (MMVF) bonded to a cured aqueous adhesive composition, wherein the aqueous adhesive composition prior to curing is include: - a first component (i) in the form of one or more oxidized lignins; as well as - a second component (iia) in the form of one or more modifiers.

19. Use of an adherent growth substrate product for growing plants, wherein the adherent growth substrate product comprises man-made vitreous fibers (MMVF) bonded to a cured aqueous binder composition, wherein the aqueous binder composition prior to curing is include: - a first component (i) in the form of one or more oxidized lignins; as well as - a second component (iia) in the form of one or more modifiers.

20. A method of making a growth substrate article, The following steps are involved: (i) provide MMVF; (ii) spraying the MMVF with an aqueous adhesive composition; (iii) collecting and consolidating the MMVF; and (iv) curing the aqueous adhesive composition; Wherein, the aqueous adhesive composition before curing comprises: - a first component (i) in the form of one or more oxidized lignins; and - a second component (iia) in the form of one or more modifiers.

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