WO2021197624A1 - Liant à l'état solide - Google Patents

Liant à l'état solide Download PDF

Info

Publication number
WO2021197624A1
WO2021197624A1 PCT/EP2020/059636 EP2020059636W WO2021197624A1 WO 2021197624 A1 WO2021197624 A1 WO 2021197624A1 EP 2020059636 W EP2020059636 W EP 2020059636W WO 2021197624 A1 WO2021197624 A1 WO 2021197624A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
binder composition
solid state
group
lignins
Prior art date
Application number
PCT/EP2020/059636
Other languages
English (en)
Inventor
Dorte BARTNIK JOHANSSON
Miroslav Nikolic
Original Assignee
Rockwool International A/S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rockwool International A/S filed Critical Rockwool International A/S
Priority to PCT/EP2020/059636 priority Critical patent/WO2021197624A1/fr
Publication of WO2021197624A1 publication Critical patent/WO2021197624A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/25—Non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J197/00—Adhesives based on lignin-containing materials
    • C09J197/005—Lignin
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/60—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in dry state, e.g. thermo-activatable agents in solid or molten state, and heat being applied subsequently

Definitions

  • the present invention relates to a binder for mineral fibre products, a method of producing a bonded mineral fibre product using said binder, and a mineral fibre product comprising mineral fibres in contact with the cured binder.
  • Mineral wool products also termed mineral fibre products generally comprise man-made vitreous fibres (MMVF) such as, e.g., glass fibres, ceramic fibres, basalt fibres, slag fibres, mineral fibres and stone fibres (rock fibres), which are bonded together by a cured thermoset polymeric binder material.
  • MMVF man-made vitreous fibres
  • bonded mineral fibre mats are generally produced by converting a melt made of suitable raw materials to fibres in conventional manner, for instance by a spinning cup process or by a cascade rotor process.
  • the binder material may be applied to the mineral fibres immediately after the fibres are formed. Alternatively, the binder material is applied to the mineral fibres in an off-line process separate from the fibre forming process.
  • the binder material in the latter case is traditionally a solid-state binder which is not in a diluted aqueous solution.
  • Such binders are also referred to as dry binders.
  • Mineral fibre products with dry binders are formed by mixing the mineral fibres and the binder material to form a mixture and applying heat and pressure to the mixture in a plate press apparatus to provide a cured mineral fibre product.
  • the binder resins of choice have been phenol-formaldehyde resins which can be economically produced and can be extended with urea prior to use as a binder.
  • the existing and proposed legislation directed to the lowering or elimination of formaldehyde emissions have led to the development of formaldehyde-free binders such as, for instance, the binder compositions based on polycarboxy polymers and polyols or polyamines.
  • non-phenol-formaldehyde binders are the addition/-elimination reaction products of aliphatic and/or aromatic anhydrides with alkanolamines, e.g., as disclosed in WO 99/36368, WO 01/05725, WO 01/96460, WO 02/06178, WO 2004/007615 and WO 2006/061249. These binder compositions are water soluble and exhibit excellent binding properties in terms of curing speed and curing density.
  • WO 2008/023032 discloses urea-modified binders of that type which provide mineral wool products having reduced moisture take-up.
  • a further effect in connection with previously known binder compositions from mineral fibres is that at least the majority of the starting materials used for the productions of these binders stem from fossil fuels.
  • a further effect in connection with previously known binder compositions for mineral fibres is that they involve components which are harmful. Emissions from the production when using phenol and formaldehyde containing binders is also a problem regarding health aspects. This requires safety measures for the persons in the working environment leading to increased costs and health issues and there is therefore a need to provide binder compositions for mineral fibres with a reduced content of harmful materials.
  • a binder composition which is particularly suitable for bonding mineral fibres, has a reduced content of harmful materials and emissions, is comparatively inexpensive to produce, has a good storability, shows good properties for bonding mineral fibre products and is including renewable materials as starting products.
  • the binder should be suitable to prepare high-density mineral fibre products or hard plates, respectively.
  • the binder should be formaldehyde-free and possibly also free of phenol.
  • a solid state binder composition in particular a formaldehyde-free, solid state binder composition, comprising:
  • ком ⁇ онент (iii) in form of one or more plasticizers optionally a component (iii) in form of one or more plasticizers.
  • a method of producing a bonded mineral fibre product which comprises the steps of contacting the mineral fibres with the solid state binder composition defined above and curing the binder composition in contact with the mineral fibres.
  • a mineral fibre product comprising mineral fibres in contact with the cured solid state binder composition defined above, preferably obtainable by the method defined above.
  • the solid state binder composition defined above is used as a binder for mineral fibres or as a glue to adhere components with each other.
  • the present inventors have surprisingly found that it is possible to prepare a binder composition for mineral fibres that is based on the combination of the components (i) and (ii) and optionally component (iii) defined above. It is highly surprising that by the combination of these components, solid state binder compositions can be prepared which are suitable for bonding mineral fibres.
  • the binder composition can be produced from inexpensive renewable materials to a large degree, does not contain, or contains only to a minor degree, any corrosive and/or harmful agents.
  • components can be used which have a comparatively low price.
  • the combination of the low price aspect and the stemming from renewable resources aspect is particularly remarkable, since "biomaterials" are often more expensive than conventional materials.
  • a binder composition based on the combination of said components can be used as a solid state binder.
  • the binders according to the present invention show excellent properties when used for binding mineral fibres.
  • the mechanical strength has an unexpected high level when subjected to ageing conditions.
  • reaction loss from curing achieved with binders according to aspects of the present invention is on the same level or higher than the reaction loss for reference binder.
  • the solid state binder composition according to the present invention comprises:
  • ком ⁇ онент (iii) in form of one or more plasticizers optionally a component (iii) in form of one or more plasticizers.
  • the solid state binder composition according to the present invention, and the mineral fibre products obtained therefrom, respectively are formaldehyde free.
  • the term "formaldehyde free” is defined to characterize a mineral wool product where the emission is below 5 pg/m 2 /h of formaldehyde from the mineral wool product, preferably below 3 pg/m 2 /h.
  • the test is carried out in accordance with ISO 16000 for testing aldehyde emissions.
  • the binder composition does not contain added formaldehyde.
  • the solid state binder composition according to the present invention, and the mineral fibre products obtained therefrom, respectively, may be phenol free or have a relatively low phenol content.
  • the solid state binder composition according to the present invention has a water content, calculated as the weight of water in relation to the weight of the total solid state binder, of ⁇ 30 %, in particular ⁇ 25 %, more preferably ⁇ 10 %.
  • the water content in the solid state binder composition can be determined based on the weight of water that evaporates at 105 °C in 1 hour at ambient pressure from the binder.
  • the binder composition of the present invention is a binder composition in a solid state.
  • the solid state binder composition of the present invention is in form of a powder.
  • the solid state binder composition generally refers to an uncured binder composition, unless otherwise stated.
  • 50 wt. % of the components of the solid state binder composition has a particle size of less than 500 m, such as less than 200 m, such as less than 100 m and more than 10 m, such as more than 20 m, such as more than 25 m.
  • the definition of the particle size is carried out by applying the binder to a screen for which the mesh width is the particle size to determined, e.g. 200 m.
  • the particles recovered after the screening thus has a particle size of less than or equal to 200 m. Thereafter, the wt. % screened can be determined.
  • the solid state binder composition of the present invention is a free-flowing binder composition.
  • the solid state binder composition is able to flow out of a model silo in a mass flow pattern, said model silo having stainless steel walls with a circular hopper, a hopper angle of 30°, and a hopper opening diameter of 20 cm.
  • a suitable test for determining whether a sample of binder is "free-flowing" is to determine whether the binder is able to flow out of a standardised hopper in a mass flow pattern.
  • the term "mass flow” is known in the art of silo design and refers to the fact that the whole contents of a silo is in movement when product is withdrawn from the bottom of the silo, i.e. the "first in - first out” principle applies to the flow, which is regular and easily controllable.
  • a less desirable flow pattern is "core flow” or “funnel flow”, where the product flows through the core of the silo, so that stagnant zones where product is at rest are found along the wall areas of the silo.
  • mass flow angle which is the angle of the hopper (to the vertical) where mass flow can still occur, may be calculated (when the internal friction and wall friction are known) or determined empirically. At angles greater than the mass flow angle, i.e. less steep hoppers, funnel flow will occur.
  • a model silo having stainless steel walls with a round hopper, a hopper angle of 30°, and a hopper opening diameter of 20 cm may be employed.
  • the silo is filled to a minimum fill level of 30 cm above the transition from the silo to the hopper, and a maximum fill level of not more than 3 m.
  • a small quantity of the binder e.g. about 5 liters
  • Product should be withdrawn evenly over the entire area of the opening.
  • binder is defined as "free-flowing" if it is able to flow out of the hopper in a mass flow pattern.
  • Non-free flowing binder on the other hand, will - if it is able to flow out of the hopper at all - flow in a funnel flow pattern.
  • the flow pattern in any given case can readily be determined by visual observation.
