method of making a collection of matter bound with a polymeric, thermoset, cured binder

专利摘要:
“METHOD OF MANUFACTURING A COLLECTION OF MATERIAL CONNECTED WITH A POLYMERIC, THERMORRIGID, CURED BINDING” A binder comprising the products of a carbohydrate and polyamine reagent is disclosed. The binder is useful for consolidating freely assembled material, such as fibers. Uncured fibrous products that comprise fibers in contact with a carbohydrate reagent and a polyamine are also disclosed. The binder composition can be cured to produce a fibrous product comprising fibers bound by a crosslinking polymer. In addition, methods are disclosed for bonding fibers with the carbohydrate reagent and a polyamine-based binder.
公开号:BR112012028525B1
申请号:R112012028525-4
申请日:2011-05-07
公开日:2020-12-08
发明作者:Charles Appley；Carl Hampson；Gert Mueller；Bénédicte Pacorel
申请人:Knauf Insulation；
IPC主号:

专利说明:

CROSS REFERENCE FOR RELATED ORDERS
This application claims the benefit of provisional patent application US 61 / 332,458, filed on May 7, 2010, which is incorporated herein by reference. TECHNICAL FIELD
This disclosure refers to a formulation of binder and materials made with it that comprises a binder based on carbohydrate and a method for preparing it. In particular, a binder comprising the reaction products of a carbohydrate reagent and a polyamine and materials made from it is described. FUNDAMENTALS
Binders are useful in the manufacture of articles because they are able to consolidate the material either not or freely assembled. For example, binders allow two or more surfaces to be joined. In particular, binders can be used to produce products that comprise 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 aldehyde-phenol, aldehyde-resorcinol, phenol / aldehyde / urea, melamine / phenol / aldehyde, and the like, are used for bonding fibers, textiles, plastics, rubbers, and many other materials.
The mineral wool and fiber board industries have historically used a formaldehyde phenol binder to bind fibers. Phenol formaldehyde type binders provide adequate properties for the final products, however, environmental considerations have motivated the development of alternative binders. One such binder alternative is a carbohydrate based on a binder derived from the reaction of a carbohydrate and a multiprotic acid, for example, published US patent application No. 2007/0027283 and PCT Application Publication W02009 / 019235. Another alternative is the binder for reaction esterification products of a polycarboxylic acid and a polyol, for example, published patent application No. 2005/0202224. Because these binders do not use formaldehyde as a reagent, they have been referred to collectively as formaldehyde-free binders.
One area of current development is to find a replacement for formaldehyde-type phenol binders across the entire product range in the construction and automotive sector (eg fiberglass insulation, particle boards, office panels, and insulation acoustic sound). In particular, the previously developed formaldehyde binders may not have all the desired properties for products in this sector. For example, binders based on acrylic acid and poly (vinyl alcohol) have shown promising performance characteristics. However, these are relatively more expensive than formaldehyde phenol binders, are essentially derived from petroleum-based resources, and have a tendency to show lower reaction rates compared to formaldehyde-based binder compositions ( requiring extended cure times or increased cure temperatures). Carbohydrate-based binder compositions are made from relatively inexpensive precursors and are derived mainly from renewable resources; however, these binders may also require reaction conditions for curing that are substantially different from the conditions under which the traditional phenol formaldehyde binder system cured. As such, easy replacement of phenol formaldehyde type binders with an existing alternative has not been easily attainable. SUMMARY
According to the present disclosure, a carbohydrate-based binder is described. The binder composition has properties that make it useful for a variety of applications, in particular, the binder can be used to bind freely assembled matter, such as fibers.
In illustrative embodiments, the present disclosure relates to a binder that comprises a polymeric product of a carbohydrate reagent and a polyamine. In one embodiment, the carbohydrate reagent is a polysaccharide. In one embodiment, the carbohydrate reagent is a monosaccharide or a disaccharide. In another embodiment, the carbohydrate is a monosaccharide in its aldose or ketosis form. In another embodiment, the carbohydrate reagent is selected from a group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In another embodiment, the polymeric product is a thermoset polymeric product.
In illustrative embodiments, the polyamine is a primary polyamine. In one embodiment, the polyamine can be a molecule having the formula of H2N-Q-NH2, where Q is an alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl radical, each of which can be optionally substituted. In one embodiment, Q represents an alkyl group selected from the group consisting of C2-C24. In another embodiment, Q is an alkyl selected from a group selected from a group consisting of C2 ~ C8. In another embodiment, Q is an alkyl selected from the group consisting of C3-C7. In yet another embodiment, Q represents an alkyl group Ce. In one embodiment, Q is selected from the group consisting of a cyclohexyl, cyclopentyl or cyclobutyl. In another embodiment, Q is benzyl.
In illustrative embodiments, the polyamine is selected from the group consisting of a diamine, triamine, tetraamine, and pentamine. In one embodiment, the polyamine is a diamine selected from a group consisting of 1,6-diamino-hexane and 1,5-diamino-2-methylpentane. In one embodiment, the diamine is 1,6-diaminohexane. In one embodiment, the polyamine is a triamine selected from the group consisting of diethylenetriamine, 1-piperazineethanamine, and bis (hexamethylene) triamine. In another embodiment, the polyamine is a tetramine such as triethylenetetramine. In another embodiment, the polyamine is a pentamine, as well as tetraethylenepentamine.
In illustrative embodiments, the primary polyamine is a polyether polyamine. In one embodiment, the polyether polyamine is a diamine or a triamine.
In illustrative embodiments, the weight ratio of the carbohydrate reagent to the polyamine is in the range of about 1: 1 to about 30: 1. In another embodiment, the weight ratio of the carbohydrate reagent to the polyamine is in the range of about 2: 1 to about 10: 1. In another embodiment, an aqueous extract of the polymeric product has a pH in the range of about 5 to about 9. In another embodiment, an aqueous extract of the polymeric product is essentially colorless. In yet another embodiment, the polymeric product is free of phenol and / or free of formaldehyde. In another embodiment, an aqueous extract of the polymeric product is capable of reducing Benedict's reagent. In another embodiment, the polymeric product absorbs light between 400 and 500 nm, for example, at 420 nm.
In an illustrative embodiment, a method of making a set of matter bound with a polymeric binder comprises preparing a solution containing the reagents for the production of the polymeric binder and a solvent, wherein the reagents include a carbohydrate reagent and a polyamine; discard the solution for the whole matter; volatilizing the solvent to form an uncured product, and subjecting the uncured product to conditions that cause the carbohydrate reagent and the polyamine to polymerize to form the polymeric binder. In one embodiment, the material assembly comprises fibers selected from a group consisting of mineral fibers (slag wool fibers, rock wool fibers or glass fibers), aramid fibers, ceramic fibers, metal fibers, fibers carbon fibers, polyimide fibers, polyester fibers, rayon fibers and cellulosic fibers. In another embodiment, the set of matter comprises particulates, such as coal or sand. In another embodiment, the whole of the material is made of glass fibers. In yet another embodiment, the glass fibers are present in the range of about 70% to about 99% by weight. In another embodiment, the material as a whole comprises cellulosic fibers. For example, cellulosic fibers can be wood shavings, sawdust, wood pulp, milled wood. In yet another embodiment, cellulosic fibers can be other natural fibers, such as jute, linen, hemp, and straw.
In illustrative embodiments, the method of producing a set of matter bound with a polymeric binder further includes preparing a solution by adding an amount of a carbohydrate reagent and an amount of a polyamine, so that the ratio in weight is in the range of about 2: 1 to about 10: 1, respectively. In one embodiment, preparation of the solution includes adding the carbohydrate reagent and the polyamine to an aqueous solution. In another embodiment, preparation of the solution includes adjusting the pH of the solution to within the range of about 8 to about 13, for example, in the range of about 8 to about 12.
In illustrative embodiments, the present disclosure relates to a composition comprising a set of matter and a binder, the binder comprises the polymeric products of a reaction between a carbohydrate reagent and a polyamine, the polymeric products being substantially insoluble in water. In one embodiment, the whole of the material includes mineral fibers (slag wool fibers, rock wool fibers or glass fibers), aramid fibers, ceramic fibers, metallic fibers, carbon fibers, polyimide fibers, polyester, rayon fibers and cellulosic fibers. For example, cellulosic fibers include wood chips, sawdust, wood pulp, and / or milled wood. In one embodiment, the carbohydrate reagent is selected from a group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In another embodiment, the polyamine is selected from the group consisting of a diamine, triamine, tetramine, and pentamine. In one embodiment, the polyamine is H2N-Q-NH2, where Q is an alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl group, each of which is optionally substituted. In another embodiment, the composition further comprises a compound containing silicon. In one embodiment, the silicon-containing compound is a functionalized silyl ether or a functionalized alkyl silyl ether, such as, for example, an amino-functionalized alkyl silyl ether. For example, in one embodiment, the silicon-containing compound can be gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyl-trimethoxysilane, or aminoethylaminopropyltrimethoxysilane, or a mixture thereof. In another embodiment, the silicon-containing compound can be an aminofunctional oligomeric siloxane. In another embodiment, the composition comprises a corrosion inhibitor selected from the group consisting of dedusting oil, monoammonium phosphate, sodium metasilicate pentahydrate, melamine, tin (II) oxalate, and a methyl- fluid emulsion. hydrogen hydrogen. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a schematic diagram of a Maillard reaction, which culminates in the production of melanoidins. Fig. 2 shows a schematic of a representative rearrangement of Amadori. Fig. 3 shows the curing temperature profile (Y axis in ° C) of the center of a glass fiber mat sample for different binders during a heat molding cycle (X axis in minutes of mold time), using a mold press with a controlled printing plate temperature at 204 ° C. Binder 1 (♦) is a formaldehyde phenol binder 1 (Comparative Example 2), Binder 2 (■) is a carbohydrate - inorganic acid binder (Comparative Example 3), and binder 3 (X) is a dextrose - ammonia binder - hexamethylene diamine (HMDA) (Example 5). DETAILED DESCRIPTION
Although the present invention is susceptible to several modifications and alternative forms, specific embodiments here will be described in detail. It should be understood, however, that there is no intention to limit the invention to the particular forms described, but, on the contrary, the intention is to cover all modifications, equivalences and alternatives falling within the spirit and scope of the invention.
The present disclosure refers to a binder composition having unexpected utility in the consolidation of the material not or freely assembled. The binder composition represents an unexpected advance in the current state of technology in the field of binder compositions. Specifically, the binder provides performance improvements and provides simpler and more advantageous manufacturing methodologies, while maintaining the ecological advantages that are characteristic of a carbohydrate-based binder system.
As used herein, the term binder solution is the solution of chemicals that can be substantially dehydrated to form an uncured binder. As used herein, the binder or binder composition can be cured, uncured or partially cured. The composition of the uncured binder is referred to as an uncured binder composition. An uncured binder is a substantially dehydrated mixture of chemicals that can be cured to form a cured binder. Substantially dehydrated means that the solvent (usually water or a mixture thereof) used to make the binder solution is vaporized as the viscosity of the remaining material (which comprises the binder and solvent reagents) is high enough to form cohesion between the freely assembled matter, thus, the resulting material is uncured binder. In one embodiment, the solvent is less than 65% of the total weight of the remaining material. In another embodiment, a substantially dehydrated binder has a moisture content between about 5% and about 65% water by weight of total binder. In another embodiment, the solvent may be less than 50% of the total weight of the remaining material. In yet another embodiment, the solvent can be less than 35% of the total weight of the remaining material. In another embodiment, a substantially dehydrated binder has between about 10% and about 35% water by weight of total binder. In another embodiment, the solvent may comprise less than about 20% of the total weight of the remaining material.
In illustrative embodiments, an uncured binder may be the colorless, white, whitish, ocher or yellow to brownish adhesive substance which is at least partially soluble in water. As used herein, the term cured binder describes the polymeric curing product of the uncured binder composition. The cured binder can have a characteristic brown to black color. Although described as brown or black, another feature is that the binder has a tendency to absorb light over a wide spectrum of wavelengths. In particular, it can be absorbance greater than about 420 nm. As the polymer is extensively cross-linked, the cured binder is substantially insoluble. For example, the binder is predominantly insoluble in water. As described herein, the uncured binder provides sufficient binding capacity to consolidate the fibers, however, the cured binder confers robust physical properties and durability, long and robust and commonly associated with crosslinked polymers.
In illustrative embodiments, the binder reagents described herein are soluble in water and the binder solution is a solution of the binder reagents in an aqueous solution. In one embodiment, a surfactant is included in the aqueous solution to increase the solubility or dispersibility of one or more binding agents or additives. For example, a surfactant can be added to the aqueous binder solution to increase the dispersibility of a particulate additive. In one embodiment, a surfactant is used to create an emulsion with a non-polar additive or binding agent. In another embodiment, the binder solution comprises between about 0.01% to about 5% of surfactant by weight, based on the weight of the binder solution.
In illustrative embodiments, the binder solutions described herein can be applied to mineral fibers (for example, sprayed on the mat or sprayed on fibers entering the forming region), during the production of mineral fiber insulation products. Once the binder solution is in contact with the mineral fibers, the residual heat of the mineral fibers (note that the glass fibers, for example, are made from molten glass and thus contain the residual heat) and the Airflow through and / or around the product will cause some of the water to evaporate from the binder solution. Removing the water leaves the remaining components of the binder on the fibers as a coating for the viscous or semi-viscous mixture with a high solids content. This high solids viscous or semi-viscous mixture coating works as a binder. At this point, the blanket has not yet healed. In other words, the uncured binder works to bind the mineral fibers in the blanket.
In addition, it should be understood that the uncured binders described above can be cured. For example, the process of making a cured insulation product may include a subsequent step, in which heat is applied in order to cause a chemical reaction in the uncured binder composition. For example, in the case of the manufacture of fiberglass insulation products or other mineral fiber insulating materials, after the binder solution has been applied to the fibers and dehydrated, the uncured insulation product can be transferred to a curing oven. . In the curing oven the uncured insulation product is heated (for example, from about 300 ° F to about 600 ° F [from about 150 ° C to about 320 ° C]), causing the binder to cure . Cured binder is a water resistant, formaldehyde-free binder that binds the fibers of the insulation product together. Note that drying and thermal curing can occur either sequentially, simultaneously, contemporaneously, or concurrently.
In illustrative embodiments, an uncured fiber product comprises about 3% to about 40% dry binder solids (total uncured solids content). In one embodiment, the uncured fiber product comprises about 5% to about 25% dry binder solids. In another embodiment, the uncured fiber product comprises about 50% to about 97% fibers by weight.
As mentioned here in relation to a mineral fiber binder, a cured binder is the curing product of binding agents. The term cured indicates that the binder has been exposed to conditions in order to initiate a chemical change. Examples of such chemical modifications include, but are not limited to, (i) covalent bonding, (ii) hydrogen bonding of binder components, and (iii) chemically crosslinking the polymers and / or oligomers in the binder. These changes can increase the binder's durability and solvent resistance when compared to an uncured binder. Curing of a binder can result in the formation of a thermoset material. In addition, a cured binder can result in increased adhesion between the material in a set compared to an uncured binder. Curing can be initiated through, for example, heat, microwave radiation, and / or conditions that initiate one or more of the aforementioned chemical modifications. While not limited to a particular theory, the cure can include the reaction of carbohydrate and polyamine to form melanoidins.
In a situation where the chemical modification in the binders results in the release of water, for example, polymerization and crosslinking, a cure can be determined by the amount of water released above what could occur from drying alone. The techniques used to measure the amount of water released during drying, as compared to when a binder is cured, are well known in the art.
One aspect of the present disclosure is that the cured binder composition comprises a nitrogenous polymer. The nitrogenous polymer is brown to black in color. While not limited to a particular theory, the cured binder composition comprises melanoidins. Melanoidins can be identified as brown, high molecular weight, complex, and polymers containing furan ring and containing nitrogen. High molecular weight, as used herein, includes those polymers that have a molecular weight greater than 100,000 Daltons. Being comprised of highly cross-linked polymeric chains, the molecular weight of the melanoidins described here approaches infinity. Therefore, the molecular weight of a melanoidin can be a function of the mass and physical dimensions of the polymer being analyzed. For example, a unit sample of melanoidins with a mass of 3 grams can be assumed to comprise a single polymer molecule, due to extensive cross-linking. Therefore, the molecular weight of the polymer would be approximately 1.8 x 104 grams per mol (being the product of the sample mass and Avogadro's number). As used herein, a high molecular weight polymer includes polymers with a molecular weight in the range of about 1 x 105 to about 1 x 1024 grams per mol.
Although not limited to a particular theory, it is known that melanoidins vary in structure according to reagents and preparation conditions. It is also known that melanoidins have a carbon to nitrogen ratio, which increases with temperature and heating time. In addition, melanoidins have a saturated, unsaturated and aromatic character. For melanoidins, the degree of unsaturation and aromaticity increases with temperature (cure temperature) and heating time (cure time). Melanoidins also contain the C-1 of those sugars incorporated as reactants in a variety of structures within the melanoidin. Melanoidins may also contain carbonyl, carboxyl, amide, amine, pyrrole, indole, azomethine, ester, anhydride, methyl ether and / or hydroxyl groups. Depending on the complexity of the structure, infrared spectroscopy can be useful in identifying one or more of these functional groups. Although described here as a melanoidin-like polymer, one skilled in the art will appreciate that the binder can also be classified according to the existence of a particular bond present, such as a polyester, polyether, polyamide, etc.
Another way in which the binder is characterized is by analyzing the gaseous compounds produced during the pyrolysis of the cured binder. Gas pyrolysis of a cured binder within the scope of the present disclosure can yield about 0.5 to about 15% (per area of the relative peak) of one or more of the following compounds: 2-cyclopenten-l-one, 2, 5-dimethyl-furan, furan, 3-methyl-2,5-furanedione, phenol, 2,3-dimethyl-2-cyclopenten-1-one, 2-methyl phenol, 4-methyl-phenol, 2,4-dimethyl phenol, dimethyl phthalate, octadecanoic acid, or erucylamide. Fingerprinting in the pyrolysis of gas chromatography mass spectrometry (Py GC-MS) performed at 770 ° C from a binder sample prepared using hexamethylenediamine as the polyamine component shows pyridine and a number of components that are pyrrole or pyridine (a methyl pyridine a methyl pyrrole, dimethyl pyridines, a dimethyl pyrrole, an ethyl methyl pyrrole, and another pyrrole related to components containing N). Another way in which the binder can be identified is whether a solution containing the binder (or a solution of the extract) is capable of reducing Benedict's reagent. In one embodiment, a solution in contact with the binder or an aqueous extract of it reduces Benedict's reagent.
One aspect of the present disclosure is that the binders described here are environmentally friendly. Parallel to the advancement of government regulation, the present disclosure describes a binder that can be made free of formaldehyde. In addition, the chemistry described here is essentially free of formaldehyde and phenol. In this sense, neither formaldehyde nor phenol is used as a reagent within the scope of this disclosure. Although both can be added to obtain a binder with potentially useful properties, one aspect of the present disclosure is a binder that can be made free of both of these reagents. In another aspect, the present binder composition can be manufactured without the use of volatile reagents. In one embodiment, the primary amine and carbohydrate are both non-volatile reagents. As used herein, a volatile reagent is one that has a vapor pressure greater than 10 kPa at 20 ° C. Likewise, as used here, a non-volatile reagent has a vapor pressure less than about 10 kPa at 20 ° C. Specifically and as an example, the present binder can be manufactured without the addition of ammonia or an ammonia releasing compound. In one embodiment, the polyamine has a vapor pressure of less than about 0.5 kPa at 60 ° C.
Another environmental aspect of the present disclosure is that the primary binder reagents are carbohydrates. Carbohydrates are considered a renewable resource. However, the current state of the art mainly uses petroleum-based reagents for the manufacture of binder compositions. In another aspect, the binder is made by means of chemical reactions that can occur at lower temperatures than the comparable systems described in the prior art. As such, curing furnaces and manufacturing equipment can be operated at lower temperatures, saving valuable resources. Alternatively and in a related manner, the described binder described here cures more quickly than comparable binders currently used when subjected to similar curing temperatures. Therefore, by any of the approaches, an aspect of the present disclosure is that the carbon footprint of a product formed using the presently disclosed binder can be substantially reduced compared to a similar binder made according to the current state of the art. , for example, a product based on phenol formaldehyde.
