COMPOSITION OF WATER-SOLUBLE PRE-REACTIVE BINDER; METHOD OF MANUFACTURING THE COMPOSITION OF PRE-REA

专利摘要:
METHOD OF PRODUCTION OF A SET OF MATERIAL CONNECTED BY A POLYMERIC BINDER; AND FIBER OR PRODUCT CONTAINING PARTICLES. The present invention relates to a pre-reacted water-soluble binder composition, a method for its manufacture, a use of said pre-reacted binder composition, a method for making a set of matter bound by a polymeric binder, a binder solution or dispersion comprising said pre-reacted binder composition, as well as products comprising the pre-reacted binder composition in a cured state.
公开号:BR112014024669B1
申请号:R112014024669-6
申请日:2013-04-04
公开日:2020-11-24
发明作者:Carl Hampson；Benedicte Pacorel；Roger Jackson
申请人:Knauf Insulation；
IPC主号:

专利说明:

[001] The present invention relates to a pre-reacted, water-soluble binder composition, a method for its manufacture and a use of said pre-reacted binder composition, a method for manufacturing a set of matter bound by a polymeric binder, a binder or dispersion solution comprising said pre-reacted binder composition, as well as products comprising the pre-reacted binder composition in a cured state.
[002] In general, binders are useful in the manufacture of articles because they are able to consolidate the unmounted or lost material. For example, binders allow two or more surfaces to become joined. In particular, the binders can be used to produce products comprising consolidated fibers. Thermoset binders can be characterized by being transformed into insoluble and infusible materials by means of heat or catalytic action. Examples of a thermosetting binder include a variety of phenol-aldehyde, urea-aldehyde, melamine-aldehyde and other condensation-polymerization materials such as furan and polyurethane resins. Binder compositions containing phenol-aldehyde, resorcinol-aldehyde, phenol / aldehyde / urea, phenol / melamine / aldehyde, and the like are widely used for bonding fibers, textiles, plastics, rubbers, and many other materials.
[003] The mineral wool and wood board industries have historically used a binder based on formaldehyde phenol, usually extended with urea. Phenol formaldehyde binders provide suitable properties for the final products; however, it needs greater sustainability and environmental considerations have motivated the development of alternative binders. Such a binder is an alternative to a carbohydrate based binder derived from the reaction of a carbohydrate and an acid, for example, US patent application No. 2007/0027283 and PCT patent application W02009 / 019235. Another alternative binder is the reaction esterification products of a polycarboxylic acid and a polyol, for example, US patent application No. 2005/0202224. Because these binders do not use formaldehyde as a reagent, they have been collectively referred to as formaldehyde-free binders.
[004] An area in current development is to find a substitute for phenol-formaldehyde-type binders through a wide range of products, including products in the civil construction and automotive sectors (for example, mineral wool insulation, wooden boards , particle boards, plywood, office panels, and sound insulation). In particular, formaldehyde-free binders developed previously may not have all the desired properties. For example, binders based on acrylic acid and polyvinyl alcohol have shown promising performance characteristics for some (not all) products. However, these are relatively more expensive than phenol-formaldehyde binders, are essentially derived from petroleum-based resources, and have a tendency to show lower reaction rates compared to phenol-formaldehyde binder compositions (requiring both extended cure time and increased cure temperature).
[005] Carbohydrate-based binder compositions are made of relatively inexpensive precursors and are derived mainly from renewable resources. However, these binders may also require curing reaction conditions that are substantially different from the conditions under which the traditional phenol formaldehyde binder system is cured.
[006] Specifically, a versatile alternative to the aforementioned phenol-formaldehyde binders is the use of carbohydrate polyamine binders which are polymeric binders obtained by reacting polyamines with carbohydrates having at least one primary amine group. These carbohydrate polyamine binders are suitable substitutes for phenol-formaldehyde binders, since they have similar or superior binding characteristics and are highly compatible with established processes.
[007] Normally, carbohydrate polyamine binders are prepared as a solution, such as an aqueous solution, and are subsequently applied over the assembled loose matter to be bound. Such wet, loose assembled matter is then, for example, heat treated to cure the carbohydrate polyamine binder.
[008] However, in place of the high concentration of solids in the carbohydrate polyamine binder solution it is linked to a number of disadvantages, such as the gelation or rapid solidification of the binder solution, as well as the recrystallization of the carbohydrate component. Based on the relatively short useful life, additional problems are observed in relation to the storage and transfer of carbohydrate polyamine binders.
[009] Therefore, the technical problem underlying the present invention is to provide better binders, particularly binders that are compatible with established processes, are environmentally acceptable and overcome the problems mentioned above.
[010] In order to solve the above technical problem, as a first aspect, the present invention provides a water-soluble pre-reacted binder composition, comprising the reaction product (s) of (i) at least a carbohydrate component, and (ii) at least one nitrogen-containing component.
[011] The pre-reacted binder can be in the form of an aqueous solution or dispersion containing at least 20% by weight, for example, at least 25% by weight, 30% by weight, 35% by weight, 40% by weight , 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight or 80% by weight of said pre-reacted binder composition and / or not more than 85% by weight, for example, not more than 80% by weight, 75% by weight or 70% by weight of said pre-reacted binder composition.
[012] In accordance with the present invention, the term "pre-reacted binder composition" is not particularly restricted and generally includes any chemical composition arising from and / or obtained by reacting a carbohydrate component and a nitrogen containing component, which can be used as a binder, for example, for bonding loose assembled binder, both in this way and under modification.
[013] The pre-reacted binder composition of preferred embodiments of the present invention is based on a carbohydrate component / nitrogen component binder system, i.e., the carbohydrate component (s) and component (s) nitrogen-containing are not only present in small amounts in the starting material to prepare the pre-reacted binder composition of the present invention, but are the main components of the starting material. Therefore, the total amount of at least one carbohydrate component and at least one nitrogen-containing component in the starting material to prepare the pre-reacted binder composition can be at least 20% by weight, based on the total weight of the binder before the pre-reaction. For example, the total amount of the component of at least one carbohydrate and at least one component containing nitrogen can be at least 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight, 80 % by weight, 90% by weight, 95% by weight, or 98% by weight before the pre-reaction.
[014] According to an embodiment of the present invention, the total amount of the reaction product (s) of (i) at least one carbohydrate component and (ii) at least one nitrogen-containing component, the unreacted carbohydrate component (s) and unreacted nitrogen-containing component (s) in the composition of the pre-reacted binder, ie (amount of reaction product (s) from (i) and (ii) ) + (amount of unreacted carbohydrate component (s)) + (value of unreacted nitrogen containing component (s)) is at least 20% by weight, based on the total weight of the pre-reacted binder composition, for example, at least 30% by weight, 40% by weight, 50 by weight, 60% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight, or 98% by weight.
[015] Compared to the state of the art where the carbohydrate and polyamine reagents are dissolved to form a binder which is applied to the loosely assembled matter and subsequently cross-linked through the application of heat to obtain a polymeric binder, the pre binder composition -reacted is a composition that: a) in comparison with the binders such as the state of the art to apply the freely assembled matter (notably before cross-linking through the application of heat) you may have: kind of intermediate reaction, such as prepolymer , in significant amounts, and / or of reduced viscosity due to solids content and / or increase in average molecular weight and / or the increase in color and / or the absorption of light (for example, UV); and / or b) in comparison with such state of the art, such binders, once partially or fully crosslinked (notably subsequent to the application of heat), may have a significantly lesser degree and / or a different type of crosslinking and / or lower viscosity.
[016] As used herein, the term "prepolymer" is not specifically restricted and includes any reaction product (s) of (i) at least the carbohydrate component and (ii) at least one nitrogen-containing component.
[017] According to an embodiment of the present invention, the total amount of the reaction product (s) of (i) at least one component of carbohydrate and (ii) at least one component containing nitrogen is at least 20 % by weight, based on the total weight of the prepolymers in the pre-reacted binder composition, for example, at least 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight , 80% by weight, 90% by weight, 95% by weight, or 98% by weight. According to a specific embodiment, the total amount of the reaction product (s) of (i) at least one carbohydrate component and (ii) at least one nitrogen-containing component is 100% by weight, based on the total weight of the prepolymers in the pre-reacted binder composition.
[018] According to one embodiment, the pre-reacted binder composition of the present invention comprises at least one prepolymer having a molecular weight in the range of 1 to 500 kDa. Preferably, said at least one prepolymer is contained, based on the total weight of the binder composition, in an amount of 2% by weight or more, for example, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, or 50% by weight or more.
[019] According to another embodiment, the pre-reacted binder composition of the present invention comprises at least one prepolymer having a molecular weight in the range of more than 80 to 500 kDa (high molecular weight prepolymer). Preferably, said at least one prepolymer with high molecular weight is contained, based on the total weight of the binder composition, in an amount of 0.2% by weight or more, for example, 0.5% or more, 0 , 75% by weight or more, 1% by weight or more, 1.75% by weight or more, 2.5% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, or 50% by weight or more.
[020] According to another embodiment, the pre-reacted binder composition of the present invention comprises at least one prepolymer having a molecular weight in the range of more than 10 to 80 kDa (intermediate molecular weight prepolymer). Preferably, said at least one prepolymer with intermediate molecular weight is contained, based on the total weight of the binder composition, in an amount of 0.3% by weight or more, for example, 0.5% or more, 1 % by weight or more, 1.5% by weight or more, 2% by weight or more, 2.5% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, or 50% by weight or more.
[021] According to another embodiment, the pre-reacted binder composition of the present invention comprises one or more compounds having a molecular weight in the range of 10 kDa or less (low molecular weight prepolymer), and which are different of (i) the at least one component of carbohydrate and (ii) the at least one component containing nitrogen. According to a specific embodiment, the low molecular weight compounds comprise one or more of a glycolaldehyde, glyceraldehyde, 2-oxopropanal, acetol, dihydroxyacetone, acetoin, butanedione, ethanal, glucosone, 1-deoxyhexosulose, 3-deoxyhexosulose, 3 deoxypentosulose, 1,4,4-dideoxyhexosulose, glyoxal, methyl-glyoxal, diacetyl and 5- (hydroxymethyl) furfural.
[022] Furthermore, in this document, the term "water-soluble" is not specifically limited and includes all types of water-solubility of the pre-reacted binder composition, as defined above. In particular, the term "water soluble" includes water solubility at 20 ° C of 100 g / 1 or more, 150 g / 1 or more, 200 g / 1 or more, or 250 g / 1 or more. For example, the term "water-soluble" can include a water-solubility of the pre-reacted binder composition, as defined above 300 g / 1 or more, 400 g / 1 or more, 500 g / 1 or more, or 600 g / 1 or more (at 20 ° C). Also, an infinite virtual water solubility can be considered to be within the scope of the present invention.
[023] In this context, the expression according to the present invention "insoluble in water" refers to cases in which the pre-reacted binder composition, as defined above, is essentially not soluble in water at 20 ° C. For example, the term insoluble includes a solubility in water at 20 ° C of 50 g / 1 or less, 40 g / 1 or less, 30 g / 1 or less, or 20 g / 1 or less. Preferably, the term insoluble in water includes cases of water solubility of 10 g / 1 or less, 5 g / 1 or less, 1 g / 1 or less, or 0.1 g / 1 or less.
[024] The pre-reacted binder composition can be dilutable with water, this means that one part by weight of the pre-reacted binder composition mixed with at least 25 parts, namely at least 50 parts or 100 parts of deionized water does not form a precipitation after mixing.
[025] According to a preferred embodiment of the present invention, an aqueous solution containing 70% by weight of the pre-reacted binder composition of the present invention has a viscosity at 20 ° C of a maximum of 2000 cP. For example, an aqueous solution containing 70% by weight of the composition of the pre-reacted binder defined above (i.e., an aqueous solution containing 70% by weight of solids) may have an initial viscosity after its preparation from 100 to 1500 cP , from 150 to 1200 cP, from 200 to 800 cP, from 220 to 600 cP, or from 250 to 400 cP. From the point of view of handling, a viscosity in the range of 280 to 350 cP is preferred. Viscosity can be measured using an LV-Torque Brookfield viscometer, spin-die LV-63 at 60 rpm.
[026] In addition, the viscosity of said aqueous solution should preferably not increase by more than 500 cP when left to stand at 20 ° C for 12 hours, 24 hours, 48 hours, 72 hours or 96 hours. According to another preferred embodiment, the viscosity of said aqueous solution must not increase by more than 500 cP within a week, 10 days, 12 days or two weeks. Longer periods, such as three or four weeks, or even two, three or more months, where viscosity does not increase by more than 500 cP are even more preferable.
[027] According to another embodiment, the amount by which viscosity increases within the first 12 hours, when a 70% by weight aqueous solution of the pre-reacted binder composition is left to stand at 20 ° C, should preferably not be greater than 450 cP, or 400 cP or even 350 cP. Preferred increases in viscosity include increases of 300 cP or less, 280 cP or less, 250 cP or less and 200 cP or less.
[028] In accordance with the present invention, the times defined above and the increases in viscosity are not limited to the examples mentioned above and can be freely combined. For example, preferably, the aforementioned aqueous solution 70% by weight of the composition of the pre-reacted binder does not increase in viscosity by more than 300 cP in the first 48 hours after its preparation, or more than 400 cP within two weeks after your preparation. Generally, if the viscosity of a respective aqueous solution becomes very high, for example, caused by gelation, the pre-reacted binder composition may become unusable.
[029] According to another embodiment, the pre-reacted binder composition defined above is capable of reacting with a cross-linking agent to obtain a water-insoluble composition, for example, to obtain one or more melanoidins as an insoluble composition in Water. In the present invention, the pre-reacted binder composition can function as a precursor or intermediate, which can further be reacted with a cross-linking agent to obtain a polymeric binder. For example, this polymeric binder can contain high molecular weight melanoidins like the products of the Maillard reaction which are essentially insoluble in water.
[030] For example, one or more melanoidins as defined above may contain the following generic structural patterns:

[031] where n is an integer of at least 1.
[032] Here, the term "crosslinking agent" is not particularly restricted, and includes any chemical or physical means to later crosslink the pre-reacted binder composition to produce a polymeric binder suitable for binding to the assembled loose matter, such as wood or mineral fibers.
[033] According to a specific embodiment of the present invention, the crosslinking agent can be the same nitrogen-containing component, which has been reacted with the carbohydrate component, or it can be a different nitrogen-containing component. For example, the pre-reacted binder composition of the present invention can be prepared by reacting a carbohydrate component with hexamethylenediamine. Subsequently, another hexamethylenediamine can be added to the pre-reacted binder composition to achieve the high degree of polymerization required in the respective application. An additional example includes the case where the pre-reacted binder composition is prepared by reacting a carbohydrate component with an aqueous ammonia solution, and for the final cure additional hexamethylenediamine is added.
[034] However, according to the present invention, the crosslinking agent is not limited to the nitrogen-containing components defined herein and includes, for example, Lewis acids, isocyanates, blocked isocyanates, epoxides, blocked epoxides, compounds containing carbonyl ( aldehydes, ketones, ie glyoxal) and organic carbonates. Specific examples of the crosslinking agent include citric acid, polycarboxylic acids and anhydrides (e.g., succinic acid, maleic anhydride, tetra- and hexahydrophthalic anhydrides, styrene-maleic anhydride copolymers), polycarboxylic acid solutions and anhydride derivatives (such as the ammonium salts thereof).
[035] According to another embodiment of the pre-reacted binder composition defined above, the ratio of the total carbonyl groups in the carbohydrate component to the total of reactive nitrogen-containing groups in the nitrogen-containing component is 5: 1 to 1: 5. For example, the ratio of carbonyl groups to groups containing reactive nitrogen can be from 5: 1 to 1: 4,5, 5: 1 to 1: 4, 5: 1 to 1: 3,5, 5: 1 to 1 : 3, 5: 1 to 1: 2,5, 5: 1 to 1: 2, 5: 1 to 1: 1, 8, 5: 1 to 1: 1, 5, 5: 1 to 1: 1.2, 5 : 1 to 1: 1, 5: 1 to 1: 0.8 and 5: 1 to 1: 0.5. Additional examples include ratios such as 4: 1 to 1: 5, 3.5: 1 to 1: 5, 3: 1 to 1: 5, 2.5: 1 to 1: 5, 2: 1 to 1: 5, 1 0.5: 1 to 1: 5, 1: 1 to 1: 5, 0.8: 1 to 1: 5 and 0.5: 1 to 1: 5. According to the present invention, the upper and lower ends of the aforementioned proportions can be freely combined.
[036] Here, the term "reactive nitrogen-containing group" is not particularly restricted, and includes any nitrogen-containing groups in the nitrogen-containing component, which are capable of reacting with the carbohydrate component. Specifically, examples of such reactive nitrogen-containing groups include primary, secondary, tertiary and quaternary amine groups, amide groups, imine and imide groups, as well as cyanate and isocyanate groups.
[037] Here, the term "carbohydrate component" is not specifically restricted and generally includes any carbohydrate compound that is capable of reacting with a nitrogen-containing component.
[038] According to a modality of the pre-reacted binder defined above, the component of at least one carbon carbohydrate is selected from the group consisting of monosaccharides, disaccharides, polysaccharides or a reaction product thereof.
[039] Preferably, the carbohydrate component is or comprises a reducing sugar and / or a component that generates reducing sugar in situ. As used herein, the term "reducing sugar" indicates one or more sugars containing keto groups or groups aldehyde, or that can isomerize, that is, tautomerize to contain keto or aldehyde groups, which groups can be oxidized, for example, with Cu ions, to obtain carboxylic acids. According to the present invention, such a carbohydrate component can be optionally substituted, such as with hydroxy, halo, alkyl, alkoxy and the like. In any carbohydrate component, one or more chiral centers may be present, and both possible optical isomers at each chiral center are included in the invention described herein. In addition, it should also be understood that various mixtures, including racemic mixtures, and other diastereomeric mixtures of the various optical isomers of any carbohydrate component, as well as the various geometric isomers thereof, can be used in one or more of the modalities described herein.
[040] Non-reducing sugars, for example, sucrose, can be used as the carbohydrate component or part of it, especially when capable and / or subjected to in situ conversion to a reducing sugar. In addition, it is also understood that a monosaccharide, disaccharide, or polysaccharide can be partially reacted with a precursor to form a product of the carbohydrate reaction. As the product of the carbohydrate reaction is obtained from a monosaccharide, a disaccharide or a polysaccharide, and maintains similar reactivity with the nitrogen-containing component to form reaction products similar to those of a monosaccharide, a disaccharide, or a polysaccharide with a nitrogen-containing component, the product of the carbohydrate reaction is within the term scope of the carbohydrate component.
[041] Preferably, any carbohydrate component should be sufficiently non-volatile to maximize its ability to remain available for reaction with the nitrogen-containing component. The carbohydrate component can be a monosaccharide in the form of aldose or ketosis, including a triosis, tetrose, pentose, hexose or heptose; or a polysaccharide; or combinations of these. For example, when a triosis serves as the carbohydrate component, or is used in combination with other reducing sugars and / or a polysaccharide, an aldotriose sugar or a ketotriose sugar can be used, such as glyceraldehyde and dihydroxyacetone, respectively. When tetrose serves as the carbohydrate component, or is used in combination with other reducing sugars and / or a polysaccharide, aldotetrose sugars, such as erythrosis and threose; and ketotetrose sugars, such as erythrulose, can be used. When a pentose serves as the carbohydrate component, or is used in combination with other reducing sugars and / or a polysaccharide, aldopentose sugars, such as ribose, arabinose, xylose, lixose; and ketopentose sugars such as ribulose, arabulose, xylulose, and lixulose, can be used. When a hexose serves as the carbohydrate component, or is used in combination with other reducing sugars and / or a polysaccharide, aldohexose sugars, such as glucose (eg, dextrose), mannose, galactose, alose, altrose, thalose, glucose, idose; and ketohexose sugars, such as fructose, psychosis, sorbose and tagatose, can be used. When a heptosis serves as the carbohydrate component, or is used in combination with other reducing sugars and / or a polysaccharide, a ketoheptose sugar such as sedoheptulose can be used. Other stereoisomers of such carbohydrate components not known to occur naturally, are also contemplated to be useful in the preparation of binder compositions as described herein. In one embodiment, the carbohydrate component is high fructose corn syrup (RFCS).
[042] As mentioned above, the carbohydrate component can be polysaccharide. For example, the carbohydrate component can be polysaccharide with a low degree of polymerization and includes, for example, molasses, starch, cellulose hydrolysates, or mixtures thereof.
[043] According to a specific example, the carbohydrate component is a starch hydrolyzate, a maltodextrin or a mixture thereof. Although carbohydrates of higher degrees of polymerization may not be preferable, they may nevertheless be useful within the scope of the present invention by in situ depolymerization.
[044] In addition, according to the present invention, the carbohydrate component can be used in combination with a non-carbohydrate polyhydroxy reagent. Examples of non-carbohydrate polyhydroxy reagents that can be used in combination with the carbohydrate component include, but are not limited to, trimethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, fully hydrolyzed polyvinyl acetate, and mixtures thereof . For example, the non-carbohydrate polyhydroxy reagent is sufficiently non-volatile to maximize its ability to remain available for reaction with a monomeric or polymeric polyamine. In addition, according to the present invention, the hydrophobia of the non-carbohydrate polyhydroxy reagent can be a factor in determining the physical properties of a binder prepared as described herein. Other co-reaction compounds, for example, as compounds containing carbonyl - aldehydes, ketones, carboxylic acids and anhydrides, can be used.
[045] In a preferred embodiment of the pre-reacted binder composition defined above, the at least carbohydrate component is selected from the group consisting of ribose, arabinose, xylose, lixose, glucose (dextrose), mannose, galactose, alose, altrose, thalose, sugar, idose, fructose, psychosis, sorbose, dihydroxyacetone, sucrose and tagatose, as well as their mixtures.
[046] In addition, the term "nitrogen-containing component" is not particularly limited here and includes any chemical compound, or mixture of compounds, that contains at least one nitrogen atom and is capable of reacting with the component of at least one carbohydrate.
[047] According to one embodiment, in the pre-reacted binder composition as defined above, the at least one nitrogen-containing component is NH3, an inorganic amine or an organic amine comprising at least one primary amine group, as well as the salts of these. For example, as the nitrogen-containing component NH3 can be used as such (for example, in the form of an aqueous solution), as well as any type of inorganic and organic ammonium salts, provided that these salts are capable of reacting with the component of carbohydrates defined above. Specific examples of inorganic ammonium salts include ammonium sulfate (AmSO4), ammonium phosphate, ammonium chloride, and ammonium nitrate.
[048] According to the present invention, the nitrogen-containing component can be a polyamine. Here, the term "polyamine" includes any organic compound with two or more amine groups, which can be independently substituted. As used herein, a "primary polyamine" is an organic compound that has two or more groups of primary amine (-NH). Within the scope of the term primary polyamine are compounds that can be modified in situ or isomerized to generate a compound having two or more primary amine groups (-NH2).
[049] For example, the polyamine can be a primary polyamine. According to an embodiment of the present invention, the primary polyamine can be a molecule having the formula H2N-Q-NH2, where Q is an alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl or, each of which can be optionally substituted. For example, Q may be an alkyl group selected from a group consisting of C2-C24, an alkyl selected from a group consisting of C2_Cg, an alkyl selected from a group consisting of C3-C7. According to a preferred embodiment, Q is a Cg alkyl. According to another embodiment, Q can be a cyclohexyl, cyclopentyl or cyclobutyl, or a benzyl group.
[050] As used herein, the term "alkyl" includes a chain of carbon atoms, which can be optionally branched. As used herein, the terms "alkenyl" and "alkynyl" independently include a chain of carbon atoms, which can be optionally branched, and which include at least one double bond or understood to be triple bond, respectively. Must & alkynyl may also include one or more double bonds. It should be understood that an alkyl group advantageously has a limited length, including C1-C24, Ci Ci2r Ci Cs, Ci Cg, and C1-C4. It should also be understood that alkenyl and / or alkynyl can each advantageously have a limited length, including C2-C24, C2-C12, C2-Csr C2-Cg and C2 C4. In particular, shorter alkyl, alkenyl, and / or alkynyl groups may add less hydrophilicity to the compound, so that they will have different reactivity with respect to the carbohydrate component and solubility in a binder solution.
[051] As used herein, the term "cycloalkyl" includes a chain of carbon atoms, which can optionally be branched, wherein at least a portion of the chain is cyclical. In addition, according to the present invention it should be noted that the term "cycloalkylalkyl" is considered to be a subset of cycloalkyl, and that the term "cycloalkyl" also includes polycyclic structures. For example, such cycloalkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, 2-methylcyclopropyl, cyclopentyl-2-yl, adamantyl, and the like. As used herein, the term "cycloalkyl" includes a chain of carbon atoms, which can optionally be branched, and includes at least one double bond, wherein at least a portion of the chain is cyclical. According to the present invention, said at least one double bond can be in said cyclical part of cycloalkenyl and / or the non-cyclic portion of cycloalkenyl. In addition, it should be understood that cycloalkenylalkyl and cycloalkylalkenyl are each considered as subsets of cycloalkenyl. In addition, according to the present invention "cycloalkyl" can be polycyclic. Examples of such cycloalkenyls include, but are not limited to, cyclopentenyl, cyclohexylethen-2-yl, cycloheptenylpropenyl, and the like. In addition, the chain forming cycloalkyl and / or cycloalkenyl is advantageously of a limited length, including C3-C24, C3-C12, C3-C8, C3-C6, and C5-C6. According to the present invention, an alkyl and / or lower alkenyl group forming cycloalkyl and / or cycloalkenyl, respectively, can add less lipophilicity to the compound, and consequently can behave differently.
[052] As used herein, the term "heteroalkyl" includes a chain of atoms that includes both carbon and at least one heteroatom and is optionally branched. Examples of such heteroatoms include nitrogen, oxygen, and sulfur. In certain variations, said heteroatoms also include phosphorus and selenium. In one embodiment, a heteroalkyl is a polyether. As used herein, the term "cycloheteroalkyl", including heterocyclic and heterocycle, includes a chain of atoms that includes both carbon and at least one heteroatom, such as heteroalkyl, and can optionally be branched where at least a portion of the chain is cyclical . Likewise, examples of cycloheteroalkyl include, but are not limited to, tetrahydrofuryl, pyrrolidinyl, tetrahydropyranyl, piperidinyl, morpholinyl, piperazinyl, homopiperazinyl, quinuclidinyl, and the like.
[053] Here, the term "optionally substituted" includes the replacement of hydrogen atoms by other functional groups in which the radical is optionally substituted. Such other functional groups include illustratively, but are not limited to, amino, hydroxyl, halo, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, aryletheroalkyl, nitro, sulfonic acids and derivatives thereof, carboxylic acids and derivatives thereof, and the like. Illustratively, any amino, hydroxyl, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, aryletheroalkyl, and / or sulfonic acid is optionally substituted.