  • the free-flowing binder also flow in a mass flow pattern using the same type of hopper and the same procedure, but with a hopper opening diameter of 15 cm.
  • Component (i) is in form of one or more oxidized lignins.
  • Lignin, cellulose and hemicellulose are the three main organic compounds in a plant cell wall. Lignin can be thought of as the glue, that holds the cellulose fibres together. Lignin contains both hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, second only to cellulose, and is estimated to represent as much as 20-30% of the total carbon contained in the biomass, which is more than 1 billion tons globally.
  • Fig. 1 shows a section from a possible lignin structure.
  • lignin There are at least four groups of technical lignins available in the market. These four groups are shown in Fig. 3.
  • a possible fifth group, Biorefinery lignin is a bit different as it is not described by the extraction process, but instead by the process origin, e.g. biorefining and it can thus be similar or different to any of the other groups mentioned.
  • Each group is different from each other and each is suitable for different applications.
  • Lignin is a complex, heterogenous material composed of up to three different phenyl propane monomers, depending on the source. Softwood lignins are made mostly with units of coniferyl alcohol, see fig.
  • Fig. 4 A summary of the properties of these technical lignins is shown in Fig. 4. Lignosulfonate from the sulfite pulping process remains the largest commercial available source of lignin, with capacity of 1.4 million tonnes. But taking these aside, the kraft process is currently the most used pulping process and is gradually replacing the sulfite process. An estimated 78 million tonnes per year of lignin are globally generated by kraft pulp production but most of it is burned for steam and energy. Current capacity for kraft recovery is estimated at 160,000 tonnes, but sources indicate that current recovery is only about 75,000 tonnes. Kraft lignin is developed from black liquour, the spent liquor from the sulfate or kraft process.
  • the kraft process introduces thiol groups, stilbene while some carbohydrates remain. Sodium sulphate is also present as an impurity due to precipitation of lignin from liquor with sulphuric acid but can potentially be avoided by altering the way lignin is isolated.
  • the kraft process leads to high amount of phenolic hydroxyl groups and this lignin is soluble in water when these groups are ionized (above pH ⁇ 10).
  • Soda lignin originates from sodium hydroxide pulping processes, which are mainly used for wheat straw, bagasse and flax. Soda lignin properties are similar to kraft lignins one in terms of solubility and T g . This process does not utilize sulphur and there is no covalently bound sulphur. The ash level is very low. Soda lignin has a low solubility in neutral and acid media but is completely soluble at pH 12 and higher.
  • the lignosulfonate process introduces large amount of sulphonate groups making the lignin soluble in water but also in acidic water solutions.
  • Lignosulfonates has up to 8% sulfur as sulphonate, whereas kraft lignin has 1-2% sulfur, mostly bonded to the lignin.
  • the molecular weight of lignosulfonate is 15.000-50.000 g/mol. This lignin contains more leftover carbohydrates compared to other types and has a higher average molecular weight.
  • the typical hydrophobic core of lignin together with large number of ionized sulphonate groups make this lignin attractive as a surfactant and it often finds application in dispersing cement etc.
  • a further group of lignins becoming available is lignins resulting from biorefining processes in which the carbohydrates are separated from the lignin by chemical or biochemical processes to produce a carbohydrate rich fraction. This remaining lignin is referred to as biorefinery lignin. Biorefineries focus on producing energy, and producing substitutes for products obtained from fossil fuels and petrochemicals as well as lignin. The lignin from this process is in general considered a low value product or even a waste product mainly used for thermal combustion or used as low grade fodder or otherwise disposed of.
  • Organosolv lignin availability is still considered on the pilot scale.
  • the process involves extraction of lignin by using water together with various organic solvents (most often ethanol) and some organic acids.
  • An advantage of this process is the higher purity of the obtained lignin but at a much higher cost compared to other technical lignins and with the solubility in organic solvents and not in water.
  • the cross-linking of a polymer in general should provide improved properties like mechanical, chemical and thermal resistance etc.
  • Lignin is especially abundant in phenolic and aliphatic hydroxyl groups that can be reacted leading to cross-linked structure of lignin.
  • Different lignins will also have other functional groups available that can potentially be used. The existence of these other groups is largely dependent on the way lignin was separated from cellulose and hemicellulose (thiols in kraft lignin, sulfonates in lignosulfonate etc.) depending on the source. It has been found that by using oxidized lignins, binder compositions for mineral fibres can be prepared which allow excellent properties of the mineral fibre product produced.
  • the component (i) is in form of one or more oxidized kraft lignins.
  • the component (i) is in form of one or more oxidized soda lignins.
  • ammonia is partially or fully replaced by an alkali metal hydroxide, in particular sodium hydroxide and/or potassium hydroxide.
  • a typical oxidation agent used for preparing the oxidized lignins is hydrogen peroxide.
  • the one or more oxidized lignins can be dried, in particular when one or more ammonia-oxidized lignins (AOLs) are used.
  • AOLs ammonia-oxidized lignins
  • the component (i) is having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups.
  • Component (ii) is in form of one or more cross-linkers.
  • the cross-linkers used are preferably solid at room temperature (21 °C), e.g. powders.
  • the component (ii) comprises in one embodiment one or more cross-linkers selected from b-hydroxyalkylamide-cross-linkers and/or oxazoline-cross-linkers.
  • b-hydroxyalkylamide-cross-linkers is a curing agent for the acid-functional macromolecules. It provides a hard, durable, corrosion resistant and solvent resistant cross-linked polymer network. It is believed the b-hydroxyalkylamide cross-linkers cure through esterification reaction to form multiple ester linkages.
  • the hydroxy functionality of the b-hydroxyalkylamide-cross-linkers should be an average of at least 2, preferably greater than 2 and more preferably 2-4 in order to obtain optimum curing response.
  • Oxazoline group containing cross-linkers are polymers containing one of more oxazoline groups in each molecule and generally, oxazoline containing crosslinkers can easily be obtained by polymerizing an oxazoline derivative.
  • the patent US6818699 B2 provides a disclosure for such a process.
  • the component (ii) is an epoxidised oil based on fatty acid triglyceride.
  • epoxidised oils based on fatty acid triglycerides are not considered hazardous and therefore the use of these compounds in the binder compositions according to the present invention do not render these compositions unsafe to handle.
  • the component (ii) is a molecule having 3 or more epoxy groups.
  • the component (ii) is one or more flexible oligomer or polymer, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
  • a low Tg acrylic based polymer such as a low Tg vinyl based polymer, such as low Tg polyether
  • reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
  • the present inventors believe that the very advantageous properties of the solid state binder compositions according to the present invention are due to the interaction of the oxidized lignins used as component (i) and the cross-linkers mentioned above. It is believed that the presence of carboxylic acid groups in the oxidized lignins enable the very effective cross-linking of the oxidized lignins.
  • the component (ii) is one or more cross-linkers selected from the group consisting of multifunctional organic amines such as an alkanolamine, diamines, such as hexamethyldiamine, triamines.
  • the component (ii) is one or more cross-linkers selected from the group consisting of polyethylene imine, polyvinyl amine, fatty amines.
  • the component (ii) is one or more fatty amides.
  • the component (ii) is one or more cross-linkers selected from the group consisting of dimethoxyethanal, glycolaldehyde, glyoxalic acid.
  • the component (ii) is one or more cross-linkers selected from polyester polyols, such as polycaprolactone.
  • the component (ii) is one or more cross-linkers selected from the group consisting of starch, modified starch, CMC.
  • the component (ii) is one or more cross-linkers in form of aliphatic multifunctional carbodiimides.
  • the component (ii) is one or more cross-linkers selected from melamine based cross-linkers, such as a hexakis(methylmethoxy)melamine (HMMM) based cross-linkers.
  • melamine based cross-linkers such as a hexakis(methylmethoxy)melamine (HMMM) based cross-linkers.
  • Picassian XL 701, 702, 725 (Stahl Polymers), such as ZOLDINE® XL-29SE (Angus Chemical Company), such as CX300 (DSM), such as Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).
  • component (ii) is Primid XL552, which has the following structur: Prim id XL-552
  • Component (ii) can also be any mixture of the above mentioned compounds.
  • the solid state binder composition may comprise a component (iii).
  • Component (iii) is in form of one or more plasticizers.
  • component (iii) is in form of one or more plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with a structure similar to lignin like vanillin, acetosyringone, solvents used as coalescing agents like alcohol ethers, polyvinyl alcohol.
  • plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds with a structure similar to lignin like vanillin, acetosyringone, solvents used as coalescing agents like alcohol ethers, polyvinyl alcohol.
  • component (iii) is in form of one or more non-reactive plasticizer selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and/or other esters, solvents used as coalescing agents like alcohol ethers, acrylic polymers, polyvinyl alcohol.
  • non-reactive plasticizer selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and/or other esters, solvents used as coalescing agents like alcohol ethers, acrylic polymers, polyvinyl alcohol.
  • component (iii) is one or more reactive plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tricarboxylic acids, such as adipic acid, or lactic acid, and/or vanillic acid and/or ferullic acid, polyurethane dispersions, acrylic based polymers with free carboxy groups, compounds with a structure similar to lignin like vanillin, acetosyringone.
  • carbonates such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tricarboxylic acids, such as adipic acid, or lactic acid, and/or vanillic acid and/or ferullic acid
  • polyurethane dispersions acrylic based polymers with free carboxy groups, compounds with a structure similar to lignin like vanillin, acetosyringone.