In addition to the environmental benefits, the present composition of binder and materials made with it can be made with performance characteristics equivalent to or superior to those of comparable binder systems, for example, phenol formaldehyde binders. In one aspect, a binder according to the present disclosure provides articles made with the same tensile strength sufficient to permit the die cut, fabrication, lamination, and installation in OEM applications. In one aspect, a binder according to the present disclosure has sustained (weather) water comparable to that of a phenol formaldehyde binder. Other performance characteristics that may be relevant for a given application include product emissions, density, loss of ignition, recovery of thickness, dust, tensile strength, strength, durability, partition resistance, bond strength, water absorption , hot surface performance, steel corrosivity, flexural stiffness, reinforcement-stiffness, compressive strength, conditioned compression strength, compression module, conditioned compression module, and development of combustion smoke. One aspect of the present disclosure is that the cured binder extract is essentially pH neutral, for example, between a pH of 6 and 8. Another aspect of the present disclosure is that the present binder allows the manufacture of products with performance characteristics comparable to the phenol formaldehyde binder compositions.
By way of illustration, in one embodiment, a binder according to the present disclosure has the advantage of producing essentially colorless aqueous extracts. This feature of the present disclosure makes the binder desirable in applications such as ceiling tiles, furniture, or office panels, where the finished product can come in contact with water. A cured article made with the present binder shows excellent resistance to discoloration or bleeding after coming in contact with moisture or water. In addition, in such an embodiment, the water that contacts the binder does not leave a residual color in other articles or parts that may come in subsequent contact to contact the binder. For example, in one embodiment, the binder can be used to bond glass fibers in an office panel application. Covering the bonded fiberglass composition can be a light-colored fabric. Advantageously, in one embodiment, the water in contact with the fiberglass composition does not leave a colored residue on the fabric after the office panel has dried.
In addition to the performance characteristics, the manufacturing processes and methods involving the currently disclosed binder have a number of unexpected advantages over previously described binders. In one aspect, as previously described with respect to environmental benefits, the present binder can be manufactured without the use of highly volatile reagents.
Thus, manufacturing emission controls are under a reduced load. In addition, the efficiency of the reaction is higher because the loss of reagent due to vaporization is reduced. Therefore, an aspect of the present disclosure is that the compounds used herein in this document are substantially non-volatile, thus, steps to be taken to reduce undesirable emissions are reduced.
According to another aspect, the reactants that react to form a binder are slow enough to react so that a one-step / pot binder system can be used. According to this aspect, the reactive compounds are slow enough to react that they can be added to a single reagent solution and stored for a reasonable period of time during which they can be applied to a product with a delivery system. This is in contrast to binder systems that react at low temperatures, resulting in insoluble reaction products within binder solution delivery systems. As used herein, a reasonable amount of time for storage without substantial polymer precipitation (> 5%) is two weeks.
Another aspect of the present disclosure is that, although the binding agent is sufficiently non-reactive under ambient temperature conditions to facilitate a pot approach, which is sufficiently reactive at elevated temperatures to cure at very low temperatures and / or very short residence time. In one aspect, the low curing temperature reduces the risk of an insulation product subjected to flameless combustion and / or making fires in line. As used here, very low temperatures are characterized as less than or equal to about 120 ° C. As used here, the short cure times are less than or equal to about 4 min.
In illustrative embodiments, the binder composition includes an acid or an acid salt to increase the shelf life of the uncured binder or binder solution. Although this acid is not a reagent or a catalyst, it can be included to reduce or inhibit the binder reagents from forming the binder, while the uncured binder or binder solution is kept under storage conditions. For example, a volatile acid or an acidic salt can be included in the solution of uncured binder or binder that slows or inhibits the curing reaction at ambient conditions. However, the acid can be removed by heating the uncured binder or binder solution, so that the acid is volatilized and the pH of the uncured binder or binder solution increases. In one embodiment, the binder composition includes an extendable acid shelf life. In another embodiment, the binder composition includes a shelf-life molar ratio of extensible acid to polyamine from about 1:20 to about 1: 1.
Another aspect of the present disclosure is a binder that has a curing rate, cycle time and curing temperature, which meets or exceeds the cure rates that a comparable type of phenol and formaldehyde binder can present, within the scope of a comparable use. In this regard, the present binder can be used as a direct substitute for formaldehyde phenol resins in applications without modification to the equipment. In addition, the present binder allows modification of the curing temperature and times, so that both the reaction temperatures and curing times can be reduced. This reduction has the effect of reducing the energy consumption of the total process and reduces the environmental impact of manufacturing the product. In addition, lower curing temperatures have the additional effect of increasing the safety of the manufacturing process. Another effect of low curing temperatures is a reduction in the risk of combustion without flame or fire.
In the manufacture of insulation products, the heat released by the exothermic hardening reaction can result in the product self-heating. Self-heating is not normally a problem, as heat dissipates from the product. However, if the heat increases the temperature of the product to the point where oxidative processes begin, self-heating can cause significant damage to the product. For example, combustion without flame or oxidation can occur when the temperature of the insulation product exceeds about 425 ° F (210 ° C). At these temperatures, the combustion or exothermic oxidation processes further promote self-heating and the binder can be destroyed. In addition, the temperature may rise to a level at which the fusion or devitrification of the glass fibers is possible. Not only does this damage to the structure and value of the insulation product, it can also create a fire hazard.
Another aspect of the present disclosure is that the binder system is essentially non-corrosive, with or without the addition of corrosion inhibitors. In addition, the binder system does not require the addition of any organic or inorganic acid, or its salts, as an active ingredient or catalyst. Therefore, an aspect of the present binder is that it can be made essentially acid free. In addition, the binder can be manufactured entirely under alkaline conditions. As used herein, the term acid includes compounds that are characterizable mainly due to their acidic character such inorganic and multiprotic organic acids (e.g., sulfuric acid and citric acid). This reduces wear and maintenance requirements on manufacturing equipment and improves worker safety.
In illustrative embodiments, a binder comprises a polymeric product of a carbohydrate reagent and a polyamine. As used herein, the term carbohydrate reagent refers to a monosaccharide, a disaccharide, a polysaccharide, or a reaction product thereof. In one embodiment, the carbohydrate reagent can be a reducing sugar. As used here, reducing sugar indicates one or more sugars that contain aldehyde groups, or that can isomerise, that is, tautomerize, to contain aldehyde groups, which groups can be oxidized with, for example, Cu + 2 to obtain acids carboxylics. It is also appreciated that any such carbohydrate reagent can be optionally substituted, for example, with hydroxy, halo, alkyl, alkoxy and the like. It is further appreciated that in any such carbohydrate reagent, one or more chiral centers are present, and that both possible optical isomers at each chiral center are contemplated to be included in the invention described herein. Furthermore, it is also to be understood that various mixtures, including racemic mixtures or other diastereomeric mixtures of the various optical isomers of any such carbohydrate reagent, as well as the various geometric isomers thereof, can be used in one or more embodiments here described. Although non-reducing sugars, for example, sucrose, may not be preferable, they may nevertheless be useful within the scope of the present disclosure by in-situ conversion to a reducing sugar (ie, the conversion of sucrose to inverted sugar is a method known in the art). 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 a similar reactivity with the polyamine in order to form reaction products similar to those of a monosaccharide, a disaccharide or a polysaccharide, with a polyamine, the carbohydrate reaction product is within the scope of the term carbohydrate reagent.
In one aspect, any carbohydrate reagent must be sufficiently non-volatile to maximize its ability to remain available for reaction with the polyamine. The carbohydrate reagent can be a monosaccharide in the form of aldose or ketosis, including a triosis, a tetrose, a pentose, a hexose or a heptose, or a polysaccharide, or combinations thereof. For example, when a triosis serves as a carbohydrate reagent, 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 a carbohydrate reagent, 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 reagent, 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 a carbohydrate reagent, or is used in combination with other reducing sugars and / or a polysaccharide, aldohexose sugars, such as glucose (eg, dextrose), mannose, galactose, alose, altrose, talose, glucose, and idose, and ketohexose sugars, such as fructose, psychosis, sorbose and tagatose, can be used. When a heptosis serves as a carbohydrate reagent, or is used in combination with other reducing sugars and / or a possacaride, a ketoheptose sugar such as sedoheptulose can be used. Other stereoisomers of such carbohydrate reagents that are known not to occur naturally are also contemplated to be useful in the preparation of binder compositions as described herein. In one embodiment, the carbohydrate reagent is fructose-rich corn syrup.
In illustrative embodiments, the carbohydrate reagent is a possible. In one embodiment, the carbohydrate reagent is a possacaryide with a low degree of polymerization. In one embodiment, the possacaride is molasses, starch, cellulose hydrolysates, or mixtures thereof. In one embodiment, the carbohydrate reagent is a starch hydrolyzate, a maltodextrin or a mixture thereof. Although carbohydrates of a higher degree of polymerization may not be preferable, they may at least be useful within the scope of the present disclosure by depolymerization in situ (i.e., depolymerization through ammonization at elevated temperatures is a method known in the art).
In addition, the carbohydrate reagent can be used in combination with a polyhydroxyl non-carbohydrate reagent. Examples of non-carbohydrate polyhydroxy reagents that can be used in combination with the carbohydrate reagent include, but are not limited to, trimethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, fully hydrolyzed polyvinyl acetate, and mixtures of these. In one aspect, the polyhydroxyl non-carbohydrate reagent is sufficiently non-volatile to maximize its ability to remain available for reaction with a monomeric or polymeric polyamine. It is appreciated that the hydrophobicity of the polyhydroxyl non-carbohydrate reagent can be a factor in determining the physical properties of a binder prepared as described herein.
As used herein, a polyamine is an organic compound that has two or more amino groups. As used herein, a primary polyamine is an organic compound with two or more primary amine groups (-NH2). Within the scope of the term primary polyamine are compounds that can be modified in situ or isomerized to generate a compound with two or more primary amine groups (-NH2). In illustrative embodiments, the polyamine is a primary polyamine. In one embodiment, the primary polyamine can be a molecule having the formula H2N-Q-NH2, where Q is an alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl radical, each of which can be optionally substituted. In one embodiment, Q represents an alkyl group selected from the group consisting of C2-C24. In another embodiment, Q represents an alkyl group selected from the group consisting of C2-Cs. In another embodiment, Q represents an alkyl group selected from the group consisting of C3-C7. In yet another embodiment, Q represents a Cg alkyl group. In one embodiment, Q is selected from the group consisting of a cyclohexyl, cyclopentyl or cyclobutyl. In another embodiment, Q represents benzyl.
As used herein, the term "alkyl" includes a chain of carbon atoms, which is optionally branched. As used herein, the term "alkenyl" and "alkynyl" includes a carbon atom chain, which is optionally branched, and includes at least one double bond or triple bond, respectively. It is to be understood that alkynyl may also include one or more double bonds. It should also be understood that the alkyl group is advantageously of limited length, including C1-C24, C1-C12, C1-C8, C1-C6, and C1-C4. It is further to be understood that alkenyl and / or alkynyl can advantageously be each of limited length, including C2-C24, C2-C12, C2-Cg, C2-C6 and C2-C4. It is appreciated here that shorter alkyl, alkenyl and / or alkynyl groups can add less hydrophilicity to the compound, and thus will have different reactivity towards the carbohydrate reagent and the solubility of a binder solution.
As used herein, the term "cycloalkyl" includes a chain of carbon atoms, which is optionally branched, in which at least part of the chain is cyclic. It is to be understood that cycloalkylalkyl is a subset of cycloalkyl. It is to be understood that it can be polycyclic cycloalkyl. Illustrative cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, 2-methylcyclopropyl, cyclopentyl-2-yl, adamantyl, and the like. As used herein, the term "cycloalkenyl" includes a carbon atom chain, which is optionally branched, and includes at least one double bond, where at least part of the chain is cyclic. It is to be understood that the one or more double bonds may have the cyclic cycloalkenyl portion and / or the non-cyclic cycloalkenyl portion. It is to be understood that cycloalkenylalkyl and cycloalkylalkenyl are each subsets of cycloalkenyl. It is to be understood that cycloalkyl can be polycyclic. Illustrative cycloalkenyls include, but are not limited to, cyclopentenyl, cyclohexylethene-2-yl, cycloheptenylpropenyl, and the like. It should also be understood that the cycloalkyl and / or cycloalkenyl chain formation is advantageously of limited length, including C3-C20 C3-C12, C3-CΘ, C3-C6, and C5-C6. Shorter alkyl and / or alkenyl chains forming cycloalkyl and / or cycloalkenyl, respectively, can add less lipophilicity to the compound and thus will behave differently.
As used herein, the term "heteroalkyl" includes a chain of atoms that includes both carbon and at least one heteroatom and is, optionally, branched. Illustrative heteroatoms include nitrogen, oxygen and sulfur. In certain variations, illustrative heteroatoms include, phosphorus and selenium. In one embodiment, a heteroalkyl is a polyether. As used herein, the term "cycloheteroalkyl" including heterocyclyl and heterocyclic, includes a chain of atoms that includes both carbon and at least one heteroatom, such as heteroalkyl, and is optionally branched, where at least part of the chain is cyclical. Illustrative heteroatoms include nitrogen, oxygen and sulfur. In certain variations, illustrative heteroatoms include, phosphorus and selenium. Illustrative cycloheteroalkyl includes, but is not limited to, tetrahydrofuryl, pyrrolidinyl, tetrahydropyranyl, piperidinyl, morpholinyl, piperazinyl, homopiperazinyl, quinuclidinyl, and the like.
The term "optionally substituted", as used herein, includes the replacement of hydrogen atoms with other functional groups in the radical that is optionally substituted. Such other functional groups illustratively include, but are not limited to, amino, hydroxyl, halo, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, nitro, sulfonic acids and their derivatives, carboxylic acids and their derivatives, and similar. By way of illustration, any amino, hydroxyl, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, and / or sulfonic acid is optionally substituted.
In illustrative embodiments, the primary polyamine is a diamine, triamine, tetramine or pentamine. In one embodiment, the polyamine is a triamine selected from a diethylenetriamine, 1-piperazine ethanolamine, or bis (hexamethylene) triamine. In another embodiment, the polyamine is a tetramine, for example triethylenetetramine. In another embodiment, the polyamine is a pentamine, for example tetraethylenepentamine.
One aspect of the primary polyamine is that it can have low steric impedance. For example, 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,12-diaminododecane, 1,4-diaminocyclohexane, 1,4-diaminobenzene, diethylenetriamine , triethylenetetramine, tetraethylenepentamine, 1-piperazineethanolamine, 2-methylpentamethylenediamine, 1,3-pentanediamine, and bis (hexamethylene) triamine, as well as 1,8-diaminooctane have low steric impediment within the scope of this disclosure. One embodiment is 1,6-diaminohexane (hexamethylenediamine). Another embodiment is 1,5-diamino-2-methyl-pentane (2-methyl-pentamethylenediamine). In another embodiment, the primary polyamine is a polyether polyamine. In another embodiment, the polyether polyamine is a diamine or a triamine. In one embodiment, the polyether polyamine is a trifunctional primary amine having an average molecular weight of 440 known as Jeffamine T-403 Polyetheramine (Huntsman Corporation).
In one embodiment, the polyamine can include a polymeric polyamine. For example, polymeric polyamines within the scope of the present disclosure include chitosan, polylysine, polyethyleneimine, poly (N-vinyl-N-methyl-amine), and polyaminostyrene polyvinylamines. In one embodiment, the polyamine comprises a polyvinyl amine. As used herein, the polyvinyl amine can be a homopolymer or a copolymer.
Although not limited to a particular theory, one aspect of the present disclosure is that the primary polyamine and the carbohydrate reagent are Maillard reagents, which react to form a melanoidin product. Fig. 1 shows a schematic diagram of a Maillard reaction, which culminates in the production of melanoidins. In its initial phase, the Maillard reaction involves a carbohydrate reagent, for example, a sugar reducer (note that the carbohydrate reagent may come from a substance capable of producing a reducing sugar under Maillard reaction conditions). it involves condensing the carbohydrate reagent (for example, reducing sugar) with an amine reagent, that is, a compound that has an amino group. In other words, the carbohydrate reagent and the amine reagent are the melanoidin reagents for a Maillard reaction. The condensation of these two components produces an N-substituted glycosylamine. For a more detailed description of the Maillard reaction see, Hodge, J.E. Chemistry of Browning Reactions in Model Systems J. Agric. Food. Chem. 1953, 1, 928-943, the disclosure of which is hereby incorporated by reference. The literature on Maillard's reactions focuses on melanoidins produced from amino acids. The present disclosure can be distinguished from such references, in which not all amino acids are polyamines. Common amino acids that are considered polyamines within the scope of the present disclosure include asparagine, glutamine, histidine, lysine and arginine.
Without being linked to theory, the covalent reaction between the polyamine and the carbohydrate reagent will be described in greater specificity. As described here, the path of the present reaction is different from those taught in the prior art, for the following reasons: (1) the present reaction can occur completely at basic pH, (2) the polyamine is di-functional in its reactivity to the reagent of carbohydrate, (3) polyamine, through its di-functional reactivity or other unrecognized phenomenon, exhibits less activation energy, within the scope of the reaction which results in an unexpected increase in the reaction rate and / or a decrease in temperature in which the reaction takes place.
The first step in the formation of melanoidins from a polyamine and a carbohydrate reagent is the condensation of the carbohydrate reagent and the polyamine. The evidence indicates that the conditions described here are especially suitable for conducting this reaction to completion. First, it is believed that the alkalinity of the binder solution leads to condensation. For example, it has been shown that sugars and amines undergo browning in aqueous solution in proportion to the basic strength of the amines employed or the pH of the solution. N-substituted glycosylamines are believed to remain undissociated in aqueous solution to an appreciable degree. Thus, the irreversible transformations that undissolved molecules undergo must be considered. Although it is known that the condensation reaction is reversible, we have found that this reaction can additionally be brought to an end, according to Le Chatelier's principle by the simultaneous dehydration of the binder solution. As such, it was found that initially a major constituent of the uncured binder composition was N-glycosyl derivatives from the primary polyamines.
Referring again to fig. 1, the second step in converting the binder reagents to melanoidin products is the so-called Amadori rearrangement. A schematic of a representative Amadori rearrangement is shown in fig. 2. With reference to fig. 2, the N-glycosyl derivatives of the primary polyamines are in equilibrium with the cation of a Schiff base. Although this balance favors N-glycosylamines, additional rearrangement of the cation of a Schiff base with the enol or keto form is known to proceed spontaneously. This spontaneous reaction was found to be further facilitated by dehydration, just as the rate was increased in dehydrated samples. One aspect of the present disclosure is that the structure of a primary polyamine specifically accelerates this rearrangement by stabilizing the positive charge that is acquired while the compound is in the form of a Schiff base cation. It is believed that this stabilizing effect has not been discussed in the prior art, or in the literature as to the improved effect of using a primary polyamine has not been previously disclosed.
Therefore, an aspect of the present disclosure is that the primary polyamine is of a type that provides stability to a Schiff base cation during an Amodori rearrangement. In another aspect, the primary polyamine is of a type that provides stability to a cation of a Schiff base during an Amadori rearrangement, while in a substantially dry state.
Another aspect of the present disclosure is that the carbohydrate structure is also believed to influence the kinetics of Amadori's rearrangement. Specifically, it is known that when the C-2 hydroxyl of a crystalline N-substituted glycosylamine was replaced, the compound was slowly transformed during storage to Amadori's rearrangement product. However, if the C-2 hydroxyl group was substituted, then the rearrangement was substantially inhibited. Therefore, an aspect of the present disclosure is that a carbohydrate of the present disclosure is unsubstituted in the C-2 hydroxyl. One aspect of the present disclosure is that the uncured binder composition comprises a mixture of N-glycosylamines, 1-amino-1-deoxy-2-ketoses in their enol and keto form. Referring again to fig. 1, after the formation of the mixture of N-glycosylamines, 1-amino-1-deoxy-2-ketoses in their enol and keto form the mixture will also include a non-negligible concentration of both unreacted primary polyamine and the carbohydrate. From then on, a series of reactions can occur that leads to what can be widely described as melanoidins. Depending on the identity of both the carbohydrate and polymeric polyamine reagent and the reaction conditions (pH, temperature, oxygen levels, humidity, and presence of additives) to one or more of the reaction pathways shown in fig. 1, can be favored. Furthermore, the preferred reaction pathway for a given melanoidin product cannot be classified as any one shown specifically in fig. 1.