[054] For example, the primary polyamine can be a diamine, triamine, tetramine, or pentamine. According to one embodiment, the polyamine is a triamine selected from a diethylenetriamine, 1-piperazine ethanamine, or bis (hexamethylene) triamine. In another embodiment, the polyamine is a tetramine, for example, tetylenetetramine. In another embodiment, the polyamine is a pentamine, for example, tetraethylenepentamine.
[055] One aspect of the primary polyamine is that it may have low steric impedance.
[056] For example, 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1, 2-diaminododecane, 1,4-diaminocyclohexane, 1, 4-diaminobenzene, diethylenetriamine, tetylenetetramine, tetraethylenepentamine, piperazine and hananamine, 1,2-methylpentamethylenediamine, 1,3-pentanediamine, and bis (hexamethylene) triamine, as well as 1,8-diaminooctane have low spatial impediment within the scope of the present invention. According to a preferred embodiment of the pre-reacted binder composition, as defined above, the nitrogen-containing component is the primary polyamine 1,6-diaminohexane (hexamethylenediamine, HMDA). In another embodiment, the nitrogen-containing component is 1,5-diamino-2-methylpentane (2-methyl-pentamethylenediamine).
[057] In another embodiment, the nitrogen-containing component is the primary polyether polyether polyamine. For example, according to the present invention, said polyether polyamine is a diamine or a triamine. In one embodiment, polyether polyamine is a trifunctional primary amine having an average molecular weight of 440 known as Jeffamine-T-403 Polyetheramine (Huntsman Corporation). EDR-104 and EDR-148 (Huntsman) can also be used.
[058] In another embodiment, the nitrogen-containing component may include a polymeric polyamine. For example, polymeric polyamines within the scope of the present invention, include chitosan, polylysine, polyethyleneimine, poly (N-vinyl-N-methylamine), poly-aminostyrene and polyvinylamines. In a specific example, the nitrogen-containing component comprises a polyvinyl amine. As used herein, the polyvinyl amine can be a homopolymer or a copolymer.
[059] The term "solvent" used here is not particularly restricted, and includes any solvent that can be used to carry out a reaction between the carbohydrate component and the nitrogen-containing component. For example, the solvent can be water, an organic solvent or mixtures thereof. Examples of organic solvents include alcohols, ethers, esters, ketones, aldehydes, alkanes and cyanoalkanes. Preferably, the solvent consists of or consists essentially of water.
[060] According to another embodiment, the pre-reacted binder composition defined above has an average molecular weight in the range of 200 to 5000 g / mol. According to the present invention, the average molecular weight of the pre-reacted binder composition can vary from 300 to 4500 g / mol, from 400 to 4000 g / mol, from 450 to 3500 g / mol, from 500 to 300 g / mol mol or from 600 to 1500 g / mol. However, the average molecular weight of the composition of the pre-reacted binder is not limited to said ranges and the upper and lower values of these can be freely combined.
[061] Another embodiment of the present invention relates to the composition of the pre-reacted binder defined above, in which the weight ratio between the carbohydrate component and the nitrogen-containing component is 0.5: 1 to 30: 1. Examples of other molar ratios include ratios from 0.7: 1 to 25: 1, 1: 1 to 22: 1, 1 0.5: 1 to 20: 1, 2: 1 to 15: 1, 2.5: 1 to 10: 1 or 3: 1 to 8: 1. However, according to the present invention, the molar ratio of the carbohydrate component to the nitrogen-containing component is not limited to said bands and the aforementioned upper and lower ends can be combined freely.
[062] Another embodiment concerns the composition of the pre-reacted binder, as defined above, comprising at least 10% of the initial carbonyl groups provided by the carbohydrate component. In particular, in some embodiments of the pre-reacted binder composition of the present invention, some of the initial carbonyl groups of the carbohydrate component have not reacted with the nitrogen-containing component and are still present in it. Other examples of the number of unreacted carbonyl groups in the composition of the pre-reacted binder include at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least minus 50%, at least 60% or at least 75% of the carbonyl groups present in the carbohydrate component before reaction with the nitrogen-containing component. According to a specific embodiment, the initial carbonyl groups are present in the form of unreacted carbohydrates.
[063] As used herein, the term "unreacted carbohydrate component" refers to any compound of (i) at least one carbohydrate component that is still present in its initial form, that is, that has not undergone any reaction . According to one embodiment, the pre-reacted binder composition comprises, based on the total weight of the binder composition, up to 80% by weight of unreacted carbohydrate, for example, up to 75% by weight, up to 70% by weight, up to 65% by weight, up to 60% by weight, up to 55% by weight or up to 50% by weight.
[064] Depending on its chemical composition, the pre-reacted binder composition of the present invention can be used as such, that is, applying it freely assembled to the material and curing it, for example, through the application of heat and / or radiation to reach a polymeric binder.
[065] In another embodiment, the pre-reacted binder composition can be used by subsequently adding a cross-linking agent, applying the mixture on the freely assembled matter and curing the mixture, thus forming a highly cross-linked polymeric binder having similar or even better properties over known carbohydrate-based binders. In this case, the composition of the pre-reacted binder of the present patent application can advantageously be prepared, stored and / or transferred, and later used and / or in a different location by adding a crosslinking agent to complete the final binder composition.
[066] If not indicated otherwise, any of the above definitions also applies to the other aspects and modalities of the present invention described below.
[067] Another aspect of the present invention relates to a method of fabricating the composition of the pre-reacted binder, as defined above, comprising the steps of: (i) providing at least one carbohydrate component, (ii) providing at least minus a nitrogen-containing component, (iii) mixing in a solvent, the carbohydrate component (s) and the nitrogen-containing component (s), and (iv) reacting the component (s) of carbohydrate and nitrogen-containing component (s) in the solution or dispersion obtained in step (iii).
[068] According to the present invention, the method of manufacturing the composition of the pre-reacted binder can be carried out under the same conditions (i.e. components and proportions) as defined above in relation to the composition of the pre-reacted binder .
[069] In a preferred embodiment, the preparation of the pre-reacted binder composition is carried out in a solvent, such as water, to directly obtain a binder solution usable for storage, transportation or as a base for the preparation of the binder composition Final. For example, the pre-reacted binder composition can be prepared in a concentrated aqueous solution of the carbohydrate component and the nitrogen-containing component. The concentrated pre-reacted binder solution thus obtained can then be used, for example, at a later time and / or at a different location, for example, by diluting and adding a cross-linking agent, such as an effective binder for consolidation of loose assembled matter.
[070] According to a preferred embodiment of the present invention, the steps above (i) to (iv) are performed while the carbohydrate component (s) and nitrogen-containing component (s) are not in contact with a set of elements that must be connected by a polymeric binder.
[071] The temperature in step (iv) of the previous method of manufacturing the pre-reacted binder composition of the present invention is not specifically limited and includes temperatures in the range of 10 to 120 ° C, 15 to 110 ° C, 20 to 100 ° C or 25 to 90 ° C. For example, the reaction temperature can range from 25 to 85 ° C, 30 to 80 ° C, from 35 to 75 ° C or 40 to 70 ° C. Specific examples of the temperature range include 40 to 90 ° C, 45 to 85 ° C and 50 to 75 ° C. According to the present invention, the temperature at which the pre-reacted binder composition is prepared is not limited to the above ranges, and the upper and lower values of said ranges can be freely combined.
[072] According to one embodiment, the reaction step (iv) of the method described above is carried out by reacting the carbohydrate component (s) and nitrogen-containing component (s) at a maximum temperature of 120 ° C, for example, maximum 115 ° C, maximum 110 ° C, maximum 105 ° C, maximum 100 ° C, maximum 95 ° C, maximum 90 ° C, maximum 85 ° C, or maximum 80 ° C.
[073] Likewise, the reaction duration of the carbohydrate component (s) and nitrogen-containing component (s) in the reaction step (iv) in the above process is not specifically limited and includes durations from 5 to 240 minutes, 5 to 210 minutes, 5 to 180 minutes, 5 to 150 minutes, 5 to 120 minutes, 5 to 90 minutes, 5 to 75 minutes 5 to 60 minutes, 5 to 40 minutes, 5 to 30 minutes and 5 to 25 minutes. Other examples include the duration of 5 to 240 minutes, 10 and 240 minutes, 15 to 240 minutes, 20 to 240 minutes, 25 to 240 minutes, 30 to 240 minutes, 40 to 240 minutes, 45 to 240 minutes, 60 to 240 minutes, 120 to 240 minutes and 180 to 240 minutes. However, the duration of up to one, two, three, four, five and six days, as well as the duration of one, two or three weeks, may also be reasonable within the scope of the present invention. According to the present invention, the duration for the preparation of the pre-reacted binder composition as defined above is not limited to the above examples and the upper and lower values of said bands can be freely combined here.
[074] According to one embodiment, the reaction step (iv) is carried out by reaction of the carbohydrate component (s) and nitrogen-containing component for a period of maximum 96 hours, for example, no maximum 90 hours, maximum 85 hours, maximum 80 hours, maximum 75 hours, maximum 70 hours, maximum 65 hours, maximum 60 hours, maximum 55 hours, maximum 50 hours, maximum 45 hours maximum 40 hours, maximum 35 hours, maximum 30 hours, maximum 25 hours, maximum 20 hours, maximum 15 hours, maximum 10 hours, maximum 5 hours or maximum 3 hours. The reaction step (iv) can be carried out by reacting the carbohydrate component (s) and the nitrogen-containing component (s) for a period of at least 5, 10, 15, 20, 25, 30 , 40, 60 12 or 180 minutes.
[075] According to a specific modality, the reaction step (iv) is carried out by reacting the carbohydrate component (s) and nitrogen containing component (s) at a temperature range of 40 to 120 ° C for a period of time. 5 to 180 minutes.
[076] According to a specific modality, the reaction step (iv) is carried out by reacting the carbohydrate component (s) and nitrogen containing component (s) at a temperature range of 20 to 30 ° C for one 1 to 96 hours.
[077] According to the present invention, the duration and temperature for carrying out the reaction step (iv) in the above method is not limited to the above examples and the upper and lower values of said ranges can be freely combined here.
[078] According to another embodiment, the viscosity of the solution or dispersion during step (iv) reacting the carbohydrate component (s) and the nitrogen-containing component (s) does not increase by more than 300 cP, when determined at 20 ° C and a starting concentration of 70% by weight of total carbohydrate. and components containing nitrogen present before said step (iv). For example, viscosity does not increase by more than 275 cP, more than 250 cP, more than 225 cP, more than 200 cP, more than 175 cP, more than 150 cP, more than 100 cP, more than than 75 cP, or more than 50 cP.
[079] The reaction step (iv) can be carried out at, or substantially at atmospheric pressure, for example, in an open reactor. Alternatively, the reaction step (iv) can be carried out in a closed reaction vessel; can be performed at a pressure above atmospheric pressure.
[080] According to another aspect, the present invention relates to a pre-reacted water-soluble binder composition that can be obtained by the method as defined above.
[081] For example, one embodiment refers to the pre-reacted binder composition, as defined above, wherein said binder composition is obtained by reaction, in a solvent, at least one carbohydrate component with at least one component containing nitrogen, at a temperature of at least 10 ° C for a period of at least 5 minutes.
[082] According to another aspect, the present invention relates to the use of a pre-reacted water-soluble binder composition as defined above in the production of a product comprising a set of matter bound by a polymeric binder.
[083] Here, the term "set of matter" is not particularly restricted, and includes any set of matter which comprises fibers selected from the group consisting of mineral fibers (including slag wool fibers, stone wool fibers, glass fibers), aramid fibers, ceramic fibers, metallic fibers, carbon fibers, polyimide fibers, polyester fibers, rayon fibers and cellulosic fibers. Other examples of a set of matter include: particles, such as coal, sand; cellulosic fibers; wood shavings, sawdust, wood pulp, floor wood, wood shavings, wood strips, wood layers; other natural fibers, such as jute, linen, hemp, and straw; wood veneers; coatings; wood coverings, particles, fabrics or non-woven materials (for example, fibers which are, in particular, of the type (s) referred to above).
[084] Another aspect of the present invention relates to a method of manufacturing a set of material bound by a polymeric binder, comprising the steps of: (i) providing a set of material, (ii) providing the binder composition pre-reacted above defined, or a pre-reacted binder composition obtained by the process as defined above, in a solvent to obtain a solution or dispersion, (iii) applying the solution or dispersion obtained in step (ii) to the whole of the material , and (iv) application of energy to the set of material containing the solution or dispersion to cure the binder composition.
[085] The step (iv) of applying energy to the whole of matter, as defined in the above process is not particularly restricted and includes, for example, heating in an oven at a temperature of 100 ° C to 350 ° C, depending the type of material, the amount of binder and other conditions.
[086] According to an embodiment of the method above, in step (ii) a cross-linking agent is added to the pre-reacted binder composition, as defined above, or the pre-reacted binder composition obtained by the process as defined. above, or the solution or dispersion thereof.
[087] In another embodiment of the above-defined set of elements, the pre-reacted binder composition as defined above, or the pre-reacted ligand composition obtained by the process as defined above has been aged for at least 24 hours before the crosslinker is added in step (ii). Other examples include aging periods of at least 48 hours, at least 72 hours, at least 96 hours, at least one, two or three weeks, or at least one or two months.