  • component (iii) is in form of one or more plasticizers selected from the group consisting of fatty alcohols, monohydroxy alcohols such as pentanol, stearyl alcohol.
  • component (iii) comprises one or more plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers.
  • plasticizers having a boiling point of more than 100 °C, in particular 140 to 250 °C strongly improves the mechanical properties of the mineral fibre products according to the present invention although, in view of their boiling point, it is likely that these plasticizers will at least in part evaporate during the curing of the solid state binders in contact with the mineral fibres.
  • component (iii) comprises one or more plasticizers having a boiling point of more than 100 °C, such as 110 to 280 °C, more preferred 120 to 260 °C, more preferred 140 to 250 °C.
  • component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50000 g/mol, in particular 150 to 4000 g/mol, more particular 150 to 1000 g/mol, preferably 150 to 500 g/mol, more preferably 200 to 400 g/mol.
  • component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4000 to 25000 g/mol, in particular 4000 to 15000 g/mol, more particular 8000 to 12000 g/mol.
  • component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxylates such as ethoxylates such as butanol ethoxylates, such as butoxytriglycol.
  • component (iii) is selected from one or more propylene glycols.
  • component (iii) is selected from one or more glycol esters.
  • component (iii) is selected from one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates.
  • component (iii) is selected from one or more plasticizers selected from the group consisting of phenol derivatives such as alkyl or aryl substituted phenols.
  • component (iii) is selected from one or more plasticizers selected from the group consisting of silanols, siloxanes.
  • component (iii) is selected from one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkyl aryl sulfonates such as alkyl sulfonates, phosphates such as tripolyphosphates; such as tributylphosphates.
  • component (iii) is selected from one or more hydroxy acids.
  • component (iii) is selected from one or more plasticizers selected from the group consisting of monomeric amides such as acetamides, benzamide, fatty acid amides such as tall oil amides.
  • component (iii) is selected from one or more plasticizers selected from the group consisting of vegetable oils such as castor oil, palm oil, linseed oil, tall oil, soybean oil.
  • component (iii) is selected from one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils.
  • component (iii) is selected from one or more fatty acid methyl esters.
  • component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucosides, gluconamides, aminoglucoseamides, sucrose esters, sorbitan esters.
  • plasticizers refers to a substance that is added to a material in order to make the material softer, more flexible (by decreasing the glass-transition temperature Tg) and easier to process.
  • Component (iii) can also be any mixture of the above mentioned compounds.
  • component (iii) is present in an amount of 0.5 to 50, preferably 2.5 to 25, more preferably 3 to 15 wt.-%, based on the dry weight of component (i).
  • Solid state binder composition for mineral fibers comprising components (i) and (iia)
  • the present inventors have found that the excellent binder properties can also be achieved by a two-component system which comprises component (i) in form of one or more oxidized lignins and a component (iia) in form of one or more modifiers, and optionally any of the other components mentioned above and below.
  • component (iia) is a modifier in form of one or more compounds selected from the group consisting of epoxidised oils based on fatty acid triglycerides.
  • component (iia) is a modifier in form of one or more flexible oligomer or polymer, such as a low Tg acrylic based polymer, such as a low Tg vinyl based polymer, such as low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.
  • component (iia) is one or more modifiers selected from the group consisting of polyethylene imine, polyvinyl amine, fatty amines.
  • the component (iia) is one or more modifiers selected from aliphatic multifunctional carbodiimides.
  • Component (iia) can also be any mixture of the above mentioned compounds.
  • the present inventors believe that the excellent binder properties achieved by the binder composition for mineral fibers comprising components (i) and (iia), and optional further components, are at least partly due to the effect that the modifiers used as components (iia) at least partly serve the function of a plasticizer and a crosslinker.
  • the solid state binder composition comprises component (iia) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, such as 6 to 12 wt.-%, based on the dry weight of the component (i).
  • the solid state binder composition according to the present invention comprises further components.
  • the further components used are preferably solid at room temperature (21 °C), e.g. powders.
  • the binder composition according to the present invention comprises a catalyst selected from inorganic acids, such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid, and/or phosphoric acid, and/or any salts thereof such as sodium hypophosphite, and/or ammonium salts, such as ammonium salts of sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid, and/or phosphoric acid, and/or sodium polyphosphate (STTP), and/or sodium metaphosphate (STMP), and/or phosphorous oxychloride.
  • a catalyst selected from inorganic acids, such as sulfuric acid, sulfamic acid, nitric acid, boric acid, hypophosphorous acid, and/or phosphoric acid, and/or any salts thereof such as sodium hypophosphite, and/or ammonium salts, such as ammonium salts of sulfuric acid, sulfamic acid
  • the solid state binder composition according to the present invention comprises a catalyst selected from Lewis acids, which can accept an electron pair from a donor compound forming a Lewis adduct, such as ZnCh, Mg (CIO z, Sn [N(S0 2 -n-C 8 Fi 7 )2] 4 .
  • a catalyst selected from Lewis acids, which can accept an electron pair from a donor compound forming a Lewis adduct, such as ZnCh, Mg (CIO z, Sn [N(S0 2 -n-C 8 Fi 7 )2] 4 .
  • the solid state binder composition according to the present invention comprises a catalyst selected from metal chlorides, such as KCI, MgCh, ZnC , FeC and SnCh.
  • the solid state binder composition according to the present invention comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, copper ions.
  • chelating agents such as transition metals, such as iron ions, chromium ions, manganese ions, copper ions.
  • the solid state binder composition according to the present invention further comprises a further component (iv) in form of one or more silanes.
  • the solid state binder composition according to the present invention comprises a further component (iv) in form of one or more coupling agents, such as organofunctional silanes.
  • the solid state binder composition according to the present invention further comprises a component (v) in form of one or more components selected from the group of bases, in particular amines or any salts thereof.
  • the present inventors have It has been found that the inclusion of bases such as amines or any salts thereof as a further component can in particular be useful when oxidized lignins are used in component (i), which oxidised lignin have not been oxidized in the presence of ammonia.
  • the solid state binder composition according to the present invention further comprises a further component in form of urea, in particular in an amount of 5 to 40 wt.-%, such as 10 to 30 wt.-%, 15 to 25 wt.-%, based on the dry weight of component (i).
  • sucrose sucrose
  • the solid state binder composition according to the present invention further comprises a further component in form of one or more carbohydrates selected from the group consisting of sucrose and reducing sugars in an amount of 5 to 50 wt.-%, such as 5 to less than 50 wt.-%, such as 10 to 40 wt.-%, such as 15 to 30 wt.-% based on the dry weight of component (i).
  • a binder composition having a sugar content of 50 wt.-% or more, based on the total dry weight of the binder components is considered to be a sugar based binder.
  • a binder composition having a sugar content of less than 50 wt.-%, based on the total dry weight of the binder components is considered a non-sugar based binder.
  • the solid state binder composition according to the present invention further comprises a further component in form of one or more surface active agents that are in the form of non-ionic and/or ionic emulsifiers such as polyoxyethylenes (4) lauryl ether, such as soy lecithin, such as sodium dodecyl sulfate.
  • non-ionic and/or ionic emulsifiers such as polyoxyethylenes (4) lauryl ether, such as soy lecithin, such as sodium dodecyl sulfate.
  • the solid state binder composition according to the present invention comprises
  • component (i) in form of one or more ammonia-oxidized lignins having a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (i);
  • component (iii) in form of one or more polyethylene glycols having an average molecular weight of 150 to 50000 g/mol, in particular 150 to 4000 g/mol, more particular 150 to 1000 g/mol, preferably 150 to 500 g/mol, more preferably 150 to 300 g/mol, or one or more polyethylene glycols having an average molecular weight of 4000 to 25000 g/mol, in particular 4000 to 15000 g/mol, more particular 8000 to 12000 g/mol; wherein preferably the solid state binder composition comprises component (ii) in an amount of 1 to 40 wt.-%, such as 4 to 20 wt.-%, 6 to 12 wt.-%, based on the dry weight of component (i), and (iii) is present in an amount of 0.5 to 50, preferably 2.5 to 25, more preferably 3 to 15 wt.-%, based on the dry weight of component (i).
  • the solid state binder composition according to the present invention comprises
  • component (i) in form of one or more ammonia-oxidized lignins having a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 1.5 mmol/g, such as 0.40 to 1.2 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (i);
  • the solid state binder composition according to the present invention comprises
  • component (i) in form of one or more ammonia-oxidized lignins having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups;
  • the solid state binder composition according to the present invention comprises
  • component (i) in form of one or more ammonia-oxidized lignins having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups, such as more than 2.5 groups;
  • the solid state binder composition according to the present invention consists essentially of
  • component (iv) in form of one or more coupling agents such as organofunctional silanes
  • the solid state binder composition according to the present invention consists essentially of
  • the present invention is also directed to a method of producing a bonded mineral fibre product which comprises the steps of contacting mineral fibres with the inventive solid state binder composition described above and curing the binder composition in contact with the mineral fibres.