In illustrative embodiments, the weight ratio of the carbohydrate reagent to the primary polyamine is in the range of about 1: 1 to about 30: 1. In another embodiment, the weight ratio of the carbohydrate reagent to the primary polyamine is in the range of about 2: 1 to about 10: 1. In yet another embodiment, the weight ratio of the carbohydrate reagent to the primary polyamine is in the range of about 3: 1 to about 6: 1. According to one aspect, the cure rate is a function of the weight ratio of the carbohydrate reagent to the primary polyamine. According to this function, it was established that the ratio decreases, the cure rate increases, thus the cure time is reduced. Therefore, an aspect of the present disclosure is that the curing time is directly related to the weight ratio of the carbohydrate reagent to the polyamine, as long as other parameters are kept equivalent. In another aspect, the curing time of the binder is reduced with the curing time of a comparable phenol formaldehyde binder composition when the weight ratio of the carbohydrate reagent to the primary polyamine is about 6: 1. Accordingly, in one embodiment, a binder according to the present disclosure has a higher cure rate than a comparable phenol formaldehyde binder system when the weight ratio of the carbohydrate reagent to the primary polyamine is in the range of about 2 : 1 to about 6: 1.
Another aspect of the reaction, as described here, is that, initially, the aqueous reagent solution (which can be dehydrated and used as a binder), as described above, has an alkaline pH. One aspect of the present disclosure is that the alkaline binder solution is less corrosive to metals in acidic solution. Therefore, an aspect of the present disclosure, which crosses a substantial barrier for the industry, is that the binder described here has low corrosivity for the manufacturing equipment that can be used for the production of materials that include the present binder because of the alkaline binder composition. A distinguishing feature of the present disclosure in relation to other recently described carbohydrate binder systems (for example, a published US patent application No. 2007/0027283), is that the reaction does not necessarily proceed via an acidic route. Rather, an aspect of the present disclosure is that the uncured binder can have an alkaline pH throughout the course of the chemical reaction that leads to the formation of the cured binder. As such, the uncured binder does not present a risk of corrosion during use and storage. In illustrative embodiments, an aqueous extract of the cured binder has a pH in the range of about 5 to about 9. In addition, an aqueous extract of the polymeric product is essentially colorless.
In illustrative embodiments, a method of making a set of matter bound with a polymeric binder comprises preparing a solution containing the reagents for the production of the polymeric binder and a solvent, wherein the reagents include a carbohydrate reagent and a polyamine; discard the solution on the set of matter; volatilizing the solvent to form an uncured product, and subjecting the uncured product to conditions that cause the carbohydrate and polyamine reagent to polymerize to form the polymeric binder.
In illustrative embodiments, the whole of the material includes insulating fibers. In one embodiment, a fiber insulation product is described that includes insulating fibers and a binder. As used herein, the term "insulating fiber" indicates heat-resistant fibers, suitable for withstanding high temperatures. Examples of such fibers include, but are not limited to, mineral fibers, (glass fibers, slag wool fibers, and rock wool fibers), aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide, certain polyester fibers and rayon fibers. Illustratively, such fibers are substantially unaffected by exposure to temperatures above about 120 ° C. In one embodiment, the fibers are insulating glass fibers. In yet another embodiment, mineral fibers are present in the range of about 70% to about 99% by weight. In illustrative embodiments, the whole of the material includes cellulosic fibers. For example, cellulosic fibers can be wood chips, sawdust, wood pulp, or milled wood. In yet another embodiment, cellulosic fibers can be other natural fibers, such as jute, linen, hemp, and straw. The binder disclosed herein can be used as in place of the binder described in published PCT application WO 2008/089847, which is incorporated herein by reference in its entirety. In one embodiment, a composite wood board comprising wood particles and a binder is disclosed. In another embodiment, the composite wood board is formaldehyde free. In one embodiment, the composite wood board has a range of nominal thickness greater than 6 mm to 13 mm, and has an elastic modulus (MOE) of at least about 1050 N / mm2, a flexural strength (MOR) of at least about 7 N / mm2 and an internal bonding force (IB) of at least 0.20 N / mm2. In another embodiment, the composite wood board has a nominal thickness range greater than 6 mm to 13 mm, and has a flexural strength (MOR) of at least about 12.5 N / mm2 and a strength internal connection (IB) of at least 0.28 N / mm2. In another embodiment, the composite wood board has a nominal thickness range greater than 6 mm to 13 mm, and has an elasticity modulus (MOE) of at least about 1800 N / mm2 a flexural strength (MOR) of at least about 13 N / mm2 and an internal bonding force (IB) of at least 0.40 N / mm2 in another embodiment, the composite wood board has an elasticity modulus (MOE) of at least about 1800 N / MNA In another embodiment, the composite wood board has an elastic modulus (MOE) of at least about 2500 N / mm2. In another embodiment, the composite wood board has a flexural strength (MOR) of at least about 14 N / mm2. In yet another embodiment, the composite wood board has a flexural strength (MOR) of at least about 18 N / mm2. In one embodiment, the composite wood board has an internal bonding strength (IB) of at least 0.28 N / mm2. In yet another embodiment, the composite wood board has an internal bonding strength (IB) of at least 0.4 N / mm2. In yet another embodiment, the composite wood board swells less than or equal to about 12%, as measured by a change in thickness, after 24 hours in water at 20 ° C. In another embodiment, the composite wood board has a water absorption after 24 hours in water at 20 ° C of less than or equal to about 40%.
In illustrative embodiments, the composite wood board is an agglomerate of wood particles, a oriented chip board, or a medium density fiberboard. In one embodiment, the binder comprises between about 8% to about 18% by weight (weight of dry resin for weight of dry wood particles) of the composite wood board. In another embodiment, the composite wood board further comprises a wax. In yet another embodiment, the composite wood board comprises from about 0.1% to about 2% by weight of the composite wood board. In illustrative embodiments, the method of producing a collection of matter bound with a polymeric binder may further include preparing a solution by adding an amount of a carbohydrate reagent and an amount of a primary polyamine as well as a weight ratio is in the range of about 2: 1 to about 10: 1. In one embodiment, the preparation of the solution includes the addition of the carbohydrate reagent and the polyamine of an aqueous solution. In another embodiment, the preparation of the solution includes adjusting the pH of the solution within the range of about 8 to about 12. In yet another embodiment, the method of producing a collection of matter bound with a binder The polymeric product may also comprise the packaging of the uncured product in a packaging material suitable for storage.
In illustrative embodiments, the present disclosure relates to a composition comprising a set of matter and a binder, the binder comprising polymeric products of the reaction between a carbohydrate reagent and a polyamine, the polymeric products that are substantially insoluble in Water. In one embodiment, the whole of the material includes mineral fibers, aramid fibers, ceramic fibers, metallic fibers, carbon fibers, polyimide fibers, polyester fibers, rayon fibers, glass fibers, cellulosic fibers or other particulates. For example, cellulosic fibers may include wood chips, sawdust, wood pulp, and / or milled wood. In one embodiment, the whole of the material includes sand and other particulate inorganic materials. In one embodiment, the material as a whole is made up of coal particles. In one embodiment, the carbohydrate reagent is selected from a group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In one embodiment, the polyamine is selected from any of the polyamines previously described herein. In another embodiment, the polyamine is selected from the group consisting of a diamine, triamine, tetramine, and pentamine. In one embodiment, the polyamine is H2NQ-NH2, where Q represents an alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl group, each of which is optionally substituted. In another embodiment, the composition further comprises a compound containing silicon. In one embodiment, the silicon-containing compound is a functionalized silyl ether or a functionalized silyl ether, such as, for example, a functionalized amino silyl ether. For example, in one embodiment, the silicon-containing compound can be gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, or aminoethylaminopropyltrimethoxysilane, or a mixture thereof. In another embodiment, the silicon-containing compound can be an aminofunctional oligomeric siloxane. In another embodiment, the composition comprises a corrosion inhibitor selected from the group consisting of dedusting oil, monoammonium phosphate, sodium metasilicate pentahydrate, melamine, tin (II) oxalate, and a silicone fluid emulsion. methyl hydrogen.
In other illustrative embodiments, the binder can be disposed on a set of fibers, substantially dehydrated, packaged and stored or sold to third parties. An uncured product sold to the other party for use in manufacturing processes may be referred to as an "uncured product." An uncured product stored for use in manufacturing processes can be referred to as an "uncured plant." When selling or storing this type of product, it is packed in suitable containers or bags.
In illustrative embodiments, a packaged uncured fiber product comprises an uncured binder composition and a set of fibers, wherein (i) the uncured binder composition is in contact with the set of fibers consolidating the set of fibers and (ii) the uncured binder composition in contact with the fiber set is packaged in a suitable packaging material. In one embodiment, the amount of moisture in the uncured binder composition can be in the range of about 1% to about 15% by weight based on the total weight of the product. In yet another embodiment, the suitable packaging material may be able to maintain the amount of moisture in the uncured binder composition within about 20% of the original moisture level for a period of one week at room temperature and at ambient pressure. In one embodiment, the packaged uncured fiber product comprises from about 3% to about 30% by weight of the uncured binder composition based on the weight of the packaged uncured fiber product regardless of the weight of the packaging material. appropriate. In one embodiment, the packaged uncured fiber product comprises from about 60 to about 97% by weight of fibers based on the weight of the packaged uncured fiber insulation product without regard to the weight of the appropriate packaging material.
One aspect of the present disclosure is that the binder described herein is unexpectedly useful in uncured shipping applications and uncured plant applications. Specifically, uncured embedded products and uncured plant products are supplied with an uncured binder, so that curing can take place at a later time and in a later place. In the case of the un-cured vessel, the curing temperature and time are the properties of the product that are of great importance to consumers. Specifically, the curing temperatures must be low enough that the product can be cured using your existing equipment. In addition, the curing time must be short enough so that the cycle time for curing products remains low. Within this industry, manufacturing equipment and acceptable cycle times have been established for uncured products comprising phenol-formaldehyde type resins. Therefore, sufficiently low curing temperatures are the appropriate curing temperatures for curing a type of product comparable to phenol formaldehyde. Likewise, sufficiently short cycle times are the cycle times that would be routine for curing a type of product comparable to phenol formaldehyde. One of skill in the art will appreciate that neither the time nor the curing temperature can be defined as defined quantities because specific applications can have drastically different parameters. However, it is well known that the curing time and curing temperatures of a model system provide sufficiently representative information about the kinetics of the basic chemical curing reaction, so that reliable predictions of binder performance in different applications can be made. .
In illustrative embodiments, the curing time and curing temperature of the binder are equal to or less than a comparable phenol formaldehyde binder composition. In one embodiment, the curing time of the binder is less than the curing time of a composition, comparable phenol formaldehyde binder. In another embodiment, the curing temperature of the binder is less than the curing temperature of a comparable phenol formaldehyde binder composition. As used herein, a comparable phenol formaldehyde binder composition is as described according to US Patent No. 6,638,882, which patent is hereby incorporated by reference in its entirety.
As discussed below, various additives can be incorporated into the binder composition. These additives give the binders of the present invention additional desirable characteristics. For example, the binder can include a silicon-containing coupling agent. Many silicon-containing coupling agents are commercially available from Dow-Corning Corporation, Evonik
Industries, and Momentive Performance Materials. By way of illustration, the silicon-containing coupling agent includes compounds such as silyl ethers and alkyl silyl ethers, each of which can be optionally substituted, such as halogen, alkoxy, amino, and the like. In one variation, the silicon-containing compound is an amino substituted silane, such as gamma-aminopropyltriethoxy silane, (SILQUEST A-1101; Momentive Performance Materials, Corporate Headquarters: 22 Corporate Woods Boulevard, Albany, NY 12211 USA). In another variation, the silicon-containing compound is an amino substituted silane, for example, aminoethylaminopropyltrimethoxy silane (Dow Z-6020, Dow Chemical, Midland, MI; USA). In another variation, the silicon-containing compound is gamma-glycidoxypropyltrimethoxysilane (SILQUEST A-187; Momentive). In yet another variation, the silicon-containing compound is an oligomeric aminofunctional siloxane (HYDROSIL 2627, Evonik Industries, 379 Interpace Pkwy, Parsippany, NJ 07054).
Silicon-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% to about 3 % based on the weight of the solids added to the aqueous solution). In one application, one or more of these silicon-containing compounds can be added to the aqueous binder solution. The binder is then applied to the material to be bonded. After that, the binder can be cured, if desired. These silicone-containing compounds increase the ability of the binder to adhere to the matter the binder is disposed of, 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 the substance (s) not or freely assembled (s).
In another illustrative embodiment, a binder of the present invention can include one or more corrosion inhibitors. These corrosion inhibitors prevent or inhibit the eating or wear of 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 corrosiveness 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. By way of illustration, 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 fluid emulsion of silicone. 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 percent by weight based on the dissolved binder solids. One aspect of the present disclosure is that the need for corrosion inhibiting additives is greatly reduced by the alkalinity of the binder solution and the substantially dehydrated uncured binder. In one embodiment, the binder is free of corrosion inhibitors and the corrosivity of the binder solution is within the acceptable range.
In illustrative embodiments, the binder can further include a non-aqueous moisturizer. The non-aqueous moisturizer can include one or more polyethers. For example, the non-aqueous moisturizer may include a condensed ethylene oxide or propylene oxide having straight and / or branched chain alkyl groups and alkaryl groups. In one embodiment, the non-aqueous moisturizer includes a polyethylene glycol, a polypropylene glycol ether, a thioether, a polyoxyalkylene glycol (for example, Jeffox TP400®), a dipropylene glycol, and / or a polypropylene glycol (for example, Pluriol P425® or Pluriol 2000®). In one embodiment, the non-aqueous moisturizer comprises a polyoxyalkylene glycol or a polypropylene glycol. In another embodiment, the non-aqueous moisturizer includes a compound based on a polyhydroxy compound (for example, a polyhydroxy compound, wholly or partially esterified). In another embodiment, the non-aqueous moisturizer includes a polyhydroxy based on a glycerin, a propylene glycol, an ethylene glycol, a glycerin acetate, a sorbitol, a xylitol or a maltitol.
In another embodiment, the non-aqueous moisturizer includes other compounds that have various hydroxyl groups based on tetrahydrofuran, a caprolactone, and / or an alkylphenoxypoli (ethyleneoxy) ethanols with alkyl groups containing about 7 to about 18 atoms of carbon and having between about 4 to about 240 ethyleneoxy units. For example, the non-aqueous moisturizer may include a heptylphenoxypoli (ethyleneoxy) ethanol and / or a nonylphenoxypoli (ethyleneoxy) ethanol. In another embodiment, the non-aqueous moisturizer includes a polyoxyalkylene derivative of hexitol, such as a sorbitan, sorbide, mannitan, and / or a mannide. In yet another embodiment, the non-aqueous moisturizer can include a partial long-chain fatty acid ester, such as a polyoxyalkylene derivative of sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, and / or sorbitan trioleate.
In illustrative embodiments, the non-aqueous moisturizer includes a condensate of ethylene oxide with a hydrophobic base, the base being formed by condensation of propylene oxide with propylene glycol. In one embodiment, the non-aqueous moisturizer includes a sulfur-containing condensate, such as those prepared by condensing ethylene oxide with a higher alkyl mercaptan (for example, nonyl, dodecyl, tetradecyl mercaptan, or alkylthiophenols having about 6 to about of 15 carbon atoms in the alkyl group). In another embodiment, the non-aqueous moisturizer includes an ethylene oxide derivative of a long-chain carboxylic acid, such as lauric, myristic, palmitic, or oleic acids. In yet another embodiment, the non-aqueous moisturizer includes an ethylene oxide derivative of a long-chain alcohol, such as octyl, decyl, lauryl, or cetyl alcohols. In another embodiment, the non-aqueous moisturizer includes an ethylene oxide / tetrahydrofuran copolymer or an ethylene oxide / propylene oxide copolymer.
The following examples illustrate specific embodiments in greater detail. These examples are provided for illustrative purposes only and should not be considered as limiting the invention or the inventive concept to a particular physical configuration in any way. EXAMPLES Example 1: A solution of 50 g of dextrose (0.278 mol), 50 g of hexamethylenediamine (0.431 mol) dissolved in 566.6 g of deionized water (15% solids solution, pH 11.9) was heated until boiling point of the solution. A brownish water insoluble polymer was observed as a precipitate in the reaction vessel. Example 2: From the solution above 50 g dextrose (0.278 mol), 50 g hexamethylenediamine (0.431 mol) dissolved in 566.6 g deionized water (15% solids solution, pH 11.9), 2 g of the binder solution was applied to a filter pad which is placed in a moisture balance and heated for 15 min at 120 ° C. A brownish water insoluble polymer formed on the filtration layer. An extraction of the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of 6.8. Example 3: A solution of 85 g of dextrose (0.472 mol), 15 g of hexamethylenediamine (0.129 mol) dissolved in 566.6 g of deionized water (15% solids solution, pH 10.8) was prepared. 2 g of the binder solution was applied on a filter pad which is placed in a moisture balance and heated for 15 min at 140 ° C. A brownish water insoluble polymer formed on the filtration layer. An extraction of the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of 6.8. Example 4: A solution of 95 g of dextrose (0.528 mol), 5 g of hexamethylenediamine (0.043 mol) dissolved in 566.6 g of deionized water (15% solids solution) was prepared. 2 g of the binder solution was applied to a filter pad which is placed in a moisture balance and heated for 15 min at 180 ° C. A brownish water insoluble polymer formed on the filtration layer. An extraction of the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of 6.8. Comparative example 1: A solution of 180 g of dextrose (1 mol) dissolved in 1020 g of deionized water (15% solids solution) was prepared. 2 g of the binder solution was applied to a filter pad which is placed in a moisture balance and heated for 15 min at 180 ° C. A water insoluble polymer was not formed on the filter pad. The resulting heat-treated binder was essentially completely soluble in water.
Curing Rate and Curing Time: square fiberglass blankets (13 "x 13"), weighing 44 g (corresponding to 34.5 g / ft2) were impregnated with a binder containing 15% solids. The excess binder is removed by suction under vacuum, and the wet mat is dried for at least 12 hours at 90 ° C in an oven (recirculation).
The dry blanket is cut into four squares of the same size. The squares are stacked on top of each other and at least one thermocouple connected to an engraver (ie oven soak) is placed in the middle of the stack between the 2nd and 3rd layers.
The temperature controlled roller mold press is heated to 400 ° F (204 ° C). The sample prepared with the thermocouple is placed in the middle of the plate, and pressed to a thickness of 5/8 "for a predetermined time (that is, 3.5 min, 4.0 min, 5.0 min, 6, 0 min, 15 min).
Each molded sample was evaluated for the degree of cure through tests of uniformity of surfaces, support in water, and extract. A sample was considered cured when the surfaces are smooth and without "bumps", the sample does not visibly weaken when immersed in water, and no significant extract color is formed when immersing the sample in water. The temperature profile of the sample center is measured over the molding cycle and is shown in Fig. 3. Comparison Example 2: Phenol formaldehyde binder. Composition on the basis of dry solids: - 2.41 parts of ammonium sulphate - 1.08 parts of ammonia - 0.21 parts of Silane A1101 - 96.3% phenol formaldehyde resin phenol: urea premix (70: 30) Comparative Example 2 is referred to as a Binder 1 within Fig. 3. Comparative Example 3: Carbohydrate-Inorganic Acid Binder. Composition based on dry solids: - 81.59 parts of dextrose - 17.09 parts of ammonium sulfate - 1 part of ammonia - 0.3 parts of Silane A1101 Comparative Example 3 is referred to as Binder 2 within Fig. 3. Example 5: Composition based on dry solids: - 80.94 parts of dextrose and ammonia solution (aqueous solution containing 2 mol / 1 dextrose and 2 mol / liter of ammonia) - 19.06 parts of hexamethylenediamine Example 5 is referred to as Binder 4 within Fig. 3. It was determined that the time required to achieve complete cure of a binder within the scope of the present disclosure is less than that of the binder systems of three comparative examples having different chemicals. This model system illustrates that the curing time, as long as the other variables are kept constant, is dependent on the chemistry of the binder system. The chemistry of an illustrative binder composition within the scope of the present disclosure achieves improved cure times compared to these other exemplary systems. The results are presented below:


Referring now to fig. 3, the characteristic temperature profile is shown for each of the binders 1, 2, and 4. It was noted that the temperature profile is characteristic for each binder. It has not been demonstrated that the cure rate and cure time is not characteristic of the cure temperature profile. However, the cure temperature profile helps to understand and predict the cure rate and cure time. Specifically, Comparative Example 3 is required the longest curing time, and likewise, the curing temperature profile required the longest time to maximize asymptotically. Likewise, Example 5 required the least amount of time to maximize asymptotically and demonstrated the least cure time.
Carbohydrate Reagent: Effect of the polyamine ratio on the curing cycle time. Wet placed blankets (WLM) were made with different ratios of dextrose monohydrate (DMH) to hexamethylenediamine (HMDA. The weight ratios tested include 75/25, 85/15, and 92/8, respectively.
The 15% Dextrose-Binder HMDA was applied to 5 WLMs. The following binder compositions were prepared:


The blankets are prepared in pieces of 13 "X 13" s, with a thickness of 3/8 ". The press used to mold the blankets is set to 400 ° F (204.44 ° C). Once the sample is molded, it is about 5/8 "thick. A temperature profile was determined within 15 minutes. The next sample was pressed for 4 minutes, which is the time it takes to cure a comparable phenol formaldehyde binder composition (results not shown). The experiments were repeated with different curing times until the minimum time required for curing each composition was determined. The extent to which each binder was cured was determined based on weight. The following results were determined:

As described above, the product based on comparable phenol formaldehyde (e.g. Comparative Example 2) cures with a cycle time of 4 minutes. In addition, a comparable carbohydrate-based binder (for example, Comparative Example 3) cures with a cycle time of 5 minutes. These results indicate that a binder within the scope of the present disclosure with a 85/15 primary polyamine carbohydrate reagent or lower cures at a rate comparable or faster than the phenol formaldehyde based product. Other experiments have shown that the curing temperature can be reduced in products with a shorter curing time to achieve curing times equivalent to lower temperatures. The results obtained agreed in principle with our expectations 5 based on the Arrhenius equation. In addition to the examples described in detail, the following examples have been carried out to ensure that the carbohydrate and polyamine reagent can comprise a wide variety of alternatives.
20 Additional dextrose - Examples of polyamine: Example 16: A suspension of 56.08 g of deionized water, 7.15 g of dextrose monohydrate, and 3.5 g of 1.12-diaminododecane was acidified with UN HCl to pH 1.0, and heated to 70 ° C, with stirring, resulting in a clear, colorless solution. The solution forms a water-insoluble thermosetting polymer at 160 ° C. (test condition: 2 g of binder solution is applied to a filter pad that is placed in a hydration equilibrium. The filter pad is heated for 15 min 30 to 160 ° C.) An extract from the cured filter pad with 100 g of deionized water it is essentially colorless. Example 17: A solution of 8.25 g of dextrose monohydrate, and 2.50 g of 1,5-diamino-2-methylpentane (Dytek A, Invista) dissolved in 56.08 g of deionized water, forms a polymer thermosetting insoluble in water at 160 ° C. (test conditions: 2 g binder solution is applied to a filter pad which is placed in a hydration equilibrium. The filter pad is heated for 15 min at 160 ° C.) An extract from the cured filter pad, with 100 g of deionized water is essentially colorless. Example 18: A solution of 8.03 g of dextrose monohydrate and 2.70 g of N- (3-aminopropyl) -1,3-propanediamine dissolved in 56.08 g of deionized water, forms a thermosetting polymer insoluble in water at 200 ° C. (Test conditions: 2 g binder solution is applied to a filter pad which is placed in a hydration balance. The filter pad is heated for 15 min at 200 ° C.) An extract of the cured filter pad with 100 g of deionized water, has a slightly yellowish color. Example 19: A solution of 1.0 g of dextrose (5.55 mmol), 1.0 g (approx. 2.27 mmol) of Jeffamine T-403 polyetheramine dissolved in 8.5 g of deionized water (19% solids solution) was prepared. 2 g of the binder solution was applied to a filter pad which is placed in a hydration equilibrium and heated for 5 minutes at 180 ° C. A brownish water-insoluble polymer formed on the filter layer. An extraction of the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of 7.1. Jeffamine T-403 polyetheramine is a trifunctional primary amine having an average molecular weight of 440. Its amine groups are located on secondary carbon atoms at the ends of the aliphatic polyether chains. Its structure can be represented as follows, where the sum of x, y, and z is 6:
Procedure for analyzing a sample of binder with gas pyrolysis. Approximately 10 g of a cured product that has the binder in it is placed in a test tube, which tube is then heated to 1000 ° F (537.77 ° C) for 2.5 minutes, in which at this time the headspace it is sampled and analyzed by gas chromatography / mass spectrometry (GC / MS), under the following conditions: Oven, 50 ° C for one minute - 10 ° C / minute up to 300 ° C for 10 minutes; Inlet, 280 ° C without division; Column, HP-5 30 mm x 0.32 mm x 0.25 µm, Column flow, 1.11 ml / minute Helium; Detector, MSD 280 ° C, Injection volume, 1 ml; Detector mode, scan 34-700 amu; Threshold, 50, and Sample rate, 22 scans / second. A computer search for the mass spectrum of a chromatographic peak in the sample is done with the Wiley library of mass spectra. The best combination is reported. A quality index (proximity of departure for the library spectra) ranging from 0 to 99 is generated. Only the identity of the peaks with a quality index greater than or equal to 90 is reported.
The following table provides representative pyrolysis data that is expected from the GC / MS analysis of 5 gaseous compounds produced during the pyrolysis of a melanoidin-binder composition.

The following is a list of the species observed in the pyrolysis gas by gas chromatography / mass spectrometry (Py GC-MS) of a binder sample prepared using hexamethylenediamine as the polyamine component. Pyrolysis was carried out at 200 ° C, 300 ° C and 770 ° C. The fingerprint shows a very significant peak that corresponds to acetic acid in the mass chromatogram, both at 200 ° C and 300 ° C, which was not observed in a sample made using dextrose and ammonium sulfate (see Comparative Example 3), 30 where the significant volatility was SO2, particularly at 300 ° C. At 77 ° C, the observed peaks, in order to increase the retention time, were designated as follows: A: Co-eluting C5H10, C5H12, acetone, possibly low pm of the acetic acid ester; B: C5Hg diene; C: C5H8 diene; D: probable pentanol; E: CgHi2 - methyl pentene; F: hexane; G: methylcyclopentane, H: a cyclohexadiene; I: CβHio - probably a methylcyclopentane; J: benzene; K: acetic acid; L: cyclohexene; M: probably nonanol, N: 2-methyl-3-pentanone; O: 2,5-dimethylfuran, P: C7H10 + unassigned co-element; Q: pyridine + unassigned co-element; R: toluene; S: possibly ten-year + unassigned co-element; T: 2-ethyl-5-methylfuran, U: a methyl pyridine; V: a methyl pyrrole; W: a xylene; X: not assigned - with an alcohol functionality; Y: not assigned; Z: an xylene + unassigned co-element; AA: not assigned; AB: a dimethyl pyrrole; AC: a dimethyl pyridine, AD: a dimethyl pyridine; AE: not assigned; AF: not assigned; AG: a methyl ethyl pyrrole + unassigned co-element; AI: an unassigned but distinct mass spectrum (containing N), related pyrrole; AJ: an unassigned but distinct mass spectrum (containing N), possibly an acetamide; AK: an unassigned but distinct mass spectrum (containing N), related pyrrole; AL: an unassigned but distinct mass spectrum (containing N), related pyrrole; AM: an unassigned but distinct mass spectrum (containing N), related pyrrole. The mass spectra seen from AI to AM peaks are not seen in the previous binder data without the polyamine component. Procedure for evaluation of resistance to dry and weathered traction. When evaluated for their dry and "intermperized" tensile strength, shell bone compositions containing glass beads prepared with a given binder provide an indication of the likely tensile strength and likely durability, respectively, of a fiberglass product prepared with the particular binder. Expected durability is based on a shell bone intermperized tensile strength: dry tensile strength ratio. Shell bones are prepared, weathered, and tested as follows, for example, for a hexamethylenediamine-dextrose binder mixture.
A shell bone mold (Dietert Foundry Testing Equipment; Heated Shell Curing Accessory, model 366, and Shell Mold Accessory) is set to a desired temperature, usually 425 ° F (218.33 ° C), and allowed to warm for at least at least an hour. While the shell bone mold is heating, approximately 100 g of an aqueous binding agent (usually 15% in paste solids) is prepared (for example, as described in example 7). Using a large glass container, 727.5 g of glass beads (Quality Ballotini Impact Beads, Spec. AD, US Sieve 70-140, 106-212 micron # 7, from Potters Industries, Inc.) are weighed by difference. The glass beads are placed in a clean, dry mixing container, which has been mounted in an electric mixer. Approximately 75 g of aqueous binding agent is slowly poured onto the glass beads in the mixing vessel. The electric mixer is then switched on and the glass beads / binder mixture is stirred for one minute. Using a large spatula, the sides of the beater (mixer) are scraped to remove any agglomerates of binder, and at the same time the scraping of the edges, where the glass beads are at the bottom of the container. The mixer is then switched on again for another minute and then the whisk (mixer) is removed from the unit, followed by removal of the mixing vessel containing the glass beads / binder mixture. Using a large spatula, both the glass beads and the binder attached to the whisk (mixer) as much as possible are removed and then stirred into the glass bead / binder mixture in the container. The container walls are then scraped to mix any excess binder that may have accumulated on the sides. At this point, the glass bead / hexamethylenediamine-dextrose binder mixture is ready for molding in a shell bone mold.
The blades of the shell bone mold are confirmed to be aligned within the bottom mold cylinder. Using a large spatula, a mixture of glass beads / hexamethylenediamine-dextrose binder is then quickly added into three mold cavities inside the shell bone mold. The surface of the mixture in each cavity is flattened, scraping the excess mixture to obtain a uniform surface area for the bone in shell. Inconsistencies or gaps in any of the cavities are filled with a mixture of additional glass beads / hexamethylenediamine-dextrose binder and then flattened. Once the mixture of glass beads / hexamethylenediamine-dextrose binder is placed in the bone cavities in the shell, and the mixture is exposed to heat, curing begins. As the handling time can affect the test results, for example, the shell bones with two differentially cured layers can be produced; bark bones are prepared consistently and quickly. With the shell bone mold filled, the upper plate is quickly placed on the lower plate. At the same time, or shortly thereafter, the measurement of the polymerization time is initiated by means of a stopwatch, which during curing the temperature of the bottom plate varied from about 400 ° F (204.44 ° C) to about 430 ° F (221.11 ° C), while the temperature of the top plate varied from about 440 ° F (226.66 ° C) to about 470 ° F (243.33 ° C) . After seven minutes, the top plate is removed and the blades pulled out so that all three bones in the shell can be removed. The fresh shelled bones are then placed on a wire rack, adjacent to the shelled bone mold plate, and allowed to cool to room temperature. Subsequently, each bone in the shell is labeled and placed individually in a suitably labeled plastic storage bag. If shelled bones cannot be tested on the day they were prepared, plastic bags containing the shelled bone were placed in a desiccator unit.
Conditioning Procedure (Weathering) for Shell Bones: The Blue M humidity chamber is turned on and then set to provide weathering conditions of 90 ° F (32.22 ° C) and 90% relative humidity (ie 90 ° F / 90% RH). The water tank on the side of the humidity chamber is checked and filled regularly, usually each time it is activated. The humidity chamber is allowed to reach the specified weathering conditions over a period of at least 4 hours, with an equilibrium period of an entire day being typical. Shell bones to be weathered are loaded quickly (since, while the doors are opened simultaneously, the humidity and temperature decrease), one at a time through the open humidity chamber doors, on the upper shelf, with a slit in the chamber. moisture. The time that shell bones are placed in the humidity chamber is noted, and weathering is conducted for a period of 24 hours. After that, the humidity chamber doors are opened and one set of shell bones at a time is quickly removed and placed individually in respective plastic storage bags, being sealed completely. Generally, four sets of shell bones at a time are weathered, as described above. Weathered shell goods are immediately taken to Instron's room and tested.
Test procedure for breaking shell bones: In the Instron room, the Shell bone test method is loaded onto the Instron 5500 R machine, ensuring that the appropriate load cell is installed (ie, 5 kN Static Load Cell), and the machine is allowed to warm up for fifteen minutes. During this time, shell bone tightness tests are checked to be installed on the machine. The load cell is zeroed and balanced, and then a set of shell bones is tested each time as follows: The boen shell is removed from its plastic packaging and then weighed. The weight (in grams) is then entered into the computer associated with the Instron machine. The measured thickness of the shell bone (in inches) is then entered, like the sample thickness, three times into the computer associated with the Instron machine. A shell bone sample is then placed in the claws on the Instron machine and the test started via the keyboard on the Instron machine. After taking a shell bone sample, the measured breakpoint is entered into the computer associated with the Instron machine and the test continued until all shell bones in a set are tested. Carbohydrate Reagent: Effect of the polyamine ratio on shell bone properties. Sell bones were made with different ratios of dextrose monohydrate (DMH) to hexamethylenediamine (HMDA) with a silane additive (ISI0200) were examined as described above, at a test speed of 25 mm / min. The weight ratios tested include 90/10, 85/15, 80/20 and 75/25, respectively.
Example: Tests with glass wool (fiberglass) Comparison of the qualities of two glucose-hexamethylenediamine binders with a standard binder in terms of curing and stiffness in a glass wool product (Ac + 032 100 mm 1200 mm) width, 32 kg / m3 - 15 m / min) were performed by measuring the separation force and density. Binder 1: glucose 85% - hexamethylenediamine 15%. Binder 2: glucose 90% - hexamethylenediamine 10%. Ordinary separation force (before autoclave) and intemperate separation force (after autoclave) can be measured as described in international patent application, publication number WO 2008/089851 or W02009 / 019235. Separating force in a standard binder: BEFORE THE AUTOCAVE
35861.4 g FS BEFORE: 298.3 gf / gpeso AFTER AUTOCLAVE
FS AFTER: 234.8 gf / gpeso Separating force on Binder 1: LOSS 63.6 gf / gpeso ie, 21.3% Separating force on binder 1: 5 BEFORE AUTOCLAVE AFTER AUTOCLAVE
FS BEFORE: 360.8 gf / gpeso AFTER THE AUTOCLAVE FS AFTER: 271.3 gf / gpeso 15 LOSS 89.5 gf / gpeso ie, 24.8% Separating force in the Binder 2: BEFORE THE AUTOCLAVE AFTER THE AUTOCLAVE
FS BEFORE: 348.88 gf / gpeso AFTER AUTOCLAVE 25 FS AFTER: 248.2 gf / gpeso LOSS 78.1 gf / gpeso ie, 19.3% 30 Observations during the test: in line with the two hexamethylenediamine. Conclusions: With The product was more brown binders of glucose glycoseaglutinants- Observations during the test: The product was browner in the line with the two binders of glucose-hexamethylenediamine. Conclusions: With the glucose-hexamethylenediamine binders, the results of the separation force (which is a longitudinal tensile strength) showed a significant improvement, and a significant improvement was observed in other three stiffness tests ("60o" test - sagging measured when leaning at 60 ° against the rail, "table" test - sagging measured against a horizontal plane, and Acermi test - sagging measured at 35 centimeters from the edge of a table). Example; Particle board assay Comparisons of particle board qualities made using a urea formaldehyde binder (UF E0) and using a polyamine carbohydrate (hexamethylenediamine) umagglutinant were performed under the following conditions. Panel size: 350 x 333 mm and mainly 10 mm thick, (2x20mm). Exposure temperature: mainly 195 ° C, but also 175 and ~ 215 ° C. Pressure: 3.5 Mpa (35 bar) Quoted - Real 35 Kg / cm2, 56 bar to reach. Target Density: 650 kg / m3 Preform prepared before pressing. Results:

All prepared plates appeared to be of high quality, with no divisions or degassing observed. The plates made with this polyamine carbohydrate formulation compete with the urea 5 formaldehyde plate, when they are cured for 150 seconds.

权利要求:
Claims (38)
[0001]
1. Method of making a collection of material bound with a cured, thermoset, polymeric binder, characterized by comprising: preparing an aqueous binder solution, said preparation comprising mixing reagents for the production of the cured, thermoset, polymeric binder, in which the reagents include a reducing sugar and a primary polyamine H2N-Q-NH2, where Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which is optionally substituted and provided that the primary polyamine does not consist of polyethyleneimine; subsequently dispose of the binder solution over the material collection; subsequently drying the binder solution to form an uncured binder and thermally curing the uncured binder to form the collection of material agglutinated with the cured, polymeric, thermal binder.
[0002]
2. Method, according to claim 1, characterized by the fact that the cured polymeric, thermoset binder is free formaldehyde.
[0003]
3. Method according to claim 1, characterized by the fact that neither formaldehyde nor phenol is used as a reagent.
[0004]
4. Method according to claim 1, characterized by the fact that the material collection comprises material selected from the group consisting of glass fibers, mineral fibers, aramid fibers, ceramic fibers, metallic fibers, carbon fibers, fibers polyimide, polyester fibers, rayon fibers, cellulosic fibers, wood chips, sawdust, wood pulp, crushed wood, jute, linen, hemp, straw, particles, charcoal particles and sand particles.
[0005]
5. Method, according to claim 1, characterized by the fact that the material collection comprises glass fibers present in the range of 70% to 99% by weight.
[0006]
6. Method, according to claim 1, characterized by the fact that the reducing sugar is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone and their mixtures.
[0007]
7. Method according to claim 1, characterized by the fact that the primary polyamine is selected from the group consisting of a diamine, triamine, tetramine and pentamine.
[0008]
8. Method according to claim 1, characterized by the fact that Q is an alkyl selected from the group consisting of C2-C8.
[0009]
9. Method according to claim 1, characterized by the fact that the primary polyamine is selected from the group consisting of 1,6-diamino-hexane, 1,5-diamino-2-methylpentane, diethylenetriamine, bis (hexamethylene) triamine, triethylenetetramine and tetraethylenepentamine.
[0010]
10. Method according to claim 1, characterized by the fact that a weight ratio of the reducing sugar to the primary polyamine is in the range of 2: 1 to 10: 1.
[0011]
11. Method, according to claim 1, characterized by the fact that a weight ratio of the reducing sugar to the primary polyamine is in the range of 3: 1 to 6: 1.
[0012]
12. Method according to claim 1, characterized by the fact that the preparation of the binder solution includes adjusting the pH of the binder solution to be within the range of 8 to 12.
[0013]
13. Method according to claim 1, characterized by the fact that the cured binder is substantially insoluble in water.
[0014]
14. Method, according to claim 1, characterized by the fact that the polymeric binder absorbs light intensely at 420 nm.
[0015]
15. Method according to claim 1, characterized by the fact that the binder solution is essentially acid-free.
[0016]
16. Method, according to claim 1, characterized by the fact that the material collection and the cured polymeric, thermosetting binder further comprise a material selected from the group consisting of a compound containing silicon, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane , aminoethylaminopropyltrimethoxysilane, an aminofunctional oligomeric siloxane and mixtures thereof.
[0017]
17. Method, according to claim 1, characterized by the fact that the material collection and the cured polymeric, thermosetting binder further comprise a corrosion inhibitor selected from the group consisting of anti-dust oil, monoammonium phosphate, metasilicate sodium pentahydrate, melamine, tin (II) oxalate, and hydrogenated methyl silicone fluid emulsion.
[0018]
18. Method according to claim 1, characterized by the fact that the binder further comprises a non-aqueous humidifier.
[0019]
19. Method according to claim 1, characterized by the fact that Q is alkyl, cycloalkyl, heteroalkyl or cycloheteroalkyl, each of which is optionally substituted by a group selected from the group consisting of amino, hydroxyl, halo, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, nitro, sulfonic acids and their derivatives, and carboxylic acids and their derivatives.
[0020]
20. Method according to claim 1, characterized by the fact that a weight ratio of the reducing sugar to the primary polyamine is in the range of 1: 1 to 30: 1.
[0021]
21. Method according to claim 1, characterized by the fact that the binder solution has an alkaline pH.
[0022]
22. Method according to claim 1, characterized in that the method is a method for making a composite wooden board comprising a collection of material comprising cellulosic fibers linked to the cured, thermosetting polymeric binder, and comprises: preparing the solution aqueous binder; subsequently dispose of the binder solution in the collection of matter comprising cellulosic fibers; subsequently drying the binder solution to form the uncured binder and thermally curing the uncured binder to form the composite wood board bound to the cured, thermoset polymeric binder; wherein the composite wood board is selected from the group consisting of: a composite wood board with an elasticity modulus (MOE) of at least 1800 N / mm2; a composite wooden board with a flexural strength (MOR) of at least 18 N / mm2; a composite wooden board with an internal bond strength (TB) of at least 0.28 N / mm2; a composite wooden board that swells less than or equal to 12%, measured by a change in thickness, after 24 hours in water at 20 ° C; a composite wooden board with water absorption after 24 hours in water at 20 ° C less than or equal to 40%; a composite wooden board comprising a wax; an oriented strandboard; and a medium density fiberboard.
[0023]
23. Method according to claim 22, characterized by the fact that the reducing sugar is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone and mixtures thereof.
[0024]
24. Method according to claim 22, characterized by the fact that Q is alkyl selected from the group consisting of C2-C8.
[0025]
25. Method according to claim 22, characterized by the fact that Q is alkyl, cycloalkyl, heteroalkyl or cycloheteroalkyl, each of which is optionally substituted by a group selected from the group consisting of amino, hydroxyl, halo, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, nitro, sulfonic acids and their derivatives, and carboxylic acids and their derivatives.
[0026]
26. Method according to claim 22, characterized by the fact that the primary polyamine is 1,6-diaminohexane.
[0027]
27. Method according to claim 22, characterized in that a weight ratio of the reducing sugar to the primary polyamine is in the range of 1: 1 to 30: 1.
[0028]
28. Method according to claim 22, characterized by the fact that a weight ratio of the reducing sugar to the primary polyamine is in the range of 2: 1 to 10: 1.
[0029]
29. Method according to claim 22, characterized in that a weight ratio of the reducing sugar to the primary polyamine is in the range of 3: 1 to 6: 1.
[0030]
30. Method according to claim 22, characterized by the fact that cellulosic fibers comprise material selected from the group consisting of wood shavings, sawdust, wood pulp, milled wood, jute, linen, hemp and straw.
[0031]
31. Method according to claim 22, characterized in that the composite wood board comprises a wax.
[0032]
32. Method according to claim 22, characterized by the fact that the composite wood board has an elasticity modulus (MOE) of at least 1800 N / mm2.
[0033]
33. Method, according to claim 22, characterized by the fact that the composite wood board has a flexural strength (MOR) of at least 18 N / mm2.
[0034]
34. Method, according to claim 22, characterized by the fact that the composite wood board has an internal bond strength (TB) of at least 0.28 N / mm2.
[0035]
35. Method, according to claim 22, characterized by the fact that the composite wooden board swells less than or equal to 12%, measured by a change in thickness, after 24 hours in water at 20 ° C.
[0036]
36. Method, according to claim 22, characterized by the fact that the composite wooden board has a water absorption after 24 hours in water at 20 ° C less than or equal to 40%.
[0037]
37. Method according to claim 22, characterized by the fact that the composite wooden board is a oriented cord or a medium density fiberboard.
[0038]
38. Method, according to claim 22, characterized by the fact that the composite wood board has 8% to 18% dry weight of the binder.

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BR112012028525A2|2016-07-19|

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CA2797147A1|2011-11-10|

---

KR20170119734A|2017-10-27|

---

PT2566904T|2021-08-30|

---

JP2013531082A|2013-08-01|

---

CN105176460B|2018-02-06|

---

CN105176460A|2015-12-23|

---

PL2566904T3|2021-12-06|

---

JP2020121560A|2020-08-13|

---

MX339814B|2016-06-02|

---

KR20130092960A|2013-08-21|

---

AU2011249759B2|2014-11-06|

---

JP2017201043A|2017-11-09|

---

US11078332B2|2021-08-03|

---

DE212011100094U1|2013-01-11|

---

MX2012012633A|2013-05-20|

---

US9505883B2|2016-11-29|

---

EA201291190A1|2013-05-30|

---

KR101837215B1|2018-03-09|

---

US20140323618A1|2014-10-30|

---

AU2011249759A1|2012-11-08|

---

CN103025778A|2013-04-03|

---

US20170037187A1|2017-02-09|

---

CN103025778B|2015-09-30|

---

JP6312337B2|2018-04-18|

---

MY160858A|2017-03-31|

---

WO2011138458A1|2011-11-10|

---

US10738160B2|2020-08-11|

---

LT2566904T|2021-10-25|

---

CA2797147C|2017-06-20|

---

US20180265633A1|2018-09-20|

---

US20200332060A1|2020-10-22|

---

EP3922655A1|2021-12-15|

---

KR102023264B1|2019-11-04|

---

US20210403645A1|2021-12-30|

---

EP3922655A4|2021-12-15|

---

CL2012003123A1|2013-07-05|

---

EA025773B1|2017-01-30|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US1886353A|1922-04-27|1932-11-01|John Stogdell Stokes|Synthetic resin and method of making same|

---

US1801052A|1923-02-06|1931-04-14|Meigsoid Corp|Resinous condensation product and process of making same|

---

US1801053A|1925-01-22|1931-04-14|Meigsoid Corp|Carbohydrate product and process of making same|

---

US1902948A|1931-08-14|1933-03-28|A M Castle & Co|Welding electrode|

---

US1964263A|1932-06-15|1934-06-26|Anker Holth Mfg Company|Spraying fixture|

---

BE420665A|1936-03-20|

---

US2261295A|1936-09-30|1941-11-04|Walther H Duisberg|Artificial textile materials|

---

US2215825A|1938-03-16|1940-09-24|Matilda Wallace|Core binder|

---

US2362086A|1941-08-26|1944-11-07|Resinous Prod & Chemical Co|Volume stabilized acid absorbing resin|

---

US2371990A|1942-02-18|1945-03-20|Du Pont|Polymeric esters|

---

BE471265A|1942-04-02|

---

BE472469A|1942-06-16|

---

US2500665A|1944-03-30|1950-03-14|Owens Corning Fiberglass Corp|High-temperature insulation and method of manufacture|

---

BE472470A|1945-07-11|

---

GB770561A|1954-11-17|1957-03-20|Corn Prod Refining Co|Improvements in or relating to core for foundry purposes and process for producing the same|

---

US2875073A|1955-05-23|1959-02-24|Corn Prod Refining Co|Core binder and process of making cores|

---

GB809675A|1955-05-23|1959-03-04|Corn Prod Refining Co|Improvements in or relating to refractory insulating block and method of making same|

---

US2894920A|1957-02-12|1959-07-14|Ramos Thomas|Resinous composition comprising epoxy resin, curing agent and mixture of dextrines, maltose and dextrose and process for preparing|

---

US2965504A|1958-04-01|1960-12-20|Corn Products Co|Process for preparation of refractory insulating blocks|

---

GB979991A|1960-01-14|1965-01-06|Polygram Casting Co Ltd|Improvements in or relating to thermosetting compositions based on carbohydrates|

---

US3038462A|1960-07-21|1962-06-12|Gen Electric|Oven liner|

---

US3231349A|1960-11-21|1966-01-25|Owens Corning Fiberglass Corp|Production of vitreous fiber products|

---

NL275294A|1961-03-08|1900-01-01|

---

US3138473A|1962-01-26|1964-06-23|Gen Mills Inc|Compositions and process to increase the wet strength of paper|

---

US3222243A|1962-07-11|1965-12-07|Owens Corning Fiberglass Corp|Thermal insulation|

---

DE1905054U|1964-03-05|1964-11-26|Guenter Manzke Produktion Und|COMPONENT FOR THE LATERAL TRACK BARRIER.|

---

US3232821A|1964-12-11|1966-02-01|Ferro Corp|Felted fibrous mat and apparatus for manufacturing same|

---

US3297419A|1965-08-17|1967-01-10|Fyr Tech Products Inc|Synthetic fuel log and method of manufacture|

---

DE1905054A1|1968-02-05|1969-08-21|Dierks Forests Inc|Thermosetting saccharide-based binder|

---

US3856606A|1968-06-17|1974-12-24|Union Carbide Corp|Coupling solid substrates using silyl peroxide compounds|

---

US3551365A|1968-11-29|1970-12-29|Ralph Matalon|Composite cross - linking agent/resin former compositions and cold-setting and heat - setting resins prepared therefrom|

---

SU374400A1|1970-07-09|1973-03-20|METHOD OF OBTAINING NONWAVE MATERIALS|

---

US3867119A|1970-07-20|1975-02-18|Paramount Glass Mfg Co Ltd|Apparatus for manufacturing glass fibers|

---

US3784408A|1970-09-16|1974-01-08|Hoffmann La Roche|Process for producing xylose|

---

US3826767A|1972-01-26|1974-07-30|Calgon Corp|Anionic dextran graft copolymers|

---

US3791807A|1972-05-02|1974-02-12|Certain Teed Prod Corp|Waste water reclamation in fiber glass operation|

---

US3961081A|1972-06-05|1976-06-01|Mckenzie Carl O|Molasses feed block for animals and method of making same|

---

US4144027A|1972-07-07|1979-03-13|Milliken Research Corporation|Product and process|

---

IT971367B|1972-11-30|1974-04-30|Sir Soc Italiana Resine Spa|PROCEDURE FOR THE CONTINUOUS PREPARATION OF UNSATURATED POLYESTERS|

---

US4054713A|1973-12-28|1977-10-18|Kao Soap Co., Ltd.|Process for preparing glass fiber mats|

---

US3955031A|1973-01-18|1976-05-04|Owens-Corning Fiberglas Corporation|Flame resistant building material|

---

CH579109A5|1973-02-22|1976-08-31|Givaudan & Cie Sa|

---

US4201857A|1973-02-22|1980-05-06|Givaudan Corporation|Novel condensation products having high activity to insolubilize proteins and protein-insolubilized products|

---

SE7410542L|1974-01-29|1976-01-12|Givaudan & Cie Sa|CONDENSATION PRODUCTS.|

---

US4186053A|1973-02-22|1980-01-29|Givaudan Corporation|Insolubilized enzyme product|

---

US4184986A|1975-08-19|1980-01-22|Givaudan Corporation|Novel condensation products having high activity to insolubilize proteins and protein-insolubilized products|