[088] According to the present invention, the composition of pre-reacted binder can change over time in its chemical composition, continuing the reaction between the carbohydrate component and the nitrogen containing component. For example, even at relatively low temperatures, such as room temperature (20 ° C) or below, maillard-type reactions can continue between the carbohydrate component and the nitrogen-containing component for the formation of melanoidins. As a consequence, aging of the pre-reacted binder composition can lead to an accelerated final curing process of the binder and / or an improved bond strength.
[089] According to another method of manufacturing a set of elements defined above, before the step of applying the solution or dispersion obtained in step (ii) to the set of matter, the set of matter is substantially free of binder .
[090] Another aspect of the present invention relates to a binder or dispersion solution comprising in a solvent the pre-reacted binder composition as defined above and a crosslinking agent.
[091] The solution of the pre-reacted binder or dispersion composition, in particular in the state applied to the material to be bonded, may comprise: • at least 5% to 10%, 15% or 18% solids and / or • less than 80%, 70% or 60% (in particular in the case of wood board applications) or less than 50%, 40% or 20% of solids (especially in the case of mineral fiber insulation applications)
[092] particularly determined how to harden solids by weight after drying at 140 ° C for 2 hours.
[093] According to another aspect, the present invention relates to a fiber or a product containing particles comprising one or more types of fibers and / or particles and the pre-reacted binder composition, as defined above in a state healed.
[094] Binders according to the present invention can be used as binders, for example, in articles selected from the group consisting of: thermal insulation materials; mineral wool insulation (including glass wool insulation and rock wool insulation); wooden boards; fiber panels; wood particle boards; chip boards; oriented particle boards; medium density fiberboard; plywood; high pressure laminates.
[095] The amount of binder in the final product, particularly in the case of mineral wool insulation, can be: • greater than: 1%, 2%, 2.5%, 3%, 3.5% or 4%; and / or • less than: 20%, 15%, 10% or 8%
[096] measured by the dry weight of the finished product.
[097] The amount of binder for mineral wool insulation is usually measured by loss on fire (LOI).
[098] Particularly, in the case of mineral fiber insulation, products can have one or more of the following strong starting points:
[099] Ordinary Starting Force of • at least 120 g / g, preferably at least 150 g / g; and / or • less than 400 g / g
[0100] Exposed Starting Force of • At least 120 g / g, preferably at least 150 g / g; and / or • less than 400 g / g
[0101]% loss between the Ordinary and Exposed Starting Force of • Less than 10%, preferably less than 5%
[0102] The separation force is expressed in grams / gram with the total breaking load of six test samples divided by their total weight.
[0103] The test is performed on mineral fiber mats as received for tests (Ordinary Starting Force) and after an accelerated aging test, as explained below (Exposed Starting Force).
[0104] A first set of six samples of the shape and dimensions indicated in figure 14 is cut from the mineral fiber blanket to be tested. The dimensions are as follows:
[0105] r: 12.7 mm radius;
[0106] DC: distance between centers of 44.5 mm;
[0107] a: 25.4 mm;
[0108] b: 121 mm.
[0109] The longest axis of the sample must be parallel to the direction of transport and the samples must be measured along the total width of the mineral surface. A second set of six samples is then collected in the same way.
[0110] The total weight of the first group of six W1 samples in grams is recorded.
[0111] The total weight of the second group of six samples in grams W2 is recorded; these samples are then placed in a preheated air autoclave and on a wire mesh shelf away from the bottom of the wet steam chamber at 35kN / m2 for one hour. They are then removed, dried in an oven at 100 ° C for five minutes and immediately tested for starting strength.
[0112] To test the starting force, each sample is mounted in turn on the clutches of an Instron and 5500 tension force machine and the maximum breaking load in grams or Newtons is recorded. If the rupture load is measured in Newtons it is converted to grams by multiplying by 101.9. Six gram results are obtained for each set of samples: G1 G2 G3 G4 and G5 G6 for the first set of samples and G7 G8 G9 G10 G1 1 and G12 for the second set of samples.
[0113] The Ordinary Starting Force is calculated from the first set of samples using the formula of the Ordinary Starting Force = (G1 + G2 + G3 + G4 + G5 + G6) / W1.
[0114] The Exposed Starting Force is calculated from the second set of samples using the Exposed Starting Force formula = (G7 + G8 + G9 + G10 + 1 + G1 G12) / W2.
[0115] When the product is mineral wool insulation, it can have one or more of the following characteristics: • The density greater than 5, 8 or 10 kg / m3; • The density less than 200, 180 or 150 km / m3 • comprises glass wool fibers and has a density greater than 5, 8 or 10 kg / m3 and / or less than 80, 60 or 50 kg / m3; • It comprises stone wool fibers and has a density greater than 15, 20 or 25 kg / m3 and / or less than 220, 200 or 180 kg / m3; A thermal conductivity ≤ less than 0.05 W / mK and / or greater than 0.02 W / mK • comprise less than 99% by weight and / or more than 80% by weight of mineral fibers. • Thickness greater than 10 mm, 15 mm or 20 mm and / or less than 400 mm, 350 mm or 300 mm.
[0116] When the product is a wooden board product, it can have one or more of the following characteristics: • The dimensions of at least 50 cm x 80 cm, preferably at least 1 m x 2 m • Thickness of at least 11 mm, 15 mm or 12 mm • Curing time less than 25, 15, 12 or 10 minutes • An internal bonding force measured in accordance with EN319 of at least: 0.4 N / mm2 or 0.45 N / mm2 ( in particular for particle boards and fiber boards), or measured according to EN300 of at least 0.28 N / mm2 (in particular for oriented particle boards) • An increase in thickness after 24 hours in water at 20 ° C according to EN317 in less than 12%, preferably less than 10% • Water absorption after 24 hours in water at 20 ° C less than 40%, preferably less than 30% • An elasticity module according to EN310 of at least: 1800 N / mm2 (in particular for particle boards and fiber boards), 2500 N / mm2 (particularly for oriented wood panels) or 3500 N / mm2 or 4800 N / mm2 • Flexural strength (MOR) of at least: 14 N / m2 (in particular for particle boards and fiber boards), 18 N / mm2 (particularly for wood panels or 20 N / mm2 or 28 N / mm2 • Wax as an additive, for example, in the range of 0.1 to 2% by weight, preferably 0.5 to 1% by weight
[0117] A binder content (weight of dry resin to weight of dry wood particles) in the range of 8 to 18% by weight, preferably 10 to 16% by weight, more preferably 12 to 14% by weight. • Be cured in a press, especially between plates or rolls that have a temperature above 180 ° C or 200 ° C and / or less than 280 ° C or 260 ° C.
[0118] Various additives can be incorporated into the binder composition. These additives give the binders of the present invention other desirable characteristics. For example, the binder can include a silicone-containing coupling agent. Many silicone-containing coupling agents are commercially available from Dow Corning Corporation, Evonik, and Momentive Performance Materials. Illustratively, the silicone-containing coupling agent includes compounds, such as alkylsilyl ethers and silylethers, each of which can be optionally substituted, such as with halogen, alkoxy, amino, and the like. In one variation, the silicone-containing compound is an amino-substituted silane, such as gamma-aminopropyltriethoxy silane (SOQUES A-l 101; Momentive Performance Materials, Headquarters: 22 Corporate Woods Boulevard, Albany, NY 1221 1 USA). In another variation, the silicone-containing compound is an amino substituted silane, for example, aminoethylaminopropyltrimethoxy silane (Dow Z-6020, Dow Chemical, Midland, Ml, USA). In another variation, the silicone-containing compound is gamma-glycidoxypropyltrimethoxysilane (SOQUES A-187; Momentive). In yet another variation, the silicone-containing compound is an aminofunctional oligomeric siloxane (Hydrosil 2627, Evonik, 379 Interpace Parkway, Parsippany, NJ 07054).
[0119] Silicone-containing coupling agents are typically present in the binder in the range of about 0.1 percent to about 1 weight percent based on dissolved binder solids (i.e., about 0.05% at about 3% based on the weight of the solids added to the aqueous solution). These silicone-containing compounds improve the ability of the binder to adhere to the material of the binder that is disposed, such as glass fibers, improving the ability of the binder to adhere to the material improves, for example, its ability to produce or promote cohesion in substance ( s) assembled (s) not tightened or tightened.
[0120] In another illustrative embodiment, a binder of the present invention can include one or more corrosion inhibitors. These corrosion inhibitors prevent or inhibit eating or wearing out a substance, such as metal, caused by chemical decomposition caused by an acid. When a corrosion inhibitor is included in a binder of the present invention, the corrosivity of the binder is decreased in comparison to the aggressiveness of the binder without the inhibitor present. In one embodiment, these corrosion inhibitors can be used to decrease the corrosion of the compositions containing mineral fibers described herein. Illustratively, corrosion inhibitors include one or more of the following, a dedusting oil, or a monoammonium phosphate, sodium metasilicate pentahydrate, melamine, tin (II) oxalate, and / or methylhydrogen silicone fluid emulsion. When included in a binder of the present invention, corrosion inhibitors are typically present in the binder in the range of about 0.5 percent to about 2 weight percent based on the dissolved binder solids.
[0121] According to one embodiment, the fiber or product containing particles, as defined above, can be obtained by the process of manufacturing a set of material, as defined above.
[0122] According to a specific modality, the fiber or the product containing particles contains one or more fructosazines. Preferably, said one or more fructosines are present in an amount of 0.001 to 5% by weight, for example, from 0.01 to 5% by weight, 0.05 to 5% by weight, from 0.1 to 5% by weight, 0.15 to 5% by weight, 0.2 to 5% by weight, 0.25 to 5% by weight, 0.3 to 5% by weight, 0.4 to 5% by weight, from 0 , 5 to 5% by weight, 0.75 to 5% by weight, from 1 to 5% by weight, from 0.5 to 5% by weight, from 2 to 5% by weight, or from 2.5 to 5 % by weight. Other examples include ranges from 0.01 to 4.5% by weight, 0.01 to 4% by weight, 0.01 to 3.5% by weight, 0.01 to 3% by weight, 0.01 to 2.5% by weight, 0.01 to 2% by weight, from 0.01 to 1 0.5% by weight, from 0.01 to 1% by weight or 0.01 to 75% by weight. According to the present invention, the amount in which the one or more fructosazines are contained in the fiber or product of the present invention containing particles is not limited to the above ranges, and the upper and lower values of said ranges can be freely combined.
[0123] The figures show:
[0124] Figure 1 shows: The cure rates of dextrose binders pre-reacted with ammonia and their pH.
[0125] Figure 2 shows: The cure rates of dextrose binders pre-reacted with HMDA and their pH.
[0126] Figure 3 shows: An average internal bond and swelling results for plaques made with pre-reacted dextrose / fructose + HMDA ligand at different ages.
[0127] Figure 4 shows: Viscosity and gel time of an aged dextrose / fructose + HMD The pre-reacted paste, measured on the same day that the plates were made.
[0128] Figure 5 shows: The pre-reacted binder (GWE2) less faded than the standard binder (GWST) during the Weatherometer test with 327 hours of exposure under xenon light.
[0129] Figure 6 shows: Evolution of viscosity for several pre-reacted binders.
[0130] Figure 7 shows: Evolution of viscosity for several pre-reacted binders.
[0131] Figure 8 shows: Evolution of viscosity for several pre-reacted binders.
[0132] Figure 9 shows: Evolution of pH for several pre-reacted binders.
[0133] Figure 10 shows: Healing time dependent on the molar ratio of HFCS / Ammonia / HMDA at a cure temperature of 120 ° C.
[0134] Figure 11 shows: HFCS / ammonia cure times pre-reacted cross-linked at 120 ° C, depending on the diamine (HMDA vs. EDR-104).
[0135] Figure 12 shows: HFCS / ammonia cure times pre-reacted cross-linked at 140 ° C, depending on the diamine (HMDA vs. EDR-104).
[0136] Figure 13 shows: HFCS / ammonia cure times pre-reacted cross-linked at 160 ° C, depending on the diamine (HMDA vs. EDR-104).
[0137] Figure 14 shows: a plan view of a mineral fiber test sample.
[0138] Figure 15 shows: Viscosity and absorbance of a pre-reacted binder composition.
[0139] Figure 16 shows: The calibration of the GPC device.
[0140] Figure 17 shows: GPC chromatograms of pre-reacted binder composition with various pre-reaction times.
[0141] Figure 18 shows: GPC chromatograms of pre-reacted binder composition with various pre-reaction temperatures.
[0142] The composition of the pre-reacted binder of the present invention advantageously overcomes a variety of known disadvantages from common carbohydrate-based binders. In particular, preferred embodiments of the pre-reacted binder composition can be stored or transported for an extended period of time without recrystallizing the carbohydrate or gelling component that would render the binder composition unusable. In addition, preferred embodiments of the composition of the pre-reacted binder of the present invention results in improved cure times, improved bond strength and reduced fading, for example, of resulting fiber products. By using preferred embodiments of the composition of the pre-reacted binder of the present invention, fiber or products containing particles can be obtained, which have a reduced content of unreacted carbohydrate components, so that they are more stable against microbial degradation.
[0143] The present invention will be further illustrated in the following examples, without limitation. EXAMPLE 1: PRE-REAGIDED COMPOSITION OF DEXTROSEEAMONY AND ETHETICULATION WITH COMHMDA, ACIDOCITRIC AND AMMONIUM SULFATE
[0144] Dextrose was pre-reacted for several times (t = 0, 1 and 3 hours), at 100 ° C, with ammonia and subsequently cross-linked with HMDA, citric acid or ammonium sulfate. t = 0 corresponds to a mixture of the carbohydrate component and the nitrogen containing component and immediately the addition of crosslinking agent, that is, without allowing any pre-reaction time. CALCULATIONS
[0145] The binders were calculated with optimal molar equivalent, where sugars with equimolar half of ammonia groups are pre-reacted and cross-linked with the other half (Tables 1, 2 and 3).
[0146] The overall proportions are: C = O of sugars / -NH3 of ammonia / -NH2 of HMDA or Am-SO4 or -COOH of citric acid equal 2/1/1.
[0147] (82.76% DMH + 3.92% ammonia) pre-reacted + 13.32% HMDA:

[0148] Table 1: Binder formulations, which pre-reacted ammonia with dextrose and are cross-linked with HMDA at alkaline pH (- 1 1)
[0149] (81.63% DMH + 3.87% ammonia) pre-reacted with 14.5% citric acid:


[0150] Table 2: The formulations of the 2 binders that pre-reacted ammonia with dextrose and are cross-linked with citric acid at acidic pH (~ 4)
[0151] (81% DMH 0.22+ 3.85% HMDA) pre-reacted + 14.93% AmSO4:

[0152] Table 3: Binder formulations that pre-reacted ammonia with dextrose and are cross-linked with citric acid at neutral pH (~ 8) CURE OF PRE-REAGED BINDERS
[0153] As described above, nine binders were prepared in 70% solids and diluted with 7% solids to cure them in microfiber filters. The filters were cured for 5 minutes (well cured), that is, 2.5 minutes (leaving a slight extract in water). In addition, binders were diluted by 22.5%, to follow their cure rates (cf. Figure 1). To follow cure rates, drops of binder were placed on glass fiber filters and cured several times. The spots were extracted in water and the absorbance of the leachate measured using a spectrophotometer. Absorbance increases initially due to the formation of soluble colored compounds. The absorption then falls due to the crosslinking of these soluble compounds. The cure speed is considered the time necessary for the absorbance to fall to the minimum value.
[0154] In this series of experiments, HMDA is the fastest crosslinking agent, followed by ammonium sulfate and citric acid. The pre-reaction of 1 hour showed better cure rates. Cross-linking with citric acid was slower, with three hours of pre-reaction. Ammonium sulfate and HMDA were cross-linked at the same rate after 1 or 3 hours of pre-reaction. EXAMPLE 2: COMPOSITION OF PRE-REACTED DEXTROSE AND HMDA BINDER
[0155] Dextrose pre-reacted for 0, 15 and 60 minutes at 60 ° C with HMDA and cross-linked with HMDA, citric acid or ammonium sulfate. CALCULATIONS
[0156] The binders were calculated based on Example 1: The overall proportions are: C = O from sugars / NH2 from HMDA / -NH2 from HMDA or AmSC> 4 or -COOH from citric acid is equal to 2 / 0.8 / 0.8 (Table 4, 5 and 6).
[0157] (80% + 10% DMH HMDA) pre-reacted + 10% HMDA:

[0158] Table 4: Formulations of the ligands that pre-reacted HMDA with dextrose and are cross-linked with HMDA at alkaline pH (-1 1)
[0159] (79.2% DMH + 9.9% HMDA) pre-reacted + 10.9% citric acid:

[0160] Table 5: Binder formulations that pre-reacted HMDA with dextrose and are cross-linked with citric acid at acidic pH (~ 6)
[0161] (78.9% DMH + 9.86% HMDA) pre-reacted + 11.24% AmSO4:

[0162] Table 6: Z Linker formulations that pre-reacted HMDA with dextrose and are cross-linked with ammonium sulfate at neutral pH (~ 9) CURE OF PRE-REAGED BINDERS
[0163] As described in the section of Example 1, binders were cured on filters (for 5 minutes at 200 ° C) and on aluminum plates. Cure rates were compared at 140 ° C (cf. Figure 2), using the procedure described in relation to Example 1 for following cure rates.
[0164] In this series of experiments, when Dextrose and HMDA are pre-reacted, HMDA is still the fastest crosslinking agent followed by citric acid and ammonium sulfate. This suggests that the polymers formed through pre-reaction with HMDA are different from those formed with ammonia, citric acid, therefore, it becomes a more efficient cross-linking agent than ammonium sulfate. EXAMPLE 3: AGING STUDY ON THE PRE-REAGED BINDER COMPOSITION GOAL
[0165] To assess how pre-reacted binders change over time with respect to particleboard production. In particular, it provides an indication of whether an aged pre-reacted ligand produces plaques with better or worse Internal Bond Strength (IB) and the effect of the degree of swelling versus the use of a fresh pre-reacted ligand. INTRODUCTION
[0166] It may take a few weeks from the initial production of a binder to use in laboratory or plant tests. This is mainly due to delivery times, production schedules and test delays. It is necessary to know if the aging of the ligand for a few weeks affects the properties of all the plaques made from it. It is believed that the pre-reacted binder will continue to react at a rate much lower than room temperature (~ 20 ° C), which may result in i) the continuation of the Maillard reaction towards melanoidins, which means that the final cure has fewer reactions and, as such, it should be faster and easier to achieve, ii) the reaction could proceed somewhat under different pathways that make the molecules than when attached as melanoidin they are stronger or possibly weaker when completely cured, and iii) these extra reactions could be producing undesirable side products, such as acids, which can delay healing. METHOD
[0167] 1.8 kg of pre-reacted binder was made, consisting of:
[0168] 616g dextrose
[0169] 560g of fructose,
[0170] 200g of HMDA and
[0171] 424g of water.
[0172] Pre-reaction was controlled for 15 minutes at 60-63 ° C. For this, an additional 200g HMDA would be needed to be added to make 2 kg of binder. The extra amount of HMDA actually needed per mixture was calculated and added as and when needed for the required amount of pre-reaction. No extra HMDA was added to the pre-reaction volume at any time.
[0173] Plates were made one day after the pre-reacted binder was made, and every 7 days thereafter. Binder viscosity and pre-reacted gel time of the binder produced from it were measured when the plates were made. Two plates were made with each mixture by pressing and curing between press plates of a press according to the following conditions;
[0174] Plate size - 300mm x 300mm x 10mm
[0175] Desired density - 650 kg / m3
[0176] Chip humidity - 3.1%
[0177]% of the binder - 10.0% by weight
[0178] Press Temperature - 195 ° C
[0179] Pressure Factor - 14s / mm
[0180] Pressure - 504 KN
[0181] Assuming that the first mixing takes place on day 0, the plates were produced on day 0, 7, 14 and 21. On days 0 and 14, only one plate was tested, as on day 0, a plate was made in 12 s / mm and on day 14, a test plate was used for a new process.
[0182] After production, the plates were packed under similar conditions for a minimum of three days before the test. Test consisted of internal bonding tests on a Testometric machine, and both swelling tests of 2 hours and 24 hours in a water bath set to 20 ° C. RESULTS