  • the optional / preferred features of the solid state binder composition as described above also applies for the inventive method.
  • the solid state binder composition comprises
  • ком ⁇ онент (iii) in form of one or more plasticizers optionally a component (iii) in form of one or more plasticizers.
  • the mineral fibres and the solid state binder composition may be simply mixed with each other, e.g. in a stirring device.
  • the mixture obtained can then be transferred to a curing device such as curing oven or a heating press.
  • the solid state binder composition is generally cured thermally, e.g. by a chemical and/or physical reaction of the binder components, usually chemical reactions (cross-linking) and optionally physical reaction.
  • the curing of the binder composition in contact with the mineral fibres takes place in a heat press.
  • the curing of a binder composition in contact with the mineral fibres in a heat press has the particular advantage that it enables the production of high-density products.
  • the binder composition according to the present invention is particularly suitable for use in such a method because it is a solid state binder and therefore the evaporation of the solution water is avoided.
  • the curing of the binder composition in contact with the mineral fibres takes place at a temperature of 150 to 300 °C, preferably 170 to 250 °C, in particular 190 to 230 °C, preferably in a heat press.
  • the curing takes place for a time of 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes. In a typical embodiment, curing takes place at a temperature of 150 to 250 °C for a time of 30 seconds to 20 minutes.
  • the temperatures above are preferably the set temperature of the heat press.
  • the binder contacted with the mineral fibres is prepared by mixing of the constituents of the solid state binder composition wherein the average water content of the constituents, calculated as the weight of water in relation to the weight of the total solid state binder, is ⁇ 30%, in particular ⁇ 25%, more preferably ⁇ 10%.
  • the solid state binder composition contacted with the mineral fibres is prepared by dissolving all constituents in water followed by evaporating water or part of the water forming a powder or any other solid state.
  • a preferred method of evaporating water or part of the water to form a powder or any other solid state involves the use of spray drying the solid state binder composition.
  • a solid state binder composition is already obtained by mixing the ingredients or further measures are to be taken such as removal of the water or a part of the water contained in the ingredients mixed.
  • the type and amount of cross-linker and/or, if used, of the plasticizer can be suitably selected such that a solid state binder compositions is obtained.
  • removal of water can be effected before the ingredients for the binder composition are mixed and/or thereafter.
  • the one or more oxidized lignins; the one or more cross-linkers; and, if added, the one or more plasticizers are all in solid form, the mixture of all ingredients will usually result in a solid state binder composition.
  • the one or more cross-linkers and/or, if added, the one or more plasticizers are in liquid form it might be necessary to remove the water or a part of water to obtain a solid state binder composition. Water is usually present in the one or more oxidized lignins, which may be removed before mixing the ingredients or thereafter.
  • ком ⁇ онент (iii) in form of one or more plasticizers optionally a component (iii) in form of one or more plasticizers.
  • binder composition which comprises component (i) in form of one or more oxidized lignins; a component (ii) in form of one or more cross-linkers; optionally a component (iii) in form of one or more plasticizers, and optionally any of the other components mentioned above and below, wherein the binder composition is in form of a slurry.
  • the binder composition in form of a slurry is a binder composition in form of a liquid wherein at least the oxidized lignin is usually present as a solid.
  • Such binder composition in form of a slurry also encompasses pasty binder compositions, i.e. binder compositions in form of a paste.
  • the binder composition in form of a slurry may comprise water. However, this water is usually bound in the one or more oxidized lignin.
  • the liquid contained in the binder composition in form of a slurry may comprise the one or more crosslinkers and/or, if added, the one or more plasticizers in liquid form.
  • the liquid contained in the binder composition in form of a slurry preferably has a low content of water such as 5-20% by weight of water, based on the total weight of the binder composition, or is free of water.
  • the binder composition in form of a slurry of the invention can be considered as a non-aqueous binder composition.
  • the present invention is also directed to a mineral fibre product, comprising mineral fibres in contact with the cured solid state binder composition described above.
  • the mineral fibre product of the invention is generally a bonded mineral fibre product.
  • the inventive mineral fibre product is preferably obtainable by the inventive method described above.
  • the optional / preferred features of the solid state binder composition as described above and of the method as described above also apply for the inventive mineral fibre product.
  • the mineral fibres employed may be any of man-made vitreous fibres (MMVF), glass fibres, ceramic fibres, basalt fibres, slag fibres, rock fibres, stone fibres and others. These fibres may be present as a wool product, e.g. like a stone wool product. In a preferred embodiment, the mineral fibres are stone fibres.
  • the man-made vitreous fibres can have any suitable oxide composition.
  • the fibres can be glass fibres, ceramic fibres, basalt fibres, slag fibres or rock or stone fibres.
  • the fibres are preferably of the types generally known as rock, stone or slag fibres, most preferably stone fibres. Stone fibres commonly comprise the following oxides, in percent by weight:
  • FeO (including Fe 2 0 3 ): 2 to 15 Na 2 0+K 2 0: not more than 10 CaO+MgO: 10 to 30
  • the MMVF have the following levels of elements, calculated as oxides in wt%:
  • AI 2 C> 3 at least 12, 16 or 17; not more than 30, 27 or 25
  • CaO at least 8 or 10; not more than 30, 25 or 20
  • MgO at least 2 or 5; not more than 25, 20 or 15
  • FeO (including Fe203): at least 4 or 5; not more than 15, 12 or 10
  • FeO+MgO at least 10, 12 or 15; not more than 30, 25 or 20
  • Na 2 0+K 2 0 zero or at least 1; not more than 10
  • Ti02 zero or at least 1; not more than 6, 4 or 2
  • B 2 03 zero or at least 1; not more than 5 or 3
  • P 2 Os zero or at least 1; not more than 8 or 5
  • the MMVF made by the method of the invention preferably have the composition in wt%:
  • Another preferred composition for the MMVF is as follows in wt%:
  • Glass fibres can also contain the following oxides, in percent by weight: Na 2 0+K 2 0: 8 to 18, in particular Na 2 0+K 2 0 greater than CaO+MgO B2O3: 3 to 12
  • Suitable fibre formation methods and subsequent production steps for manufacturing the mineral fibre product are those conventional in the art.
  • the mineral fibre products produced for instance, have the form of woven and nonwoven fabrics, mats, batts, slabs, sheets, plates, strips, rolls, and other shaped articles which find use, for example, as thermal or acoustical insulation materials, vibration damping, construction materials such as window profiles, facade insulation, reinforcing materials for roofing or flooring applications, as filter stock and in other applications.
  • composite materials by combining the bonded mineral fibre product with suitable composite layers or laminate layers such as, e.g., metal, wood, plaster boards, glass surfacing mats and other woven or non-woven materials.
  • the mineral fibre product may have a density of 80 to 1400 kg/m 3 , but the inventive mineral fibre product is preferably a high-density product so that the mineral fibre product preferably has a density of 500 to 1400 kg/m 3 , more preferably 1000 to 1300 kg/m 3 , in particular 1100 to 1200 kg/m 3 , in particular when the mineral fibre product is in form of a plate.
  • the mineral fibre product according to the present invention has an ignition loss of 3 to 30 wt.-%, in particular 5 to 25 wt.-%, more particular 10 to 20 wt.-%.
  • binder composition according to the present invention is particularly useful for bonding mineral fibres, it may equally be employed in other applications typical for binders, e.g. as a binder for foundry sand, chipboard, glass fibre tissue, cellulosic fibres, non-woven paper products, composites, moulded articles, coatings etc.
  • the components may be two components of the same material or of different material.
  • Oxidised lignins which can be used as component in the binder composition for mineral fibres according to the present invention and method for preparing such oxidised lignins
  • oxidised lignins which can be used as component of the binder composition and their preparation.
  • component (a) comprising one or more lignins
  • component (b) comprising ammonia, one or more amine components, and/or any salt thereof.
  • component (c) comprising one or more oxidation agents.
  • Component (a) comprises one or more lignins.
  • component (a) comprises one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from biorefining processess of lignocellulosic feedstocks, or any mixture thereof.
  • component (a) comprises one or more kraft lignins.
  • component (b) comprises ammonia, one or more amino components, and/or any salts thereof.
  • the present inventors have surprisingly found that the lignins oxidised by an oxidation agent in the presence of ammonia or amines contain significant amounts of nitrogen as a part of the structure of the oxidised lignins. Without wanting to be bound to any particular theory, the present inventors believe that the improved fire resistance properties of the oxidised lignins when used in products where they are comprised in a binder composition, said oxidised lignins prepared by the method according to the present invention, are at least partly due to the nitrogen content of the structure of the oxidised lignins.
  • component (b) comprises ammonia and/or any salt thereof.
  • component (b), besides ammonia, one or more amino components, and/or any salts thereof, also comprises a comparably small amount of an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
  • component (b) comprises alkali and/or earth alkali metal hydroxides, such as sodium hydroxide and/or potassium hydroxide, as a component in addition to the ammonia, one or more amino components, and/or any salts thereof
  • the amount of the alkali and/or earth alkali metal hydroxides is usually small, such as 5 to 70 weight parts, such as 10 to 20 weight parts alkali and/or earth alkali metal hydroxide, based on ammonia.
  • component (c) comprises one or more oxidation agents.
  • component (c) comprises one or more oxidation agents in form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen containing oxidation agents, or any mixture thereof.