---

US3802897A|1973-02-23|1974-04-09|Anheuser Busch|Water resistant starch adhesive|

---

US3809664A|1973-08-16|1974-05-07|Us Agriculture|Method of preparing starch graft polymers|

---

DE2360876A1|1973-12-06|1975-06-12|Bayer Ag|CATIONIC COLORS|

---

GB1469331A|1974-02-18|1977-04-06|Pfizer Ltd|Flavouring agent|

---

US4183997A|1974-02-22|1980-01-15|John Jansky|Bonding of solid lignocellulosic material|

---

US4107379A|1974-02-22|1978-08-15|John Stofko|Bonding of solid lignocellulosic material|

---

US4014726A|1974-03-18|1977-03-29|Owens-Corning Fiberglas Corporation|Production of glass fiber products|

---

US3907724A|1974-04-10|1975-09-23|Monsanto Co|Phenolic binders for mineral fiber thermal insulation|

---

US3919134A|1974-04-10|1975-11-11|Monsanto Co|Thermal insulation of mineral fiber matrix bound with phenolic resin|

---

US3922466A|1974-09-16|1975-11-25|Owens Corning Fiberglass Corp|Silane coupling agents|

---

US3956204A|1975-03-10|1976-05-11|Monsanto Company|Antipunking phenolic resin binder systems for mineral fiber thermal insulation|

---

CH594370A5|1975-08-26|1978-01-13|Maggi Ag|

---

US4028290A|1975-10-23|1977-06-07|Hercules Incorporated|Highly absorbent modified polysaccharides|

---

JPS5428180B2|1976-05-24|1979-09-14|

---

CA1090026A|1976-07-22|1980-11-18|John P. Gibbons|Carbohydrate-phenol based condensation resins incorporating nitrogen-containing compounds|

---

US4048127A|1976-07-22|1977-09-13|Cpc International Inc.|Carbohydrate-based condensation resin|

---

US4217414A|1976-11-01|1980-08-12|Cpc International Inc.|Process for separating and recovering vital wheat gluten from wheat flour and the like|

---

US4148765A|1977-01-10|1979-04-10|The Dow Chemical Company|Polyester resins containing dicyclopentadiene|

---

US4097427A|1977-02-14|1978-06-27|Nalco Chemical Company|Cationization of starch utilizing alkali metal hydroxide, cationic water-soluble polymer and oxidant for improved wet end strength|

---

JPS5717850Y2|1977-02-16|1982-04-14|

---

JPS5629600B2|1977-03-17|1981-07-09|

---

DE2721186C2|1977-05-11|1986-04-24|Bayer Ag, 5090 Leverkusen|Process for the preparation of a mixture of low molecular weight polyhydroxyl compounds|

---

US4201247A|1977-06-29|1980-05-06|Owens-Corning Fiberglas Corporation|Fibrous product and method and apparatus for producing same|

---

AU530553B2|1978-05-09|1983-07-21|Commonwealth Scientific And Industrial Research Organisation|Treatment of textile materials|

---

DE2833138A1|1978-07-28|1980-02-07|Bayer Ag|METHYLOLATED MONO AND OLIGOSACCHARIDES|

---

US4506684A|1978-08-02|1985-03-26|Philip Morris Incorporated|Modified cellulosic smoking material and method for its preparation|

---

US4333484A|1978-08-02|1982-06-08|Philip Morris Incorporated|Modified cellulosic smoking material and method for its preparation|

---

HU186349B|1979-01-23|1985-07-29|Magyar Tudomanyos Akademia|Process for producing polymeres containing metals of side-groups in complex bond|

---

US4265963A|1979-01-26|1981-05-05|Arco Polymers, Inc.|Flameproof and fireproof products containing monoethanolamine, diethylamine or morpholine|

---

US4233432A|1979-05-10|1980-11-11|United States Steel Corporation|Dicyclopentadiene polyester resins|

---

US4310585A|1979-06-15|1982-01-12|Owens-Corning Fiberglas Corporation|Fibrous product formed of layers of compressed fibers|

---

US4296173A|1979-09-13|1981-10-20|Ppg Industries, Inc.|Glass fibers with reduced tendency to form gumming deposits and sizing composition comprising two starches with different amylose content|

---

US4259190A|1979-09-13|1981-03-31|Ppg Industries, Inc.|Glass fibers with reduced tendency to form gumming deposits and sizing composition|

---

US4246367A|1979-09-24|1981-01-20|United States Steel Corporation|Dicyclopentadiene polyester resins|

---

US4278573A|1980-04-07|1981-07-14|National Starch And Chemical Corporation|Preparation of cationic starch graft copolymers from starch, N,N-methylenebisacrylamide, and polyamines|

---

US4379101A|1980-06-04|1983-04-05|Allen Industries, Inc.|Forming apparatus and method|

---

US4330443A|1980-06-18|1982-05-18|The United States Of America As Represented By The Secretary Of Agriculture|Dry chemical process for grafting acrylic and methyl acrylic ester and amide monomers onto starch-containing materials|

---

GB2078805A|1980-06-27|1982-01-13|Tba Industrial Products Ltd|Fire and Weld Splash Resistant for Glass Fabric|

---

EP0044614A3|1980-06-27|1982-05-19|TBA Industrial Products Limited|Improvements in and relating to glass fabrics|

---

US4361588A|1980-07-30|1982-11-30|Nutrisearch Company|Fabricated food products from textured protein particles|

---

US4400496A|1980-09-22|1983-08-23|University Of Florida|Water-soluble graft copolymers of starch-acrylamide and uses therefor|

---

JPS57101100U|1980-12-12|1982-06-22|

---

JPS57101100A|1980-12-15|1982-06-23|Nitto Boseki Co Ltd|Production of mineral fiberboard|

---

JPS5811193B2|1981-02-02|1983-03-01|Mitsubishi Gas Chemical Co|

---

US4396430A|1981-02-04|1983-08-02|Ralph Matalon|Novel foundry sand binding compositions|

---

US4357194A|1981-04-14|1982-11-02|John Stofko|Steam bonding of solid lignocellulosic material|

---

US4393019A|1981-11-30|1983-07-12|The United States Of America As Represented By The Secretary Of Agriculture|Method of pressing reconstituted lignocellulosic materials|

---

FR2529917B1|1982-07-06|1985-03-08|Saint Gobain Isover|

---

US4464523A|1983-05-16|1984-08-07|National Starch And Chemical Corporation|Process for the preparation of graft copolymers of cellulose derivatives and diallyl, dialkyl ammonium halides|

---

US4668716A|1983-09-30|1987-05-26|Union Carbide Corporation|Novel fatty ethenoid acylaminoorganosilicon compounds and their use as a coupling agent|

---

US4524164A|1983-12-02|1985-06-18|Chemical Process Corporation|Thermosetting adhesive resins|

---

US4654259A|1984-02-14|1987-03-31|Carbocol Inc.|Method and composition for bonding solid lignocellulosic material|

---

FR2559793B1|1984-02-17|1986-12-19|Saint Gobain Isover|PROCESS FOR PRODUCING MINERAL FIBER MATTRESS FROM MOLTEN MATERIAL|

---

US4714727A|1984-07-25|1987-12-22|H. B. Fuller Company|Aqueous emulsion coating for individual fibers of a cellulosic sheet providing improved wet strength|

---

GB2170208B|1985-01-29|1988-06-22|Enigma Nv|A formaldehyde binder|

---

JPS61195647A|1985-02-27|1986-08-29|Kanebo Shokuhin Kk|Production of bitter chocolate|

---

US4754056A|1985-04-05|1988-06-28|Desoto, Inc.|Radiation-curable coatings containing reactive pigment dispersants|

---

JPS61195647U|1985-05-27|1986-12-05|

---

SE8504501D0|1985-09-30|1985-09-30|Astra Meditec Ab|METHOD OF FORMING AN IMPROVED HYDROPHILIC COATING ON A POLYMER SURFACE|

---

US4828643A|1986-02-19|1989-05-09|Masonite Corporation|Liquified cellulosic fiber, resin binders and articles manufactured therewith, and method of manufacturing same|

---

US4692478A|1986-03-14|1987-09-08|Chemical Process Corporation|Process for preparation of resin and resin obtained|

---

US4780339A|1986-07-30|1988-10-25|National Starch And Chemical Corporation|Sized glass fibers and method for production thereof|

---

FR2614388A1|1987-04-22|1988-10-28|Micropore International Ltd|Process for the manufacture of a lagging material for use at high temperature|

---

DE3629470A1|1986-08-29|1988-03-10|Basf Lacke & Farben|CARBOXYL GROUPS AND TERTIAL AMINO GROUPS CONTAINING POLYCONDENSATION AND / OR ADDITION PRODUCT, COATING AGENTS BASED ON THE SAME AND THEIR USE|

---

IL80298A|1986-10-14|1993-01-31|Res & Dev Co Ltd|Eye drops|

---

US4720295A|1986-10-20|1988-01-19|Boris Bronshtein|Controlled process for making a chemically homogeneous melt for producing mineral wool insulation|

---

US4734996A|1986-12-15|1988-04-05|Owens-Corning Fiberglas Corporation|Method and apparatus for heating mineral fibers|

---

US5013405A|1987-01-12|1991-05-07|Usg Interiors, Inc.|Method of making a low density frothed mineral wool|

---

US4845162A|1987-06-01|1989-07-04|Allied-Signal Inc.|Curable phenolic and polyamide blends|

---

DE3734752A1|1987-10-14|1989-05-03|Basf Ag|METHOD FOR THE PRODUCTION OF AQUEOUS ACRYLIC ACID ESTER COPOLYMER DISPERSIONS IN TWO STAGES AND THE USE THEREOF AS IMPREGNANT, COATING AND BINDING AGENT FOR FLAT FIBER FABRICS|

---

SE464687B|1987-11-10|1991-06-03|Biocarb Ab|PROCEDURES FOR PREPARING A GEL PRODUCT|

---

US5095054A|1988-02-03|1992-03-10|Warner-Lambert Company|Polymer compositions containing destructurized starch|

---

FR2626578B1|1988-02-03|1992-02-21|Inst Francais Du Petrole|AMINO-SUBSTITUTED POLYMERS AND THEIR USE AS ADDITIVES FOR MODIFYING THE COLD PROPERTIES OF MEDIUM HYDROCARBON DISTILLATES|

---

US5441713A|1988-04-29|1995-08-15|Nalco Fuel Tech|Hardness suppression in urea solutions|

---

JPH0299655A|1988-08-03|1990-04-11|Sequa Chemicals Inc|Starchy binder composition for fiber mat and its production|

---

US4988780A|1988-08-15|1991-01-29|Allied-Signal|Flame resistant article made of phenolic triazine and related method using a pure cyanato novolac|

---

US4918861A|1988-11-15|1990-04-24|Hobbs Bonded Fibers|Plant growth bed with high loft textile fibers|

---

DE3839171A1|1988-11-19|1990-05-23|Bayer Ag|AQUEOUS COATING AGENT, A METHOD FOR PRODUCING IT AND ITS USE|

---

US5371194A|1988-12-28|1994-12-06|Ferretti; Arthur|Biomass derived thermosetting resin|

---

CA2005321A1|1988-12-28|1990-06-28|Arthur Ferretti|Thermosettable resin intermediate|

---

US5582682A|1988-12-28|1996-12-10|Ferretti; Arthur|Process and a composition for making cellulosic composites|

---

US4992519A|1989-02-01|1991-02-12|Borden, Inc.|Binder composition with low formaldehyde emission and process for its preparation|

---

US5198492A|1989-02-13|1993-03-30|Rohn And Haas Company|Low viscosity, fast curing binder for cellulose|

---

US5278222A|1989-02-13|1994-01-11|Rohm And Haas Company|Low viscosity, fast curing binder for cellulose|

---

JPH0734023Y2|1989-04-17|1995-08-02|川崎重工業株式会社|Weighing and transporting device for powder and granules|

---

AT393272B|1989-06-07|1991-09-25|Rettenbacher Markus Dipl Ing|METHOD FOR PRODUCING EXTRUDED, DIRECTLY EXPANDED BIOPOLYMER PRODUCTS AND WOOD FIBER PANELS, PACKAGING AND INSULATING MATERIALS|

---

US5037930A|1989-09-22|1991-08-06|Gaf Chemicals Corporation|Heterocyclic quaternized nitrogen-containing cellulosic graft polymers|

---

ES2014208T3|1989-11-08|1994-11-16|Shell Int Research|FLEXIBLE AND SOFT POLYURETHANE FOAMS, A PROCEDURE FOR PREPARING THEM, AND A COMPOSITION OF POLIOL USEFUL IN SUCH PROCEDURE.|

---

JP2515411B2|1989-12-01|1996-07-10|新王子製紙株式会社|Method for manufacturing thermal recording material|

---

JP2926513B2|1989-12-11|1999-07-28|住友化学工業株式会社|Resin composition and method for producing the same|

---

US5151465A|1990-01-04|1992-09-29|Arco Chemical Technology, L.P.|Polymer compositions and absorbent fibers produced therefrom|

---

US5032431A|1990-02-06|1991-07-16|Georgia-Pacific Resins, Inc.|Glass fiber insulation binder|

---

EP0442406B1|1990-02-14|1995-07-26|Material Engineering Technology Laboratory, Inc.|Filled and sealed, self-contained mixing container|

---

JP2574051B2|1990-02-28|1997-01-22|明治製菓株式会社|Gene encoding indole acetate biosynthesis enzyme|

---

AT113307T|1990-03-03|1994-11-15|Basf Ag|MOLDED BODY.|

---

RU1765996C|1990-06-11|1995-08-27|Назаров Петр Васильевич|Method of making heat- and soundproofing articles|

---

FR2663049B1|1990-06-12|1994-05-13|Isover Saint Gobain|RECYCLING OF FIBROUS PRODUCTS IN A MATTRESS PRODUCTION LINE FROM FIBERS.|

---

US5041595A|1990-09-26|1991-08-20|Union Carbide Chemicals And Plastics Technology Corporation|Method for manufacturing vinylalkoxysilanes|

---

US6495656B1|1990-11-30|2002-12-17|Eastman Chemical Company|Copolyesters and fibrous materials formed therefrom|

---

AT224435T|1990-12-28|2002-10-15|K C Shen Technology Internat L|HEAT-CURABLE RESIN AND COMPOSITE MADE OF LIGNOCELLULOSE MATERIAL|

---

GB9100277D0|1991-01-07|1991-02-20|Courtaulds Fibres Ltd|Adhesive|

---

US5240498A|1991-01-09|1993-08-31|Martin Marietta Magnesia Specialties Inc.|Carbonaceous binder|

---

US5217741A|1991-01-25|1993-06-08|Snow Brand Milk Products Co., Ltd.|Solution containing whey protein, whey protein gel, whey protein powder and processed food product produced by using the same|

---

GB9108604D0|1991-04-22|1991-06-05|Nadreph Ltd|Gel products and a process for making them|

---

US5143582A|1991-05-06|1992-09-01|Rohm And Haas Company|Heat-resistant nonwoven fabrics|

---

US5128407A|1991-07-25|1992-07-07|Miles Inc.|Urea extended polyisocyanates|

---

DE4127733A1|1991-08-22|1993-02-25|Basf Ag|Graft polymers of natural substances containing saccharide structures or derivatives thereof and ethylenically unsaturated compounds and their use.|

---

US5123949A|1991-09-06|1992-06-23|Manville Corporation|Method of introducing addivites to fibrous products|

---

GB9126828D0|1991-12-18|1992-02-19|British American Tobacco Co|Improvements relating to smoking articles|

---

DE4142261A1|1991-12-20|1993-06-24|Man Technologie Gmbh|Coating and infiltration of substrates in a short time - by heating substrate using body which matches the component contour at gas outflow side and opt. gas entry side|

---

JPH05186635A|1992-01-10|1993-07-27|Goyo Paper Working Co Ltd|Packaging material|

---

DE4202248A1|1992-01-28|1993-07-29|Belland Ag|METHOD FOR RECOVERY OF POLYMERS SOLVED IN AQUEOUS ALKALINE OR ACID MILIEU|

---

FR2688791B1|1992-03-20|1995-06-16|Roquette Freres|BINDING COMPOSITION FOR THE PREPARATION OF A NEW AGGLOMERATE BASED ON FINELY DIVIDED MATERIALS, PROCESS USING THIS COMPOSITION AND NEW AGGLOMERATE OBTAINED.|

---

US5550189A|1992-04-17|1996-08-27|Kimberly-Clark Corporation|Modified polysaccharides having improved absorbent properties and process for the preparation thereof|

---

US5534612A|1992-05-19|1996-07-09|Schuller International, Inc.|Glass fiber binding compositions, process of making glass fiber binding compositions, process of binding glass fibers, and glass fiber compositions|

---

US6077883A|1992-05-19|2000-06-20|Johns Manville International, Inc.|Emulsified furan resin based glass fiber binding compositions, process of binding glass fibers, and glass fiber compositions|

---

AT141245T|1992-05-19|1996-08-15|Schuller Int Inc|BINDER COMPOSITIONS FOR GLASS FIBERS, METHOD FOR BINDING GLASS FIBERS AND GLASS FIBER COMPOSITIONS|

---

US5389716A|1992-06-26|1995-02-14|Georgia-Pacific Resins, Inc.|Fire resistant cured binder for fibrous mats|

---

BR9406219A|1993-01-23|1996-01-09|Helmut Schiwek|Glass fiber production process and installation|

---

US5661213A|1992-08-06|1997-08-26|Rohm And Haas Company|Curable aqueous composition and use as fiberglass nonwoven binder|

---

US5582670A|1992-08-11|1996-12-10|E. Khashoggi Industries|Methods for the manufacture of sheets having a highly inorganically filled organic polymer matrix|

---

US5434233A|1992-08-12|1995-07-18|Kiely; Donald E.|Polyaldaramide polymers useful for films and adhesives|

---

US7144474B1|1992-08-17|2006-12-05|Weyerhaeuser Co.|Method of binding particles to binder treated fibers|

---

US5641561A|1992-08-17|1997-06-24|Weyerhaeuser Company|Particle binding to fibers|

---

US5352480A|1992-08-17|1994-10-04|Weyerhaeuser Company|Method for binding particles to fibers using reactivatable binders|

---

US6340411B1|1992-08-17|2002-01-22|Weyerhaeuser Company|Fibrous product containing densifying agent|