[0183] Table 7: Test results for internal connection and swelling (see also Figure 3). EXAMPLE 4: PREPARATION PROCESS FOR THE PRODUCTION OF PRE-REAGED BINDING COMPOSITIONS
[0184] A pre-reacted binder composition can be manufactured by the following process: 1. Add the required amount of hot water to the required amount of sugar (s). 2. Record the total weight of the beaker, solution and mixing rod. 3. Apply heat and mix to help dissolve. A hot plate and electric stirrer work well. This can take 30 minutes or more. Make sure that all crystals have dissolved and the solution is clear. 4. Temperature of the carbohydrate solution (eg, dextrose) should be around 55 ° C to 60 ° C, once dissolved. If not, then adjust it to suit this. 5. Check the weight of the beaker, solution and agitator and reach the weight recorded in (2) with water, to take into account evaporation. 6. Add the required amount of nitrogen-containing component (eg HMDA) and record a new total weight, then apply agitation. 7. The reaction temperature should rise to 60 ° C and be maintained between 60-63 ° C, using a heating plate, if necessary. 8. Maintain the temperature for 15 minutes, stirring constantly with an electric stirrer. The solution should turn yellow -> brown -> very dark brown. 9. Check the weight and make up to the weight recorded in (6), to take evaporation into account. 10. Cool the solution quickly in loosely closed containers to avoid evaporation as much as possible. A water bath works well, as does the solution to divide into several parts to aid cooling. It is important that the reaction mixture is cooled before use, and the potential for evaporation is reduced. 11. Once cooled, the pre-reacted solution is complete. Viscosity at 20 ° C should be in the region of 300- 320cp. EXAMPLE 5: XYLO5E STABILITY: FRUITOSE + PRE-REACTED HMDA BINDERS
[0185] Without pre-reaction, when a carbohydrate solution containing 50% xylose is combined, gelation usually occurs within 5 minutes. Therefore, the orientation of plates using such a binder is impossible. With pre-reaction, however, it is possible to make a stable binder, which was successfully used to create wooden panels.
[0186] Table 8 shows the results of the stability tests of a pre-reacted binder (Xylose: Fructose, HMDA 44.44: 44.44: 11.11% by weight of the reagent). Table 9 shows the stability results of the assay of these pre-reacted binders following another addition of HMDA after the pre-reaction was carried out to obtain the total reagent content by weight of xylose: Fructose, HMDA 40:40:20 ( which can also be expressed as: (Xylose: Fructose, HMDA) pre-reacted + then added HMDA (40:40:10) + 10). Different pre-reaction times were tested.
Table 8- Showing stability of the xylose pre-reactions: fructose, heated to different lengths, over time. Little difference was observed in pre-reactions over 15 minutes. Viscosity work and water content analysis are needed to show major differences.


[0187] Table 9 - Showing stability of xylose ligands: fructose, following the pre-reaction and 2nd addition of HMDA, based on different pre-reactions (see Table 8).
[0188] In this series of experiments, little difference was shown in ligands created from 22.5 minutes of pre-reacted ligand solutions and above. It can be noted that the binder made from the 15-minute pre-reaction had gelled, while the other binders had cured.
[0189] Previous work on the stability of the xylose ligand has shown that a pre-reaction time of 22.5 minutes is the lowest known to create a stable ligand. The real point is somewhere between 15 and 22.5 minutes. The curing speed shown by xylose binders is clearly visible here as a binder cured at room temperature in 3 days. EXAMPLE 6: COMPARISON OF PRE-REACTED BINDER WITH CONVENTIONAL BINDER
[0190] In this series of experiments, the binder's recipe was as follows:
[0191] 85% DMH (dextrose monohydrate) + 15% ArnSOí (ammonium sulfate) + 1.25% NH4OH + 9% oil emulsion + 0.3% ISI0200 (silane)
[0192] For pre-reacted binder, DMH and AmSO4 were pre-reacted for 2 hours at 100 ° C with 65% solids. On the day of the test, this binder was diluted; ammonia, oil emulsion and silane were added to it.
[0193] 240 kg of pre-reacted binder (65% solids) were prepared in the laboratory. On the test day, this binder was diluted, silane and oil emulsion were also added to generate a 15% solids binder.
[0194] The unreacted binder was made by combining the ingredients on the test day without heating.
[0195] The binders were used in the production of 25 mm thick mineral wool insulation (CS32 universal slab), density = 32 kg / m3, with a binder content (% by weight measured as LOI) = 7.5 %.
[0196] It was found that the pre-reacted binder generated a product that was more rigid and without suspension than with a standard unreacted binder. Increased suspension may indicate that the binder has been over-cured. The cure and binder content (wt% measured as LOI) with the pre-reacted and unreacted binder were similar. The pre-reacted binder also faded less when exposed to light, which shows the pre-reacted polymer generates a different chromophore (cf. Figure 5).
[0197] Table 10 below shows that: i) The two binders generated a glass wool insulation product with similar LOI, curing and starting strength. The pre-reacted binder was more rigid and without suspension. The increase in powder may be partly explained by a higher density of the product made with the pre-reacted binder. ii) The ramp humidity varies at locations on the surface may be due to an imbalance between the suction under the forming conveyor.

[0198] Table 10: Comparison of standard ligand with pre-reacted ligand
[0199] Figure 5 shows the pre-reacted ligand (GWE2) less faded than the standard ligand (GWST) during the Weatherometer test with 327 hours of exposure under xenon light.
[0200] This exposure time is representative of the four month exposure in the United Kingdom.
[0201] The pre-reacted binder showed an advantage of the rigidity of the manufactured product. Other potential advantages of having pre-reacted DMH consist of less recrystallization before the curing oven and decreased level of bacteria in the wash water. Experiments have shown that the fading of the pre-reacted binder fades less. EXAMPLE 7: THE VISCOSITY OF PRE-REAGED BINDING COMPOSITIONS PREPARATION OF PRE-REAGED BINDER
[0202] Pre-reacted DMH / HMDA were prepared by mixing DMH (88.89% by weight, based on the total weight of the binder composition without water) and HMDA (11.11% by weight based on the total weight of the binder composition without water), ie 5.16 molar equivalent of DMH and 1 molar equivalent of HMDA, in water (at 70% solids) in a sealed pressure glass vial and heated to 60 ° C for 20 minutes to prepare a pre-reacted binder composition.
[0203] The composition of the pre-reacted binder was further heated for 11 days at 60 ° C, while following the viscosity and absorbance of the binder solution. As shown in Figure 15, in this series of experiments only absorbance of the pre-reactor increased steadily over the pre-reaction time, while the viscosity of the pre-reactor did not increase until the last phase of the pre-reaction. EXAMPLE 8: THE GPC ANALYSIS OF THE VARIOUS REACTIVE BINDING COMPOSITIONS GPC ANALYSIS CONFIGURATION HPLC CONFIGURATION
[0204] Shimadzu LC-9A pump
[0205] Autosampler / Shimadzu SIL-6B / Shimadzu SCL 6B system controller
[0206] Shimadzu CBM-10A communication bus module
[0207] Refractive index of the RID-6A Shimadzu Detector
[0208] Diode array detector Shimadzu SPD-M10A
[0209] Shimadzu Class LC-10 evaluation software METHOD
CONFIGURATION
[0210] Column temperature 20 ° C
[0211] Isocratic concentration gradient
[0212] Solvent Water (deionized)
[0213] Flow 1 ml / min
[0214] Analysis time 35 min GPC COLUMNS
[0215] Agilent pre-column, GPC / SEC Guard columns, PL aquagel-OH Guard, 8 pm, 50x7.5 mm
[0216] 1. TosoHaas column, TSKgel L 3000, 10 pm, 300x7.5 mm
[0217] 2. TosoHaas column, TSKgel L 4000 PWXL, 10 pm, 300x7.8 mm
[0218] The GPC apparatus described above was calibrated using sucrose and several pullulans (Figure 16).
[0219] D-glucose (44.45% by weight, based on the total amount of the binder composition without water), D-fructose (44.45% by weight, based on the total amount of the binder composition without water) and HMDA (11.1% by weight, based on the total amount of the binder composition with the water) were mixed in water to obtain a binder composition. GPC ANALYSIS AFTER VARIOUS PRE-REACTION PERIODS
[0220] Figure 17 shows GPC chromatograms (standard: sucrose) of the previous binder composition when pre-reacted at 60 ° C for 0 min, 20 min, 40 min and 60 min.
[0221] The GPC diagram clearly shows the presence of prepolymers having a relatively high molecular weight (GPC retention of about 10 to 15 minutes), of medium molecular weight prepolymers (retention GPC of approximately 15 to 20 minutes) minutes) and the low molecular fraction of the pre-reacted binder composition (about GPC retention> 20 minutes). GPC ANALYSIS AT VARIOUS PRE-REACTION TEMPERATURES
[0222] Figure 18 shows GPC chromatograms (standard: sucrose) of the previous binder composition when pre-reacted for 20 min at 60 ° C, 80 ° C and 100 ° C. The GPC diagram clearly shows the presence of prepolymers having a relatively high molecular weight (GPC retention of about 10 to 15 minutes), prepolymer of average molecular weight (retention GPC of approximately 15 to 20 minutes) and the low molecular fraction of the pre-reacted binder composition (about 20 minute GPO retention).