  • active radicals from the oxidant will typically abstract the proton from the phenolic group as that bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize radicals through mesomerism multiple pathways open up to continue (but also terminate) the reaction and various intermediate and final products are obtained.
  • the average molecular weight can both increase and decrease due to this complexity (and chosen conditions) and in their experiments, the inventors have typically seen moderate increase of average molecular weight of around 30%.
  • component (c) comprises hydrogen peroxide.
  • Hydrogen peroxide is perhaps the most commonly employed oxidant due to combination of low price, good efficiency and relatively low environmental impact.
  • the present inventors have found that the derivatized lignins prepared with the method according to the present invention contain increased amounts of carboxylic acid groups as a result of the oxidation process. Without wanting to be bound by any particular theory, the present inventors believe that the carboxylic acid group content of the oxidised lignins prepared in the process according to the present invention plays an important role in the desirable reactivity properties of the derivatized lignins prepared by the method according to the present invention.
  • oxidised lignin is more hydrophilic. Higher hydrophilicity can enhance solubility in water and facilitate the adhesion to polar substrates such as mineral fibers.
  • the method according to the present invention comprises further components, in particular a component (d) in form of an oxidation catalyst, such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
  • a component (d) in form of an oxidation catalyst such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
  • component (a) comprises one or more lignins - a component (b) comprises ammonia
  • component (c) comprises one or more oxidation agents in form of hydrogen peroxide, wherein the mass ratios of lignin, ammonia and hydrogen peroxide are such that the amount of ammonia is 0.01 to 0.5 weight parts, such as 0.1 to 0.3, such as 0.15 to 0.25 weight parts ammonia, based on the dry weight of lignin, and wherein the amount of hydrogen peroxide is 0.025 to 1.0 weight parts, such as 0.05 to 0.2 weight parts, such as 0.075 to 0.125 weight parts hydrogen peroxide, based on the dry weight of lignin.
  • the method comprises the steps of:
  • component (a) in form of an aqueous solution and/or dispersion of one more lignins, the lignin content of the aqueous solution being 1 to 50 weight-%, such as 5 to 25 weight-%, such as 15 to 22 weight- %, such as 18 to 20 weight-%, based on the total weight of the aqueous solution;
  • component (b) comprising an aqueous solution of ammonia, one or more amine components, and/or any salt thereof;
  • the pH adjusting step is carried so that the resulting aqueous solution and/or dispersion is having a pH > 9, such as > 10, such as > 10.5.
  • the pH adjusting step is carried out so that the resulting aqueous solution and/or dispersion is having a pH in the range of 10.5 to 12. In one embodiment, the pH adjusting step is carried out so that the temperature is allowed to raise to > 25 °C and then controlled in the range of 25 - 50 °C, such as 30 - 45 °C, such as 35 - 40 °C.
  • the temperature is allowed to raise > 35 °C and is then controlled in the range of 35 - 150 °C, such as 40 - 90 °C, such as 45 - 80 °C.
  • the oxidation step is carried out for a time of 1 second to 48 hours, such as 10 seconds to 36 hours, such as 1 minute to 24 hours such as 2 - 5 hours.
  • Oxidised lignins which can be used as component for the binders used in the present invention can be prepared by a method comprising bringing into contact
  • component (a) comprising one or more lignins
  • component (b) comprising ammonia and/or one or more amine components, and/or any salt thereof and/or an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide
  • component (c) comprising one or more oxidation agents
  • component (d) in form of one or more plasticizers in form of one or more plasticizers.
  • component (a) comprises one or more kraft lignins, one or more soda lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from biorefining processess of lignocellulosic feedstocks, or any mixture thereof.
  • component (a) comprises one or more kraft lignins.
  • component (b) comprises ammonia, one or more amino components, and/or any salts thereof and/or an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
  • Ammonia-oxidized lignins is to be understood as a lignin that has been oxidized by an oxidation agent in the presence of ammonia.
  • AOL ammonia-oxidized lignin
  • component (b) comprises ammonia and/or any salt thereof.
  • the present inventors believe that the improved stability properties of the derivatized lignins prepared according to the present invention with component (b) being ammonia and/or any salt thereof are 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.
  • component (b), besides ammonia, one or more amino components, and/or any salts thereof, also comprises a comparably small amount of an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide.
  • component (b) comprises alkali and/or earth alkali metal hydroxides, such as sodium hydroxide and/or potassium hydroxide, as a component in addition to the ammonia, one or more amino components, and/or any salts thereof
  • the amount of the alkali and/or earth alkali metal hydroxides is usually small, such as 5 to 70 weight parts, such as 10 to 20 weight parts alkali and/or earth alkali metal hydroxide, based on ammonia.
  • component (c) comprises one or more oxidation agents.
  • component (c) comprises one or more oxidation agents in form of hydrogen peroxide, organic or inorganic peroxides, molecular oxygen, ozone, air, halogen containing oxidation agents, or any mixture thereof.
  • active radicals from the oxidant will typically abstract the proton from the phenolic group as that bond has the lowest dissociation energy in lignin. Due to lignin's potential to stabilize radicals through mesomerism, multiple pathways open up to continue (but also terminate) the reaction and various intermediate and final products are obtained.
  • the average molecular weight can both increase and decrease due to this complexity (and chosen conditions) and in their experiments, the inventors have typically seen moderate increase of average molecular weight of around 30%.
  • component (c) comprises hydrogen peroxide.
  • Hydrogen peroxide is perhaps the most commonly employed oxidant due to combination of low price, good efficiency and relatively low environmental impact. When hydrogen peroxide is used without the presence of catalysts, alkaline conditions and temperature are important due to the following reactions leading to radical formation:
  • the present inventors have found that the derivatized lignins prepared with the method according to the present invention contain increased amounts of carboxylic acid groups as a result of the oxidation process. Without wanting to be bound by any particular theory, the present inventors believe that the carboxylic acid group content of the oxidized lignins prepared in the process according to the present invention plays an important role in the desirable reactivity properties of the derivatized lignins prepared by the method according to the present invention. Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. Higher hydrophilicity can enhance solubility in water and facilitate the adhesion to polar substrates such as mineral fibres.
  • Component (d) comprises one or more plasticizers.
  • component (d) comprises one or more plasticizers in form of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers, polyethers, phthalates and/or acids, such as adipic acid, vanillic acid, lactic acid and/or ferullic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea., or any mixtures thereof.
  • polyols such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyethylene glycol ethers, polyethers, phthalates and
  • component (d) in form of one or more plasticizers provides a decrease of the viscosity of the reaction mixture which allows a very efficient method to produce oxidised lignins.
  • component (d) comprises one or more plasticizers in form of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyvinyl alcohol, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea, or any mixtures thereof.
  • polyols such as carbohydrates, hydrogenated sugars, such as sorbitol, erythriol, glycerol, monoethylene glycol, polyethylene glycols, polyvinyl alcohol, acrylic based polymers with free carboxy groups and/or polyurethane dispersions with free carboxy groups, polyamides, amides such as carbamide/urea, or any mixtures thereof.
  • component (d) comprises one or more plasticizers selected from the group of polyethylene glycols, polyvinyl alcohol, urea or any mixtures thereof.
  • the method according to the present invention comprises further components, in particular a component (v) in form of an oxidation catalyst, such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
  • a component (v) in form of an oxidation catalyst such as one or more transition metal catalyst, such as iron sulfate, such as manganese, palladium, selenium, tungsten containing catalysts.
  • Such oxidation catalysts can increase the rate of the reaction, thereby improving the properties of the oxidized lignins prepared by the method.
  • the method according to the present invention is carried out such that the method comprises
  • component (a) comprises one or more lignins
  • component (b) comprises ammonia
  • component (c) comprises one more oxidation agents in form of hydrogen peroxide
  • the "dry weight of lignin" is preferably defined as the weight of the lignin in the supplied form.
  • the method comprises the steps of:
  • component (a) in form of an aqueous solution and/or dispersion of one more lignins, the lignin content of the aqueous solution being 5 to 90 weight-%, such as 10 to 85 weight-
  • % such as 15 to 70 weight-%, based on the total weight of the aqueous solution
  • component (c) comprising an oxidation agent
  • the pH adjusting step is carried so that the resulting aqueous solution and/or dispersion is having a pH > 9, such as > 10, such as > 10.5.
  • the pH adjusting step is carried out so that the resulting aqueous solution and/or dispersion is having a pH in the range of 9.5 to 12.
  • the pH adjusting step is carried out so that the temperature is allowed to raise to > 25 °C and then controlled in the range of 25 - 50 °C, such as 30 - 45 °C, such as 35 - 40 °C.
  • the temperature is allowed to raise to > 35 °C and is then controlled in the range of 35 - 150 °C, such as 40 - 90 °C, such as 45 - 80 °C.
  • the present inventors have found that the process according to the present invention allows to produce a high dry matter content of the reaction mixture and therefore a high throughput is possible in the process according to the present invention which allows the reaction product in form of the oxidised lignins to be used as a component in industrial mass production products such as mineral fibre products.