---

US6391453B1|1992-08-17|2002-05-21|Weyernaeuser Company|Binder treated particles|

---

EP1217120A1|1992-08-17|2002-06-26|Weyerhaeuser Company|Particle binding to fibers|

---

US5538783A|1992-08-17|1996-07-23|Hansen; Michael R.|Non-polymeric organic binders for binding particles to fibers|

---

US5543215A|1992-08-17|1996-08-06|Weyerhaeuser Company|Polymeric binders for binding particles to fibers|

---

US5589256A|1992-08-17|1996-12-31|Weyerhaeuser Company|Particle binders that enhance fiber densification|

---

US5807364A|1992-08-17|1998-09-15|Weyerhaeuser Company|Binder treated fibrous webs and products|

---

US5547541A|1992-08-17|1996-08-20|Weyerhaeuser Company|Method for densifying fibers using a densifying agent|

---

US5300192A|1992-08-17|1994-04-05|Weyerhaeuser Company|Wet laid fiber sheet manufacturing with reactivatable binders for binding particles to fibers|

---

US5308896A|1992-08-17|1994-05-03|Weyerhaeuser Company|Particle binders for high bulk fibers|

---

FR2694894B1|1992-08-20|1994-11-10|Coletica|Use of a transacylation reaction between an esterified polysaccharide and a polyamine or polyhydroxylated substance for the manufacture of microparticles, process and composition.|

---

US5367849A|1992-09-08|1994-11-29|Bullock; Thomas W.|Insulation configurations and method of installation|

---

DE4233622C2|1992-10-06|2000-01-05|Rolf Hesch|Pressing process for coating a workpiece and press for carrying out the process|

---

FR2697023B1|1992-10-16|1994-12-30|Roquette Freres|Low-calorie glucose soluble polymer and process for the preparation of this polymer.|

---

US5300144A|1992-11-02|1994-04-05|Martin Marietta Magnesia Specialties, Inc.|Binder composition|

---

EP0601417A3|1992-12-11|1998-07-01|Hoechst Aktiengesellschaft|Physiologically compatible and degradable polymer-based carbohydrate receptor blockers, a method for their preparation and their use|

---

US5376614A|1992-12-11|1994-12-27|United Technologies Corporation|Regenerable supported amine-polyol sorbent|

---

US5545279A|1992-12-30|1996-08-13|Hall; Herbert L.|Method of making an insulation assembly|

---

US5672659A|1993-01-06|1997-09-30|Kinerton Limited|Ionic molecular conjugates of biodegradable polyesters and bioactive polypeptides|

---

US5863985A|1995-06-29|1999-01-26|Kinerton Limited|Ionic molecular conjugates of biodegradable polyesters and bioactive polypeptides|

---

US6221958B1|1993-01-06|2001-04-24|Societe De Conseils De Recherches Et D'applications Scientifiques, Sas|Ionic molecular conjugates of biodegradable polyesters and bioactive polypeptides|

---

IL104734D0|1993-02-15|1993-06-10|Univ Bar Ilan|Bioactive conjugates of cellulose with amino compounds|

---

EP0615166B1|1993-02-26|1998-09-23|Mitsui Chemicals, Inc.|Resins for electrophotographic toners|

---

US6090925A|1993-03-09|2000-07-18|Epic Therapeutics, Inc.|Macromolecular microparticles and methods of production and use|

---

US5981719A|1993-03-09|1999-11-09|Epic Therapeutics, Inc.|Macromolecular microparticles and methods of production and use|

---

US5554730A|1993-03-09|1996-09-10|Middlesex Sciences, Inc.|Method and kit for making a polysaccharide-protein conjugate|

---

DE4308089B4|1993-03-13|2004-05-19|Basf Ag|Formaldehyde-free binders for wood|

---

US5929184A|1993-06-02|1999-07-27|Geltex Pharmaceuticals, Inc.|Hydrophilic nonamine-containing and amine-containing copolymers and their use as bile acid sequestrants|

---

US6855337B1|1993-06-17|2005-02-15|Carle Development Foundation|Bear derived isolate and method|

---

US5318990A|1993-06-21|1994-06-07|Owens-Corning Fiberglas Technology Inc.|Fibrous glass binders|

---

US5340868A|1993-06-21|1994-08-23|Owens-Corning Fiberglass Technology Inc.|Fibrous glass binders|

---

US5942123A|1995-09-05|1999-08-24|Mcardle; Blaise|Method of using a filter aid protein-polysaccharide complex composition|

---

JP3399588B2|1993-07-20|2003-04-21|東洋紡績株式会社|Ink for writing implements|

---

AU687886B2|1993-09-29|1998-03-05|W.R. Grace & Co.-Conn.|Improved cement admixture product having improved rheological properties and process of forming same|

---

US5416139A|1993-10-07|1995-05-16|Zeiszler; Dennis E.|Structural building materials or articles obtained from crop plants or residues therefrom and/or polyolefin materials|

---

US5393849A|1993-10-19|1995-02-28|Georgia-Pacific Resins, Inc.|Curable polyester/polyamino compositions|

---

JP2811540B2|1993-10-20|1998-10-15|呉羽化学工業株式会社|Gas barrier film and method for producing the same|

---

US5503920A|1993-12-27|1996-04-02|Owens-Corning Fiberglass Technology, Inc.|Process for improving parting strength of fiberglass insulation|

---

DE4406172C2|1994-02-25|2003-10-02|Sanol Arznei Schwarz Gmbh|polyester|

---

DE4408688A1|1994-03-15|1995-09-21|Basf Ag|Formaldehyde-free binding, impregnating or coating compositions for fibrous webs|

---

GB9411080D0|1994-06-02|1994-07-20|Unilever Plc|Treatment|

---

GB9412007D0|1994-06-15|1994-08-03|Rockwell International A S|Production of mineral fibres|

---

US5580856A|1994-07-15|1996-12-03|Prestrelski; Steven J.|Formulation of a reconstituted protein, and method and kit for the production thereof|

---

US5492756A|1994-07-22|1996-02-20|Mississippi State University|Kenaf core board material|

---

US5955448A|1994-08-19|1999-09-21|Quadrant Holdings Cambridge Limited|Method for stabilization of biological substances during drying and subsequent storage and compositions thereof|

---

DE4432899A1|1994-09-15|1996-03-21|Wacker Chemie Gmbh|Crosslinkable polymer powder compositions|

---

CN1079811C|1994-11-21|2002-02-27|旭化成株式会社|Polymeric composite material|

---

US6441122B1|1995-01-05|2002-08-27|Johns Manville International, Inc.|Melamine in urea-extended phenol/formaldehyde fiberglass binders|

---

US5932344A|1995-02-07|1999-08-03|Daicel-Huels Ltd.|Cement retarder and cement retardative sheet|

---

EE9700180A|1995-02-21|1998-02-16|Rockwool Lapinus B.V.|Method of making a mineral wool product|

---

EP0735065B1|1995-03-24|1997-05-28|Giulini Chemie GmbH|Amphoteric polymer dispersion, process for preparation and its use|

---

US5919831A|1995-05-01|1999-07-06|Philipp; Warren H.|Process for making an ion exchange material|

---

US5670585A|1995-06-13|1997-09-23|Schuller International, Inc.|Use of polyacrylic acid and other polymers as additives in fiberglass formaldehyde based binders|

---

US5562740A|1995-06-15|1996-10-08|The Procter & Gamble Company|Process for preparing reduced odor and improved brightness individualized, polycarboxylic acid crosslinked fibers|

---

US5720796A|1995-08-08|1998-02-24|W. R. Grace & Co.-Conn.|Process of using roll press grinding aid for granulated blast furnace slag|

---

US5788423A|1995-09-08|1998-08-04|G.P. Industries, Inc.|Masonry block retaining wall with attached keylock facing panels and method of constructing the same|

---

US6458889B1|1995-12-18|2002-10-01|Cohesion Technologies, Inc.|Compositions and systems for forming crosslinked biomaterials and associated methods of preparation and use|

---

US7883693B2|1995-12-18|2011-02-08|Angiodevice International Gmbh|Compositions and systems for forming crosslinked biomaterials and methods of preparation of use|

---

ES2175168T3|1995-11-28|2002-11-16|Kimberly Clark Co|COLOR COMPOUNDS STABILIZED BY LIGHT.|

---

JPH09157627A|1995-12-13|1997-06-17|Sekisui Chem Co Ltd|Water-soluble tacky adhesive agent composition|

---

US6407225B1|1995-12-21|2002-06-18|The Dow Chemical Company|Compositions comprising hydroxy-functional polymers|

---

AU682630B2|1996-01-11|1997-10-09|Kowng Young Pharm. & Chem. Co., Ltd.|Non-heating food binder|

---

US5788243A|1996-01-23|1998-08-04|Harshaw; Bob F.|Biodegradable target|

---

DE19606394A1|1996-02-21|1997-08-28|Basf Ag|Formaldehyde-free, aqueous binders|

---

US6139619A|1996-02-29|2000-10-31|Borden Chemical, Inc.|Binders for cores and molds|

---

US5922403A|1996-03-12|1999-07-13|Tecle; Berhan|Method for isolating ultrafine and fine particles|

---

US6072086A|1996-04-12|2000-06-06|Intergen Company|Method and composition for controlling formaldehyde fixation by delayed quenching|

---

US6319683B1|1996-04-12|2001-11-20|Intergen Company|Method and composition for controlling formaldehyde fixation by delayed quenching|

---

DE19621573A1|1996-05-29|1997-12-04|Basf Ag|Thermally curable, aqueous compositions|

---

US5719092A|1996-05-31|1998-02-17|Eastman Kodak Company|Fiber/polymer composite for use as a photographic support|

---

US6299677B1|1996-06-25|2001-10-09|Borden Chemical, Inc.|Binders for cores and molds|

---

US5733624A|1996-07-22|1998-03-31|Guardian Fiberglass, Inc.|Mineral fiber insulation batt impregnated with coextruded polymer layering system|

---

AU742125B2|1996-08-21|2001-12-20|Rohm And Haas Company|A formaldehyde-free, accelerated cure aqueous composition for bonding glass fiber-heat resistant nonwovens|

---

US6067821A|1996-10-07|2000-05-30|Owens Corning Fiberglas Technology, Inc.|Process for making mineral wool fibers from lumps of uncalcined raw bauxite|

---

NL1004379C2|1996-10-29|1998-05-08|Borculo Cooep Weiprod|Use of sugar amines and sugar amides as an adhesive, as well as new sugar amines and sugar amides.|

---

KR20000053019A|1996-11-04|2000-08-25|네바드 에드워드 죤|Rigid polyurethane foams|

---

US20020161108A1|2000-03-09|2002-10-31|Stepan Company, A Corporation Of The State Of Delaware|Emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids|

---

US6310227B1|1997-01-31|2001-10-30|The Procter & Gamble Co.|Reduced calorie cooking and frying oils having improved hydrolytic stability, and process for preparing|

---

CZ293298B6|1997-02-03|2004-03-17|Isover Saint-Gobain|Biding agent for mineral wool and product of mineral wool bonded thereby|

---

US5932665A|1997-02-06|1999-08-03|Johns Manville International, Inc.|Polycarboxy polymer acid binders having reduced cure temperatures|

---

JPH10234314A|1997-02-24|1998-09-08|Miyoujiyou Shokuhin Kk|Composition for giving scorch on food|

---

US6475552B1|1997-03-19|2002-11-05|Danisco Finland Oy|Polymerization of mono and disaccharides using low levels of polycarboxylic acids|

---

AU6764998A|1997-03-19|1998-10-12|Cultor Food Science, Inc.|Polymerization of mono-and disaccharides using low levels of mineral acids|

---

CN1089727C|1997-04-11|2002-08-28|广州市环境保护科学研究所|Method for preparing cation/amphoteric graft polyacrylamide flocculating agent|

---

TW408152B|1997-04-25|2000-10-11|Rohm & Haas|Formaldehyde-free curable composition and method for bonding heat-resistant fibers of a nonwoven material by using the composition|

---

DE59806542D1|1997-05-02|2003-01-16|Henkel Dorus Gmbh & Co Kg|THERMOPLASTIC COMPOSITE MATERIAL|

---

US5954869A|1997-05-07|1999-09-21|Bioshield Technologies, Inc.|Water-stabilized organosilane compounds and methods for using the same|

---

EP0878135B1|1997-05-15|2002-03-13|Societe Des Produits Nestle S.A.|Process for preparing and extracting aromas|

---

DE19721691A1|1997-05-23|1998-11-26|Basf Ag|Adhesives based on an aqueous polymer dispersion, process for their preparation and their use|

---

IT1292024B1|1997-05-28|1999-01-25|Balzaretti Modigliani Spa|PROCESS AND DEVICE FOR THE RECYCLING OF WASTE IN A PRODUCTION OF MINERAL FIBERS|

---

DE19729161A1|1997-07-08|1999-01-14|Basf Ag|Thermally curable, aqueous compositions|

---

JP3188657B2|1997-07-24|2001-07-16|株式会社第一化成|Tablet or granular product|

---

US5977232A|1997-08-01|1999-11-02|Rohm And Haas Company|Formaldehyde-free, accelerated cure, aqueous composition for bonding glass fiber heat-resistant nonwovens|

---

DE19735959A1|1997-08-19|1999-02-25|Basf Ag|Thermally curable, aqueous binding agent composition|

---

US5895804A|1997-10-27|1999-04-20|National Starch And Chemical Investment Holding Corporation|Thermosetting polysaccharides|

---

US5983586A|1997-11-24|1999-11-16|Owens Corning Fiberglas Technology, Inc.|Fibrous insulation having integrated mineral fibers and organic fibers, and building structures insulated with such fibrous insulation|

---

US6171654B1|1997-11-28|2001-01-09|Seydel Research, Inc.|Method for bonding glass fibers with cross-linkable polyester resins|

---

JP3721530B2|1997-12-12|2005-11-30|昭和電工株式会社|Textile treatment composition|

---

US6379814B1|1997-12-19|2002-04-30|Georgia-Pacific Resins, Inc.|Cyclic urea-formaldehyde prepolymer for use in phenol-formaldehyde and melamine-formaldehyde resin-based binders|

---

US6143243A|1997-12-29|2000-11-07|Prestone Products Corporation|Method of inhibiting cavitation-erosion corrosion of aluminum surfaces using carboxylic acid based compositions comprising polymerizable-acid graft polymers|

---

NL1008041C2|1998-01-16|1999-07-19|Tidis B V I O|Application of a water-soluble binder system for the production of glass or rock wool.|

---

EP0933021A1|1998-02-02|1999-08-04|Rockwool International A/S|Process for the manufacture of a mineral wool planth growth substrate and the obtainable mineral wool plant growth substrate|

---

EP0936060A1|1998-02-13|1999-08-18|Rockwool International A/S|Man-made vitreous fibre products and their use in fire protection systems|

---

AT244799T|1998-03-19|2003-07-15|Rockwool Int|METHOD AND DEVICE FOR PRODUCING A MINERAL FIBER PRODUCT.|

---

US6140445A|1998-04-17|2000-10-31|Crompton Corporation|Silane functional oligomer|

---

US6291023B1|1998-04-22|2001-09-18|Sri International|Method and composition for textile printing|

---

US6171444B1|1998-04-22|2001-01-09|Sri International|Method and composition for the sizing of paper with a mixture of a polyacid and a polybase|

---

SI1084167T2|1998-05-18|2010-12-31|Rockwool Int|Stabilized aqueous phenolic binder for mineral wool and production of mineral wool products|

---

AT464334T|1998-05-18|2010-04-15|Knauf Fiber Glass Gmbh|BINDER COMPOSITION FOR GLASS FIBER AND METHOD OF MANUFACTURING|

---

CA2458333C|1998-05-28|2005-08-09|Owens Corning|Corrosion inhibiting composition for polyacrylic acid based binders|

---

CA2332621C|1998-05-28|2004-07-20|Owens Corning|Corrosion inhibiting composition for polyacrylic acid based binders|

---

JP3907837B2|1998-06-12|2007-04-18|富士フイルム株式会社|Image recording material|

---

US5993709A|1998-06-23|1999-11-30|Bonomo; Brian|Method for making composite board using phenol formaldehyde binder|

---

DE19833920A1|1998-07-28|2000-02-03|Basf Ag|Textile fabrics|

---

US6468668B1|1998-09-14|2002-10-22|Canon Kabushiki Kaisha|Cellulosic composite product and a method of producing the same|

---

EP0990727A1|1998-10-02|2000-04-05|Johns Manville International Inc.|Polycarboxy/polyol fiberglass binder|

---

US6331350B1|1998-10-02|2001-12-18|Johns Manville International, Inc.|Polycarboxy/polyol fiberglass binder of low pH|

---

US6231721B1|1998-10-09|2001-05-15|Weyerhaeuser Company|Compressible wood pulp product|

---

JP4554012B2|1998-10-13|2010-09-29|パナソニック株式会社|Aluminum electrolytic capacitor|

---

CN1251738A|1998-10-21|2000-05-03|朱国和|Medium product for soilless culture and its production method|

---

US6214265B1|1998-12-17|2001-04-10|Bayer Corporation|Mixed PMDI/resole resin binders for the production of wood composite products|

---

ES2307487T3|1999-03-19|2008-12-01|Saint-Gobain Cultilene B.V.|GROUND SUBSTRATE WITHOUT SOIL.|

---

CA2364626A1|1999-03-31|2000-10-05|Saul Rogols|Packaging and structural materials comprising potato peel waste|

---

US6210472B1|1999-04-08|2001-04-03|Marconi Data Systems Inc.|Transparent coating for laser marking|

---

US7029717B1|1999-04-16|2006-04-18|San-Ei Gen F.F.I., Inc.|Sucralose-containing composition and edible products containing the composition|

---

US6331513B1|1999-04-28|2001-12-18|Jacam Chemicals L.L.C.|Compositions for dissolving metal sulfates|

---

CA2372226A1|1999-05-14|2000-11-23|The Dow Chemical Company|Process for preparing starch and epoxy-based thermoplastic polymer compositions|

---

DE19923118A1|1999-05-19|2000-11-23|Henkel Kgaa|Polymerizable composition for the anticorrosion coating of metallic substrates contains an organic titanium, silicon or zirconium compound|

---

JP2000327841A|1999-05-24|2000-11-28|Canon Inc|Molding comprising sugar chain polymer compound|