权利要求:
Claims (38)
[0001]
1. METHOD OF PRODUCTION OF A SET OF MATERIAL CONNECTED BY A POLYMERIC BINDER, characterized by comprising the steps: (i) providing a set of material, (ii) providing a composition of pre-reacted water-soluble binder comprising the (s) reaction product (s) of (a) a reducing sugar, and (b) a nitrogen-containing component selected from the group consisting of an organic amine comprising a primary amine group, salts of an organic amine comprising a primary amine group , a primary polyamine and a polymeric polyamine, wherein the pre-reacted binder composition comprises a prepolymer having a molecular weight in the range of 1 to 500 kDa in an amount of 2% by weight or more, based on the total weight of the pre-reacted binder composition, and wherein the pre-reacted binder composition is a pre-reacted binder prepared by mixing starting materials comprising reducing sugar (a), and the nitrogen-containing component (b) and in that the amount The total amount of reducing sugar (a) and nitrogen-containing component (b) in the starting materials with respect to the total weight of the binder composition before the pre-reaction is at least 20% by weight. (iii) applying the pre-reacted binder composition in the form of an aqueous solution or dispersion containing no more than 80% by weight of said pre-reacted binder composition obtained in step (ii) for the set of matter, and (iv) applying the energy to the set of matter containing said solution or dispersion to cure the binder composition.
[0002]
Method according to claim 1, characterized by step (ii) comprising the addition of a crosslinker to the pre-reacted binder composition.
[0003]
METHOD according to claim 2, characterized in that the crosslinker comprises hexamethylenediamine.
[0004]
METHOD, according to any one of claims 1 to 3, characterized in that said prepolymer having a molecular weight in the range of 1 to 500 kDa is contained in an amount of 5% by weight or more, based on the total weight of the binder composition.
[0005]
5. METHOD according to claim 4, characterized in that said prepolymer having a molecular weight in the range of 1 to 500 kDa is contained in an amount of 10% by weight or more based on the total weight of the binder composition.
[0006]
6. METHOD according to claim 4, characterized in that said prepolymer having a molecular weight in the range of 1 to 500 kDa is contained in an amount of 20% by weight or more based on the total weight of the binder composition.
[0007]
METHOD according to claim 4, characterized in that said prepolymer having a molecular weight in the range of 1 to 500 kDa is contained in an amount of 35% by weight or more based on the total weight of the binder composition.
[0008]
METHOD according to claim 4, characterized in that said prepolymer having a molecular weight in the range of 1 to 500 kDa is contained in an amount of 50% by weight or more based on the total weight of the binder composition.
[0009]
Method according to any one of claims 1 to 8, characterized in that the pre-reacted binder is in the form of an aqueous solution or dispersion containing at least 30% by weight of said pre-reacted binder composition.
[0010]
METHOD according to claim 9, characterized in that the pre-reacted binder is in the form of an aqueous solution or dispersion containing at least 40% by weight of said pre-reacted binder composition.
[0011]
METHOD according to claim 9, characterized in that the pre-reacted binder is in the form of an aqueous solution or dispersion containing at least 50% by weight of said pre-reacted binder composition.
[0012]
METHOD according to claim 9, characterized in that the pre-reacted binder is in the form of an aqueous solution or dispersion containing at least 55% by weight of said pre-reacted binder composition.
[0013]
13. METHOD according to any one of claims 1 to 12, characterized in that said pre-reacted binder composition comprises a prepolymer having a molecular weight in the range of 80 to 500 kDa in an amount of 0.2% by weight or more, based on the total weight of the pre-reacted binder composition.
[0014]
METHOD according to claim 13, characterized in that said pre-reacted binder composition comprises a prepolymer having a molecular weight in the range of 80 to 500 kDa in an amount of 0.5% by weight or more based on in the total weight of the pre-reacted binder composition.
[0015]
15. METHOD according to claim 13, characterized in that said pre-reacted binder composition comprises a prepolymer having a molecular weight in the range of 80 to 500 kDa in an amount of 0.75% by weight or more based on in the total weight of the pre-reacted binder composition.
[0016]
16. METHOD according to any one of claims 1 to 15, characterized in that said pre-reacted binder composition comprises a prepolymer having a molecular weight in the range of 10 to 80 kDa in an amount of 1% by weight or more , based on the total weight of the pre-reacted binder composition.
[0017]
17. METHOD according to claim 16, characterized in that said pre-reacted binder composition comprises a prepolymer having a molecular weight in the range of 10 to 80 kDa in an amount of 5% by weight or more based on weight total pre-reacted binder composition.
[0018]
18. METHOD according to claim 16, characterized in that said pre-reacted binder composition comprises a prepolymer having a molecular weight in the range of 10 to 80 kDa in an amount of 10% by weight or more based on weight total pre-reacted binder composition.
[0019]
19. METHOD according to claim 16, characterized in that said pre-reacted binder composition comprises a prepolymer having a molecular weight in the range of 10 to 80 kDa in an amount of 30% by weight or more based on weight total pre-reacted binder composition.
[0020]
20. METHOD according to claim 16, characterized in that said pre-reacted binder composition comprises a prepolymer having a molecular weight in the range of 10 to 80 kDa in an amount of 50% by weight or more based on weight total pre-reacted binder composition.
[0021]
21. METHOD according to any one of claims 1 to 20, characterized in that said binder composition comprises a compound having a molecular weight of 10 kDa or less, and which is different from (a) reducing sugar and (b) component containing nitrogen.
[0022]
22. METHOD according to claim 21, characterized in that the low molecular weight compound comprises a compound selected from the group consisting of a glycoaldehyde, glyceraldehyde, 2-oxopropanal, acetol, dihydroxyacetone, acetoin, butanedione, ethanane, glycosone, 1 -deoxyhexosulose, 3-deoxyhexosulose, 3-deoxypentosulose, 1,4-dideoxyhexosulose, glyoxal, methylglioxal, diacetyl and 5- (hydroxymethyl) furfural.
[0023]
23. METHOD according to any one of claims 1 to 22, characterized in that the reducing sugar of the pre-reacted binder composition is selected from the group consisting of monosaccharides, disaccharides and polysaccharides or a mixture thereof.
[0024]
24. METHOD according to claim 23, characterized in that the reducing sugar of the pre-reacted binder composition is selected from the group consisting of ribose, arabinose, xylose, lixose, glucose (dextrose), mannose, galactose, alose, altrose, thalose, sugar, idose, fructose, psychosis, sorbose, dihydroxyacetone, tagatose, or a mixture of these.
[0025]
25. METHOD according to any one of claims 1 to 24, characterized in that the nitrogen-containing component of the pre-reacted binder composition is hexamethylenediamine.
[0026]
26. METHOD according to any one of claims 1 to 25, characterized in that the set of material comprises the material selected from the group consisting of mineral fibers, slag wool fibers, rock wool fibers, glass fibers, aramid fibers, ceramic fibers, metallic fibers, carbon fibers, polyamide fibers, polyester fibers, rayon fibers, cellulose fibers, coal, sand, wood agglomerate, sawdust, wood pulp, milled wood, wood chips wood, wood strips, wood layers, jute, linen, hemp, wood veneers, coverings, wood coverings, particles and woven or non-woven materials.
[0027]
27. METHOD according to any one of claims 1 to 26, characterized in that an aqueous solution containing 70% by weight of said pre-reacted binder composition has a viscosity at 20 ° C of a maximum of 2000 cP.
[0028]
28. METHOD according to any one of claims 1 to 27, characterized in that the viscosity of an aqueous solution containing 70% by weight of said pre-reacted binder composition does not increase by more than 500 cP, when left to stand at 20 ° C. ° C for 12 hours.
[0029]
29. METHOD according to any one of claims 1 to 28, characterized by the total amount of reducing sugar (a) and the nitrogen-containing component (b) in the starting materials to prepare the pre-reacted binder composition with respect to the total weight of the binder composition before the pre-reaction is at least 40% by weight.
[0030]
30. METHOD according to claim 29, characterized by the total amount of reducing sugar (a) and the nitrogen-containing component (b) in the starting materials with respect to the total weight of the binder composition before the pre-reaction is at least minus 60% by weight.
[0031]
31. METHOD according to claim 29, characterized by the total amount of reducing sugar (a) and the nitrogen-containing component (b) in the starting materials with respect to the total weight of the binder composition before the pre-reaction is at least minus 80% by weight.
[0032]
32. METHOD according to claim 29, characterized by the total amount of reducing sugar (a) and the nitrogen-containing component (b) in the starting materials, with respect to the total weight of the binder composition before the pre-reaction is at least 95% by weight.
[0033]
33. METHOD according to any one of claims 1 to 32, characterized by the total quantity of the reducing sugar reaction product (s) (a), and the nitrogen-containing component (b) in relation to the total weight of the pre-reaction binder composition is at least 20% by weight.
[0034]
34. METHOD according to claim 33, characterized by the total amount of the reducing sugar reaction product (s) (a), and the nitrogen-containing component (b) in relation to the total weight of the pre-reacted binder composition being at least 40% by weight.
[0035]
35. METHOD according to claim 33, characterized by the total amount of the reducing sugar reaction product (s) (a), and the nitrogen-containing component (b) in relation to the total weight of the pre binder composition -react to be at least 60% by weight.
[0036]
36. METHOD according to claim 33, characterized by the total amount of the reducing sugar reaction product (s) (a), and the nitrogen-containing component (b) in relation to the total weight of the pre binder composition -react to be at least 80% by weight.
[0037]
37. METHOD according to claim 33, characterized by the total amount of the reducing sugar reaction product (s) (a), and the nitrogen-containing component (b) in relation to the total weight of the pre binder composition -react to be at least 95% by weight.
[0038]
38. FIBER OR PRODUCT CONTAINING PARTICLES, characterized by being obtained by the method as defined in any one of claims 1 to 37.

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BR112014024669B1|2020-11-24|COMPOSITION OF WATER-SOLUBLE PRE-REACTIVE BINDER; METHOD OF MANUFACTURING THE COMPOSITION OF PRE-REAGED BINDER; USE OF A COMPOSITION OF WATER SOLUBLE PRE-REACTIVE BINDER; METHOD OF MANUFACTURING A MATERIAL SET CONNECTED BY A POLYMERIC BINDER; BINDING SOLUTION OR DISPERSION; AND FIBER OR A PRODUCT CONTAINING PARTICLES

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MX2014012028A|2015-07-06|

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US10287462B2|2019-05-14|

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US20150053114A1|2015-02-26|

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WO2013150123A1|2013-10-10|

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KR102176816B1|2020-11-11|

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EP3409683A1|2018-12-05|

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US20180002577A1|2018-01-04|

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AU2013244901A1|2014-11-06|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-05-19| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-06-30| B06J| Correction of requirement [chapter 6.10 patent gazette]|Free format text: REFERENTE A RPI 2576 DE 19/05/2020 |

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2020-10-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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GB1206193.3|2012-04-05|

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GBGB1206193.3A|GB201206193D0|2012-04-05|2012-04-05|Binders and associated products|

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PCT/EP2013/057151|WO2013150123A1|2012-04-05|2013-04-04|Binders and associated products|

---