  • the method according to the present invention is carried out such that the dry matter content of the reaction mixture is 20 to 80 wt.%, such as 40 to 70 wt.%.
  • the method according to the present invention is carried out such that the viscosity of the oxidised 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.
  • viscosity is dynamic viscosity and is defined as the resistance of the liquid/paste to a change in shape, or movement of neighbouring portions relative to one another.
  • the viscosity is measured in centipoise (cP), which is the equivalent of 1 mPa s (milipascal second).
  • Viscosity is measured at 20°C using a viscometer.
  • the dynamic viscosity can be measured at 20°C by a Cone Plate Wells Brookfield Viscometer.
  • the method according to the present invention is carried out such that the method comprises a rotator-stator device.
  • the apparatus for performing the method comprises:
  • the apparatus is constructed in such a way that the inlets for the premix of the components (a), (b) and (d) are to the rotor-stator device and the apparatus furthermore comprises a chamber, said chamber having an inlet for component (c) and said chamber having an outlet for an oxidised lignin.
  • a rotator-stator device is a device for processing materials comprising a stator configured as an inner cone provided with gear rings.
  • the stator cooperates with a rotor having arms projecting from a hub. Each of these arms bears teeth meshing with the teeth of the gear rings of the stator. With each turn of the rotor, the material to be processed is transported farther outward by one stage, while being subjected to an intensive shear effect, mixing and redistribution.
  • the rotor arm and the subjacent container chamber of the upright device allow for a permanent rearrangement of the material from the inside to the outside and provide for a multiple processing of dry and/or highly viscous matter so that the device is of excellent utility for the intensive mixing, kneading, fibrillating, disintegrating and similar processes important in industrial production.
  • the upright arrangement of the housing facilitates the material's falling back from the periphery toward the center of the device.
  • the rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator.
  • the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow.
  • a feed screw is provided that feeds towards the working region of the device.
  • the guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
  • the method is carried out such that the method uses one rotator-stator device.
  • the mixing of the components and the reaction of the components is carried out in the same rotator-stator device.
  • the method is carried out such that the method uses two or more rotator-stator devices, wherein at least one rotator-stator device is used for the mixing of the components and at least one rotator-stator device is used for reacting the components.
  • This process can be divided into two steps:
  • Inline rotor-/stator machine which has much higher shear forces - circumferential speeds of up to 55 m/s) - and creates beneficial conditions for a very quick chemical reaction.
  • the machine is to be used continuously.
  • the highly concentrated (45 to 50 wt-%) mass of Lignin/water is prepared.
  • the lignin powder is added slowly to the warm water (30 to 60 deg.C) in which the correct amount of watery ammonia and/or alkali base have been added. This can be done in batch mode, or the materials are added intermittently/continuously creating a continuous flow of mass to the next step.
  • the created mass should be kept at a temperature of about 60 deg. to keep the viscosity as low as possible and hence the material pumpable.
  • the hot mass of lignin/water at a pH of 9 to 12 is then transferred using a suitable pump, e.g. progressive cavity pump or another volumetric pump, to the oxidation step.
  • a suitable pump e.g. progressive cavity pump or another volumetric pump
  • the oxidation is done in a closed rotor-/stator system in a continuous inline reaction.
  • a watery solution of ammonia and/or alkali base is dosed with a dosing pump into the rotor-/stator chamber at the point of highest turbulence/shear. This ensures a rapid oxidation reaction.
  • the oxidized material (AOL) leaves the inline-reactor and is collected in suitable tanks.
  • the present inventors have surprisingly found, that the oxidized lignins prepared have very desirable reactivity properties and at the same time display improved fire resistance properties when used in products where they are comprised in a binder composition, and improved long term stability over previously known oxidized lignins.
  • the oxidised lignin also displays improved hydrophilicity.
  • An important parameter for the reactivity of the oxidized lignins prepared is the carboxylic acid group content of the oxidized lignins.
  • the oxidized lignin prepared has a carboxylic acid group content of 0.05 to 10 mmol/g, such as 0.1 to 5 mmol/g, such as 0.20 to 2.0 mmol/g, such as 0.40 to 1.5 mmol/g, such as 0.45 to 1.0 mmol/g, based on the dry weight of component (a).
  • carboxylic acid group content is by using average carboxylic acid group content per lignin macromolecule according to the following formula: total moles COOH
  • 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.
  • Oxidised lignins which can be used as a component for the binder used in the present invention can be prepared by a method comprising bringing into contact
  • component (b) comprising ammonia and/or one or more amine components, and/or any salt thereof and/or an alkali and/or earth alkali metal hydroxide, such as sodium hydroxide and/or potassium hydroxide,
  • component (c) comprising one or more oxidation agents
  • a component (d) in form of one or more plasticizers optionally a component (d) in form of one or more plasticizers, and allowing a mixing/oxidation step, wherein an oxidised mixture is produced, followed by an oxidation step, wherein the oxidised mixture is allowed to continue to react for a dwell time of dwell time of 1 second to 10 hours, such as 10 seconds to 6 hours, such as 30 seconds to 2 hours.
  • Components (a), (b), (c) and (d) are as defined above under Method II to prepare oxidised lignins.
  • the process comprises a premixing step in which components are brought into contact with each other.
  • the premixing step is carried out as a separate step and the mixing/oxidation step is carried out subsequently to the premixing step.
  • component (c) is then added to the premixture produced in the premixing step.
  • the premixing step corresponds to the mixing/oxidation step.
  • the components for example component (a), component (b) and component (c) are mixed and an oxidation process is started at the same time. It is possible that the subsequent dwell time is performed in the same device as that used to perform the mixing/oxidation step.
  • component (c) is air.
  • the present inventors have found out that by allowing a mixing/oxidation step followed by an oxidation step, in which the reaction mixture is preferably not continued to be mixed, the oxidation rate can be controlled in a very efficient manner. At the same time, the costs for performing the method are reduced because the oxidation step subsequent to the mixing/oxidation step requires less complex equipment.
  • oxidized lignin which is produced is particularly stable.
  • the oxidized lignin produced is very well adjustable in terms of viscosity.
  • concentration of the oxidized lignin can be very high.
  • the dwell time is so chosen that the oxidation reaction is brought to the desired degree of completion, preferably to full completion.
  • the system comprises one or more inlets for component (c) and/or component (d).
  • the system comprises a premixing device.
  • the premixing device can comprise one or more inlets for water and/or component (a) and/or component (b) and/or component (c) and/or component (d).
  • the premixing device comprises inlets for water and component (a) and component (b).
  • component (c) is also mixed with the three mentioned ingredients (water, component (a) and component (b)). It is then possible that the premixing device has a further inlet for component (c). If component (c) is air, it is possible that the premixing device is formed by an open mixing vessel, so that in this case component (c) is already brought into contact with the other components (water, component (a) and component (b)) through the opening of the vessel. Also in this embodiment of the invention, it is possible that the premixing device optionally comprises an inlet for component (d).
  • the system is constructed in such a way that the inlets for components (a), (b) and (d) are inlets of a premixing device, in particular of an open rotor-stator device, whereby the system furthermore comprises an additional rotor-stator device, said additional rotor-stator device having an inlet for component (c) and said additional rotor-stator device having an outlet for an oxidized lignin.
  • the premixing step and the mixing/oxidizing step are carried out simultaneously.
  • the premixing device and the mixing/oxidizing device are a single device, i. e. a rotor-stator device.
  • one rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator.
  • the rotator -stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow.
  • a feed screw is provided that feeds towards the working region of the device. The guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
  • system for performing the method comprises:
  • mixer/heat-exchanger which is arranged downstream in the process flow direction to the at least one or more of the outlets, whereby the mixer/heat-exchanger comprises a temperature control device.
  • the system comprises additional one or more inlets for component (c) and/or component (d).
  • the system comprises a premixing device.
  • the premixing device can comprise one or more inlets for water and/or component (a) and/or component (b) and/or component (c) and/or component (d).
  • the premixing device comprises inlets for water and component (a) and component (b).
  • component (c) is also mixed with the three mentioned ingredients (water, component (a) and component (b)). It is then possible that the premixing device has a further inlet for component (c). If component (c) is air, it is possible that the premixing device is formed by an open mixing vessel, so that in this case component (c) is already brought into contact with the other components (water, component (a) and component (b)) through the opening of the vessel. Also in this embodiment of the invention, it is possible that the premixing device optionally comprises an inlet for component (d).
  • 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 furthermore comprises a mixer/heat-exchanger, having an inlet for component (c) and an outlet for an oxidized lignin.
  • premixing step and the mixing/oxidizing step are carried out simultaneously.
  • the premixing device and the mixing/oxidizing device are a single device.
  • one rotator-stator device used in the method according to the present invention comprises a stator with gear rings and a rotor with teeth meshing with the teeth of the stator.
  • the rotator-stator device has the following features: Between arms of the rotor protrudes a guiding funnel that concentrates the material flow coming in from above to the central area of the container. The outer surface of the guiding funnel defines an annular gap throttling the material flow.
  • a feed screw is provided that feeds towards the working region of the device. The guiding funnel retains the product in the active region of the device and the feed screw generates an increased material pressure in the center.
  • premixing devices can also be used as premixing devices.
  • the premixing step is carried out in the mixing and oxidizing apparatus.
  • the mixing and oxidizing apparatus is a static mixer.
  • a static mixer is a device for the continuous mixing of fluid materials, without moving components.
  • One design of static mixer is the plate-type mixer and another common device type consists of mixer elements contained in a cylindrical (tube) or squared housing.
  • the mixer/heat-exchanger is constructed as multitube heat exchanger with mixing elements.
  • the mixing element are preferably fixed installations through which the mixture has to flow, whereby mixing is carried out as a result of the flowing through.
  • the mixer/heat-exchanger can be constructed as a plug flow reactor. Examples I
  • kraft lignin is soluble in water at relatively high pH, it is known that at certain weight percentage the viscosity of the solution will strongly increase. It is typically believed that the reason for the viscosity increase lies in a combination of strong hydrogen bonding and interactions of n-electrons of numerous aromatic rings present in lignin. For kraft lignin an abrupt increase in viscosity around 21- 22 wt.-% in water was observed and 19 wt.-% of kraft lignin were used in the example presented.
  • the oxidation is an exothermic reaction and increase in temperature is noted upon addition of peroxide.
  • temperature was kept at 60 °C during three hours of reaction.
  • Vi s are endpoint volumes of a sample while and Vi b are the volume for the blank.
  • C aci is 0.1M HCI in this case and m s is the weight of the sample.
  • Table IA4 The values obtained from aqueous titration before and after oxidation are shown in table IA4.
  • the average COOH functionality can also be quantified by a saponification value which represents the number of mg of KOH required to saponify 1 g lignin. Such a method can be found in AOCS Official Method Cd 3-25.
  • Average molecular weight was also determined before and after oxidation with a PSS PolarSil column (9: 1 (v/v) dimethyl sulphoxide/water eluent with 0.05 M LiBr) and UV detector at 280nm. Combination of COOH concentration and average molecular weight also allowed calculating average carboxylic acid group content per lignin macromolecule and these results are shown in table IA5.
  • Example IB upscaling the lignin oxidation in ammonia by hydrogen peroxide to pilot scale
  • the next scale up step was done in a closed 200 L reactor with efficient water jacket and an efficient propeller stirrer.
  • the scale was this time 180 L and hydrogen peroxide was added in two steps with appr. 30 minute separation.
  • This up-scaling went relatively well, though quite some foaming was an issue partly due to the high degree reactor filling.
  • To control the foaming a small amount of food grade defoamer was sprayed on to the foam. Most importantly the temperature controllable and end temperatures below 70 °C were obtained using external watercooling.
  • the pilot scale reactions were performed in an 800 L reactor with a water cooling jacket and a twin blade propeller stirring. 158 kg of lignin (UPM LignoBoost TM BioPiva 100) with a dry-matter content of 67 wt.-% was de-lumped and suspended in 224 kg of water and stirred to form a homogenous suspension. With continued stirring 103 kg of 25% ammonia in water was pumped into the reactor and stirred another 2 hours to from a dark viscous solution of lignin.
  • UPM LignoBoost TM BioPiva 100 UPM LignoBoost TM BioPiva 100
  • COOH group content in mmol/g as determined by aqueous titration sample COOH groups (mmol/g) kraft lignin 0.5 ammonia oxidised kraft ⁇ g lignin
  • Component solids content The content of each of the components in a given oxidised lignin solution is based on the anhydrous mass of the components or as stated below.
  • Kraft lignin was supplier by UPM as BioPivalOOTM as dry powder.
  • NH 4 OH 25% was supplied by Sigma-Aldrich and used in supplied form.
  • H 2 O 2 , 30% (Cas no 7722-84- 1) was supplied by Sigma-Aldrich and used in supplied form or by dilution with water.
  • PEG 200 was supplied by Sigma-Aldrich and were assumed anhydrous for simplicity and used as such.
  • PVA Mw 89.000-98.000, Mw 85.000-124.000, Mw 130.000, Mw 146.000-186.000
  • Cas no 9002-89-5 were supplied by Sigma-Aldrich and were assumed anhydrous for simplicity and used as such.
  • Urea (Cas no 57-13- 6) was supplied by Sigma-Aldrich and used in supplied form or diluted with water.
  • Glycerol (Cas no 56-81-5) was supplied by Sigma-Aldrich and was assumed anhydrous for simplicity and used as such.
  • the content of the oxidised Iignin after heating to 200 °C for lh is termed "Dry solid matter" and stated as a percentage of remaining weight after the heating.
  • Disc-shaped stone wool samples (diameter: 5 cm; height 1 cm) were cut out of stone wool and heat-treated at 580 °C for at least 30 minutes to remove all organics.
  • the solids of the binder mixture were measured by distributing a sample of the binder mixture (approx. 2 g) onto a heat treated stone wool disc in a tin foil container. The weight of the tin foil container containing the stone wool disc was weighed before and directly after addition of the binder mixture.
  • the change in COOH group content was also determined by aqueous titration and utilization of the following formula: Where 1 r and V is are endpoint volumes of a sample while I & and Vi b are the volume for a blank sample. C aCid is 0.1M HCI in this case and m s , g is the weight of the sample.
  • entry numbers of the oxidised lignin example correspond to the entry numbers used in Table II.
  • This premix was then transferred to a rotor-stator device and a reaction device where the oxidation was made by use of H2O2 (17,5 vol%).
  • the reaction device used in this case has at least partially a reaction tube and a reaction vessel. Dosage of the premixture was 150 l/h and the H2O2 was dosed at 18 l/h.
  • a Cavitron CD1000 rotor-stator device was used to carry out the mixing/oxidation step.
  • the rotor-stator device was run at 250 Hz (55 m/s circumferential speed) with a counter pressure at 2 bar.
  • the dwell time in the reaction tube was 3,2 minutes and in the reaction vessel 2 hours.
  • the final product was analysed for the COOH group content, dry solid matter, pH, viscosity and remaining H2O2.
  • This premixture was then transferred to a static mixer and a mixer/heat- exchanger, where the oxidation was made by use of H2O2 (35 vol%). Dosage of the premixture was 600 l/h and the H2O2 was dosed at 17,2 l/h. The dwell time in the mixer/heat-exchanger was 20 minutes.
  • the temperature of the mixture increased during the oxidation step up to 95 °C.
  • a binder was made 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 yield 19% solids; and then used for test of mechanical properties in bar tests.
  • the mechanical strength of the binders was tested in a bar test. For each binder, 16 bars were manufactured from a mixture of the binder and stone wool shots from the stone wool spinning production.
  • Prefere® 94 8182U0 Novolac resin was supplied by Prefere Resins and used as supplied. This resin has a hexamine content of 9.0 ⁇ 0.5%.
  • H2O2, 30% (Cas no 7722-84-1) was supplied by Sigma-Aldrich and used in supplied form or by dilution with water.
  • PEG 200 was supplied by Sigma-Aldrich and were assumed anhydrous for simplicity and used as such.
  • Primid XL552 is a hydroxyalkylamide crosslinker and supplied by EMS-CHEMIE AG
  • Dextrose, 96% anhydrous (cas no 158968) was supplied by Sigma-Aldrich and used in the supplied form.
  • Ammonium sulfamate, 98%(cas no 228745) was supplied by Sigma-Aldrich and used in the supplied form.
  • Ammonium hypophosphite (cas no 04401) was supplied by Sigma-Aldrich and used in the supplied form.
  • Binder mixing The reagents were mixed well and the resulting mixture was milled portion-wise (50-100 g per portion) in a Herzog milling machine (running time: 12 seconds for each portion).
  • a foam dampening agent (Skumdaemper 11-10 from NCA-Verodan) is added. Temperature of the batch is maintained at 40°C.
  • Comparative binder 1 (shot bars ' ):
  • Comparative binder 2 (shot bars ' ):
  • Ammonium sulfamate (14,0 g) was ground very thoroughly in a mortar.
  • Dextrose (14,0 g) was added to the mortar and the resulting mixture was ground very thoroughly. This mixture was then mixed well with the remaining amount of dextrose (686, Og). This mixture has a dry solid matter of 66,4% and is called comparative binder 3.
  • Comparative binder 4 fiber bars '
  • binder 1 Solid state binder example, binder 1
  • binder 2 Solid state binder example, binder 2
  • AOL 19% (ammonia oxidized lignin) was left for drying at room temperature for 48h.
  • Primid XL-552 (100%) and PEG10.000 100% were used in the formulation.
  • Fibre bars were prepared as in Example A1 but by use of Prefere® 94 8182U0 Novolac resin (95,5% dry solid matter), and these materials were tested by use of NEN-EN-323 for density and NEN-EN-310 for bending strength.
  • Fibre bars were prepared as in Example A1 with the binder of Comparative Example 1 (Prefere® 94 8182U0 Novolac resin (95,5% dry solid matter)) as described below in the Fibre Bar Test.
  • the aged bars as well as five unaged bars were broken in a 3 point bending test (test speed: 10.0 mm/min; rupture level: 50%; nominal strength: 30 N/mm2; support distance: 40 mm; max deflection 20 mm; nominal E-module 10000 N/mm2) on a Bent Tram machine to investigate their mechanical strengths.
  • the fibers were used as supplied or after crushing for 2 min at 150 kN.
  • the stone wool is opened in the Liidige mixer to ensure proper mixing with the binder. This is done by filling the mixer with ⁇ 1.7 kg wool, and mixing / opening it for approximately 20 seconds.
  • the quantity of organic material (loss of ignition) is determined as the loss of weight of the specimen obtained by burning away of organic material.
  • the organic material is binder and impregnating oil. This is done as specified in EN 13820.
  • the binder content is taken as the LOI.
  • the binder includes oil and other binder additives, if present.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Biochemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de liant à l'état solide, destiné en particulier à la préparation de produits à base de fibres minérales.
PCT/EP2020/059636 2020-04-03 2020-04-03 Liant à l'état solide WO2021197624A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2020/059636 WO2021197624A1 (fr) 2020-04-03 2020-04-03 Liant à l'état solide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2020/059636 WO2021197624A1 (fr) 2020-04-03 2020-04-03 Liant à l'état solide

Publications (1)

Publication Number Publication Date
WO2021197624A1 true WO2021197624A1 (fr) 2021-10-07

Family

ID=70224361

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/059636 WO2021197624A1 (fr) 2020-04-03 2020-04-03 Liant à l'état solide

Country Status (1)

Country Link
WO (1) WO2021197624A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116190660A (zh) * 2023-03-10 2023-05-30 南京航空航天大学 一种粘结剂及其制备方法和应用、一种硅基负极及其制备方法

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285801A (en) * 1961-11-21 1966-11-15 West Virginia Pulp & Paper Co Lignin containing resin binder
DE4226329A1 (de) * 1991-11-07 1993-05-13 Ruetgerswerke Ag Ligninmodifizierte bindemittelgemische und verfahren zu deren herstellung
US5382608A (en) * 1992-12-10 1995-01-17 Rutgerswerke Aktiengesellschaft Binder mixtures containing reactive group containing lignin and novolaks
WO1999036368A1 (fr) 1998-01-16 1999-07-22 Rockwool International A/S Compose servant de liant de fibres minerales et son procede de preparation
WO2001005725A1 (fr) 1999-07-16 2001-01-25 Rockwool International A/S Resine destinee a un liant pour laine minerale et comprenant le produit de reaction d'une amine avec un premier et un second anhydride
WO2001096460A2 (fr) 2000-06-16 2001-12-20 Rockwool International A/S Liants pour produits de laine minerale
WO2002006178A1 (fr) 2000-07-04 2002-01-24 Rockwool International A/S Liant pour produits du type laine minerale
US20030042344A1 (en) 2001-08-29 2003-03-06 Klaus Fisch Device for processing materials
WO2004007615A1 (fr) 2002-07-15 2004-01-22 Rockwool International A/S Composition de liant aqueuse sans formaldehyde pour fibres minerales
US6818699B2 (en) 2000-09-28 2004-11-16 Unitika Ltd. Aqueous dispersion of polyester resin, production method of the same, and aqueous coating composition
WO2006061249A1 (fr) 2004-12-10 2006-06-15 Rockwool International A/S Liant aqueux destine a des fibres minerales
WO2008023032A1 (fr) 2006-08-23 2008-02-28 Rockwool International A/S Liant aqueux modifié par l'urée pour fibres minérales
WO2011042610A1 (fr) * 2009-10-08 2011-04-14 Upm-Kymmene Wood Oy Bioadhésif et planche de bois
CN107286873A (zh) * 2017-06-28 2017-10-24 常州明华运输有限公司 一种纸管胶及其制备方法
EP3299421A1 (fr) * 2015-05-20 2018-03-28 KCC Corporation Composition de liant et procédé pour lier de la matière fibreuse au moyen de cette composition
EP3632866A1 (fr) * 2018-10-05 2020-04-08 Rockwool International A/S Composition de liant aqueux

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285801A (en) * 1961-11-21 1966-11-15 West Virginia Pulp & Paper Co Lignin containing resin binder
DE4226329A1 (de) * 1991-11-07 1993-05-13 Ruetgerswerke Ag Ligninmodifizierte bindemittelgemische und verfahren zu deren herstellung
US5382608A (en) * 1992-12-10 1995-01-17 Rutgerswerke Aktiengesellschaft Binder mixtures containing reactive group containing lignin and novolaks
WO1999036368A1 (fr) 1998-01-16 1999-07-22 Rockwool International A/S Compose servant de liant de fibres minerales et son procede de preparation
US6706853B1 (en) 1998-01-16 2004-03-16 Rockwool International A/S Compound for use as a mineral fibre binder and process for providing such
WO2001005725A1 (fr) 1999-07-16 2001-01-25 Rockwool International A/S Resine destinee a un liant pour laine minerale et comprenant le produit de reaction d'une amine avec un premier et un second anhydride
WO2001096460A2 (fr) 2000-06-16 2001-12-20 Rockwool International A/S Liants pour produits de laine minerale
WO2002006178A1 (fr) 2000-07-04 2002-01-24 Rockwool International A/S Liant pour produits du type laine minerale
US6818699B2 (en) 2000-09-28 2004-11-16 Unitika Ltd. Aqueous dispersion of polyester resin, production method of the same, and aqueous coating composition
US20030042344A1 (en) 2001-08-29 2003-03-06 Klaus Fisch Device for processing materials
WO2004007615A1 (fr) 2002-07-15 2004-01-22 Rockwool International A/S Composition de liant aqueuse sans formaldehyde pour fibres minerales
WO2006061249A1 (fr) 2004-12-10 2006-06-15 Rockwool International A/S Liant aqueux destine a des fibres minerales
WO2008023032A1 (fr) 2006-08-23 2008-02-28 Rockwool International A/S Liant aqueux modifié par l'urée pour fibres minérales
WO2011042610A1 (fr) * 2009-10-08 2011-04-14 Upm-Kymmene Wood Oy Bioadhésif et planche de bois
EP3299421A1 (fr) * 2015-05-20 2018-03-28 KCC Corporation Composition de liant et procédé pour lier de la matière fibreuse au moyen de cette composition
CN107286873A (zh) * 2017-06-28 2017-10-24 常州明华运输有限公司 一种纸管胶及其制备方法
EP3632866A1 (fr) * 2018-10-05 2020-04-08 Rockwool International A/S Composition de liant aqueux

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 9002-89-5
XIANGWEI ZHU ET AL: "Bio-Based Wood Adhesive from Camelina Protein (a Biodiesel Residue) and Depolymerized Lignin with Improved Water Resistance", ACS OMEGA, vol. 2, no. 11, 16 November 2017 (2017-11-16), pages 7996 - 8004, XP055582474, ISSN: 2470-1343, DOI: 10.1021/acsomega.7b01093 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116190660A (zh) * 2023-03-10 2023-05-30 南京航空航天大学 一种粘结剂及其制备方法和应用、一种硅基负极及其制备方法
CN116190660B (zh) * 2023-03-10 2024-01-30 南京航空航天大学 一种粘结剂及其制备方法和应用、一种硅基负极及其制备方法

Similar Documents

Publication Publication Date Title
EP3860960B1 (fr) Composition de liant aqueux
EP4127067B1 (fr) Composition de liant aqueuse
US20230174783A1 (en) High temperature low emitting mineral wool product
WO2021197624A1 (fr) Liant à l'état solide
US20230175178A1 (en) Low chloride mineral wool product
US20230169947A1 (en) Acoustic products
WO2021197627A1 (fr) Procédé de fabrication de produits à base de fibres vitreuses synthétiques
RU2804295C2 (ru) Водная композиция связующего
US20230166479A1 (en) Insulation products
US20230141991A1 (en) Roofing system and insulation element for a flat roof or a flat inclined roof
US20230142020A1 (en) Façade system and insulation element for a façade system
WO2021197633A1 (fr) Système de toit
CA3174400A1 (fr) Procede de culture de plantes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20717615

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20717615

Country of ref document: EP

Kind code of ref document: A1