---

US6194512B1|1999-06-28|2001-02-27|Owens Corning Fiberglas Technology, Inc.|Phenol/formaldehyde and polyacrylic acid co-binder and low emissions process for making the same|

---

DE19930555C1|1999-07-02|2001-01-18|Basf Coatings Ag|Aqueous coating material, especially an aqueous filler or stone chip protection primer|

---

US6133347A|1999-07-09|2000-10-17|Mbt Holding Ag|Oligomeric dispersant|

---

EP1086932A1|1999-07-16|2001-03-28|Rockwool International A/S|Resin for a mineral wool binder comprising the reaction product of an amine with a first and second anhydride|

---

EP2267094A1|1999-07-26|2010-12-29|Minnesota Corn Processors LLC|De-icing composition|

---

US6306997B1|1999-07-29|2001-10-23|Iowa State University Research Foundation, Inc.|Soybean-based adhesive resins and composite products utilizing such adhesives|

---

US6281298B1|1999-08-20|2001-08-28|H. B. Fuller Licensing & Financing Inc.|Water-based pressure sensitive adhesives having enhanced characteristics|

---

EP1268702B2|2000-02-11|2009-09-23|Heartland Resource Technologies LLC|Vegetable protein adhesive compositions|

---

US20030148084A1|2000-02-11|2003-08-07|Trocino Frank S.|Vegetable protein adhesive compositions|

---

AU5121701A|2000-03-31|2001-10-15|Norman L Holy|Compostable, degradable plastic compositions and articles thereof|

---

US6410036B1|2000-05-04|2002-06-25|E-L Management Corp.|Eutectic mixtures in cosmetic compositions|

---

US20020096278A1|2000-05-24|2002-07-25|Armstrong World Industries, Inc.|Durable acoustical panel and method of making the same|

---

EP1164163A1|2000-06-16|2001-12-19|Rockwool International A/S|Binder for mineral wool products|

---

DE10030563B4|2000-06-21|2005-06-30|Agrolinz Melamin Gmbh|Fiber composites high dimensional stability, weathering resistance and flame resistance, process for their preparation and their use|

---

EP1170265A1|2000-07-04|2002-01-09|Rockwool International A/S|Binder for mineral wool products|

---

US6379739B1|2000-09-20|2002-04-30|Griffith Laboratories Worldwide, Inc.|Acidulant system for marinades|

---

AU782086B2|2000-09-20|2005-06-30|Akzo Nobel N.V.|Mono urea and polysaccharide crosslinking systems|

---

US6613378B1|2000-10-18|2003-09-02|The United States Of America As Represented By The Secretary Of Agriculture|Sugar-based edible adhesives|

---

US6525009B2|2000-12-07|2003-02-25|International Business Machines Corporation|Polycarboxylates-based aqueous compositions for cleaning of screening apparatus|

---

DE10101944A1|2001-01-17|2002-07-18|Basf Ag|A new binder for finely divided materials, useful for preparation of flat-shaped articles from finely divided materials, comprises the reaction product of di or tricarboxylic acid or its anhydride with ammonia|

---

FR2820736B1|2001-02-14|2003-11-14|Saint Gobain Isover|PROCESS AND DEVICE FOR FORMING MINERAL WOOL|

---

US7816514B2|2001-02-16|2010-10-19|Cargill, Incorporated|Glucosamine and method of making glucosamine from microbial biomass|

---

JP3750552B2|2001-03-28|2006-03-01|日東紡績株式会社|Method for producing glass fiber wound body and method for producing glass fiber fabric|

---

US20020197352A1|2001-04-02|2002-12-26|Pacifichealth Laboratories, Inc.|Sports drink composition for enhancing glucose uptake into the muscle and extending endurance during physical exercise|

---

US6989171B2|2001-04-02|2006-01-24|Pacifichealth Laboratories, Inc.|Sports drink composition for enhancing glucose uptake into the muscle and extending endurance during physical exercise|

---

DE10116810A1|2001-04-04|2002-12-19|Wacker Chemie Gmbh|Binders and their use in processes for the production of molded parts based on mineral fibers|

---

PL373506A1|2001-04-10|2005-09-05|Danisco Usa|Polymerization of mono and disaccharides with monocarboxylic acids and lactones|

---

NZ549563A|2001-04-10|2008-01-31|Danisco Usa Inc|Carbohydrate polymers prepared by the polymerization of mono and disaccharides with monocarboxylic acids and lactones|

---

US20030040239A1|2001-05-17|2003-02-27|Certainteed Corporation|Thermal insulation containing supplemental infrared radiation absorbing material|

---

US7157524B2|2001-05-31|2007-01-02|Owens Corning Fiberglas Technology, Inc.|Surfactant-containing insulation binder|

---

NL1018568C2|2001-07-17|2003-01-21|Tno|Extraction of polysaccharides from vegetable and microbial material.|

---

US6755938B2|2001-08-20|2004-06-29|Armstrong World Industries, Inc.|Fibrous sheet binders|

---

JP4135387B2|2001-08-31|2008-08-20|東洋製罐株式会社|Gas barrier material, production method thereof, coating liquid for forming gas barrier layer and packaging material provided with gas barrier material|

---

US20040161993A1|2001-09-06|2004-08-19|Gary Tripp|Inorganic fiber insulation made from glass fibers and polymer bonding fibers|

---

TWI320039B|2001-09-21|2010-02-01|Lactam-containing compounds and derivatives thereof as factor xa inhibitors|

---

US20030087095A1|2001-09-28|2003-05-08|Lewis Irwin Charles|Sugar additive blend useful as a binder or impregnant for carbon products|

---

US6592211B2|2001-10-17|2003-07-15|Hewlett-Packard Development Company, L.P.|Electrostatic mechanism for inkjet printers resulting in improved image quality|

---

WO2003035740A1|2001-10-24|2003-05-01|Temple-Inland Forest Products Corporation|Saccharide-based resin for the preparation of composite products|

---

US6858074B2|2001-11-05|2005-02-22|Construction Research & Technology Gmbh|High early-strength cementitious composition|

---

JP3787085B2|2001-12-04|2006-06-21|関東化学株式会社|Composition for removing photoresist residue|

---

JP4464596B2|2002-02-15|2010-05-19|日本合成化学工業株式会社|binder|

---

PT1483347E|2002-02-20|2006-08-31|Du Pont|VARNISHS CONTAINING HIGHLY BRANCHED COPOLIESTER-POLYOL|

---

ES2331118T3|2002-02-22|2009-12-22|Genencor International, Inc.|GOLD AGENT.|

---

WO2003072637A1|2002-02-22|2003-09-04|Insert Therapeutics, Inc.|Carbohydrate-modified polymers, compositions and uses related thereto|

---

US6992203B2|2002-03-26|2006-01-31|Jh Biotech, Inc.|Metal complexes produced by Maillard Reaction products|

---

DE10218871A1|2002-04-26|2003-11-13|Degussa|Process for impregnating porous mineral substrates|

---

US6955844B2|2002-05-24|2005-10-18|Innovative Construction And Building Materials|Construction materials containing surface modified fibers|

---

FR2839966B1|2002-05-27|2004-07-23|Saint Gobain Isover|FILTERING MEDIA COMPRISING MINERAL FIBERS OBTAINED BY CENTRIFUGATION|

---

WO2003104284A2|2002-06-06|2003-12-18|Georgia-Pacific Resins, Inc.|Epoxide-type formaldehyde free insulation binder|

---

CA2489385C|2002-06-18|2011-12-20|Georgia-Pacific Resins, Inc.|Polyester-type formaldehyde free insulation binder|

---

US20040002567A1|2002-06-27|2004-01-01|Liang Chen|Odor free molding media having a polycarboxylic acid binder|

---

FR2842189B1|2002-07-12|2005-03-04|Saint Gobain Isover|THERMALLY INSULATING PRODUCT AND MANUFACTURING METHOD THEREOF|

---

EP1382642A1|2002-07-15|2004-01-21|Rockwool International A/S|Formaldehyde-free aqueous binder composition for mineral fibers|

---

JP2004060058A|2002-07-24|2004-02-26|Mitsubishi Heavy Ind Ltd|Fiber substrate for composite material|

---

US6887961B2|2002-07-26|2005-05-03|Kimberly-Clark Worldwide, Inc.|Absorbent binder composition and method of making it|

---

US6962714B2|2002-08-06|2005-11-08|Ecolab, Inc.|Critical fluid antimicrobial compositions and their use and generation|

---

US7384881B2|2002-08-16|2008-06-10|H.B. Fuller Licensing & Financing, Inc.|Aqueous formaldehyde-free composition and fiberglass insulation including the same|

---

US20040048531A1|2002-09-09|2004-03-11|Hector Belmares|Low formaldehyde emission panel|

---

US7494566B2|2002-09-13|2009-02-24|University Of Pittsburgh - Of The Commonwealth System Of Higher Education|Composition for increasing cellulosic product strength and method of increasing cellulosic product strength|

---

US7090745B2|2002-09-13|2006-08-15|University Of Pittsburgh|Method for increasing the strength of a cellulosic product|

---

US7202326B2|2002-09-24|2007-04-10|Asahi Kasei Chemicals Corporation|Glycolic acid copolymer and method for production thereof|

---

US7814512B2|2002-09-27|2010-10-12|Microsoft Corporation|Dynamic adjustment of EPG level of detail based on user behavior|

---

EP2431048B1|2002-10-08|2015-03-11|Danisco US Inc.|Phenolic binding peptides|

---

US6818694B2|2002-10-10|2004-11-16|Johns Manville International, Inc.|Filler extended fiberglass binder|

---

US7201825B2|2002-10-25|2007-04-10|Weyerhaeuser Company|Process for making a flowable and meterable densified fiber particle|

---

US7141626B2|2002-10-29|2006-11-28|National Starch And Chemical Investment Holding Corporation|Fiberglass non-woven catalyst|

---

US6699945B1|2002-12-03|2004-03-02|Owens Corning Fiberglas Technology, Inc.|Polycarboxylic acid based co-binder|

---

US7026390B2|2002-12-19|2006-04-11|Owens Corning Fiberglas Technology, Inc.|Extended binder compositions|

---

US20040131874A1|2003-01-08|2004-07-08|Georgia-Pacific Resins, Inc.|Reducing odor in fiberglass insulation bonded with urea-extended phenol-formaldehyde resins|

---

US7201778B2|2003-01-13|2007-04-10|North Carolina State University|Ionic cross-linking of ionic cotton with small molecular weight anionic or cationic molecules|

---

US6884849B2|2003-02-21|2005-04-26|Owens-Corning Fiberglas Technology, Inc.|Poly alcohol-based binder composition|

---

US7265169B2|2003-03-20|2007-09-04|State of Oregon Acting by and trhough the State Board of Higher Education on Behalf of Oregon State University|Adhesive compositions and methods of using and making the same|

---

US7056563B2|2003-04-04|2006-06-06|Weyerhaeuser Company|Hot cup made from an insulating paperboard|

---

DE10317937A1|2003-04-17|2004-11-04|Saint-Gobain Isover G+H Ag|Process for the production of pipe shells made of mineral wool and such pipe shells|

---

FR2854626B1|2003-05-07|2006-12-15|Saint Gobain Isover|MINERAL FIBER-BASED PRODUCT AND FIBER OBTAINING DEVICE|

---

US7947766B2|2003-06-06|2011-05-24|The Procter & Gamble Company|Crosslinking systems for hydroxyl polymers|

---

CA2470783A1|2003-06-12|2004-12-12|National Starch And Chemical Investment Holding Corporation|Fiberglass nonwoven binder|

---

US20040254285A1|2003-06-12|2004-12-16|Rodrigues Klein A.|Fiberglass nonwoven binder|

---

US7807077B2|2003-06-16|2010-10-05|Voxeljet Technology Gmbh|Methods and systems for the manufacture of layered three-dimensional forms|

---

US8870814B2|2003-07-31|2014-10-28|Boston Scientific Scimed, Inc.|Implantable or insertable medical devices containing silicone copolymer for controlled delivery of therapeutic agent|

---

CN1251738C|2003-08-05|2006-04-19|王春荣|Chinese medicine for treating ashen nail and its preparation method|

---

AU2004201002B2|2003-08-26|2009-08-06|Rohm And Haas Company|Curable aqueous composition and use as heat-resistant nonwoven binder|

---

US20050059770A1|2003-09-15|2005-03-17|Georgia-Pacific Resins Corporation|Formaldehyde free insulation binder|

---

DE10342858A1|2003-09-15|2005-04-21|Basf Ag|Use of formaldehyde-free aqueous binders for substrates|

---

DE10344926B3|2003-09-25|2005-01-20|Dynea Erkner Gmbh|Wooden components, eg boards, with one or more strand layers with a binding agent system, are produced by partial hardening during a first stage, and forming during a second stage|

---

EP1522642A1|2003-10-06|2005-04-13|Saint-Gobain Isover G+H Ag|Insulating mat of mineral fibre wound in a roll for press fitting between beams|

---

BRPI0414847B1|2003-10-06|2016-04-12|Saint Gobain Isover|insulation material element|

---

US20070009582A1|2003-10-07|2007-01-11|Madsen Niels J|Composition useful as an adhesive and use of such a composition|

---

EP1524282A1|2003-10-15|2005-04-20|Sika Technology AG|Two-component polyurethane composition having high early strength|

---

US20050208095A1|2003-11-20|2005-09-22|Angiotech International Ag|Polymer compositions and methods for their use|

---

US7833338B2|2004-02-18|2010-11-16|Meadwestvaco Packaging Systems, Llc|Method for producing bitumen compositions|

---

ZA200606788B|2004-02-18|2007-12-27|Meadwestvaco Corp|Method for producing bituminous compositions|

---

US7297204B2|2004-02-18|2007-11-20|Meadwestvaco Corporation|Water-in-oil bituminous dispersions and methods for producing paving compositions from the same|

---

US7842382B2|2004-03-11|2010-11-30|Knauf Insulation Gmbh|Binder compositions and associated methods|

---

DE102004033561B4|2004-03-11|2007-09-13|German Carbon Teterow Gmbh|Process for the preparation of form activated carbon|

---

UA89952C2|2004-03-11|2010-03-25|Кнауф Инсулейшн Гмбх|Binder compositions, method of bonding fiberglass material|

---

DE102004013390A1|2004-03-17|2005-10-06|Basf Ag|roofing sheets|

---

US20050215153A1|2004-03-23|2005-09-29|Cossement Marc R|Dextrin binder composition for heat resistant non-wovens|

---

JP4527435B2|2004-04-19|2010-08-18|関西ペイント株式会社|CURABLE COMPOSITION AND COATING METHOD USING THE COMPOSITION|

---

US7404875B2|2004-04-28|2008-07-29|Georgia-Pacific Consumer Products Lp|Modified creping adhesive composition and method of use thereof|

---

US6977116B2|2004-04-29|2005-12-20|The Procter & Gamble Company|Polymeric structures and method for making same|

---

EP1769004B1|2004-06-21|2017-08-09|Evonik Degussa GmbH|Water-absorbing polysaccharide and method for producing the same|

---

US7781512B2|2004-07-09|2010-08-24|Johns Manville|Control of product in curing ovens for formaldehyde-free glass fiber products|

---

US20060044302A1|2004-08-25|2006-03-02|Wilson Chen|Notebook DC power sharing arrangement|

---

WO2006044302A1|2004-10-13|2006-04-27|Knauf Insulation Gmbh|Polyester binding compositions|

---

DE102004051861A1|2004-10-26|2006-04-27|Degussa Ag|Use of an aqueous dispersion based on an unsaturated, amorphous polyester based on certain dicidol isomers|

---

US20060099870A1|2004-11-08|2006-05-11|Garcia Ruben G|Fiber mat bound with a formaldehyde free binder, asphalt coated mat and method|

---

US7514027B2|2005-02-17|2009-04-07|Saint-Gobain Isover|Process for manufacturing products of mineral wool, in particular monolayer and multilayer products|

---

FR2882366B1|2005-02-18|2008-04-18|Coletica Sa|RETICULATED CARBOHYDRATE POLYMER, IN PARTICULAR BASED ON POLYSACCHARIDES AND / OR POLYOLS|

---

KR100712970B1|2005-03-03|2007-05-02|롬 앤드 하아스 컴패니|Method for reducing corrosion|

---

US20060231487A1|2005-04-13|2006-10-19|Bartley Stuart L|Coated filter media|

---

JP2008542451A|2005-05-06|2008-11-27|ディネア オイ|Polyvinyl alcohol-based curable aqueous composition containing no formaldehyde|

---

DE102005023431A1|2005-05-20|2006-11-23|Juchem Gmbh|Water-based solution for application to dough pieces useful for producing laugengebaeck comprises an alkali metal or ammonium carbonate or bicarbonate and a sugar|

---

DE102005029479A1|2005-06-24|2007-01-04|Saint-Gobain Isover G+H Ag|Process for producing bonded mineral wool and binder therefor|

---

US8048257B2|2006-06-23|2011-11-01|Akzo Nobel Coating International B.V.|Adhesive system and method of producing a wood based product|

---

EP1741726A1|2005-07-08|2007-01-10|Rohm and Haas France SAS|Curable aqueous composition and use as water repellant fiberglass nonwoven binder|

---

US7579289B2|2006-07-05|2009-08-25|Rohm And Haas Company|Water repellant curable aqueous compositions|

---

EA019802B1|2005-07-26|2014-06-30|Кнауф Инзулацьон Гмбх|Formaldehyde-free uncured binder, composition comprising same and method for preparing fibers bound by a binder|

---

DE602006020736D1|2005-08-26|2011-04-28|Asahi Fibreglass Co|AQUEOUS BINDER FOR INORGANIC FIBERS AND THE USE THEREOF FOR HEAT AND / OR SOUND INSULATION|

---

ES2285618T3|2005-09-14|2007-11-16|National Starch And Chemical Investment Holding Corporation|NEW WATER-BASED ADHESIVES FOR INDUSTRIAL APPLICATIONS.|

---

CA2624983A1|2005-10-26|2007-05-03|Polymer Ventures, Inc.|Grease and water resistant article|

---

DE102005056792B4|2005-11-28|2008-06-19|Saint-Gobain Isover G+H Ag|Composition for formaldehyde-free phenolic resin binder and its use|

---

US7872088B2|2006-02-16|2011-01-18|Knauf Insulation Gmbh|Low formaldehyde emission fiberglass|

---

US20070270070A1|2006-05-19|2007-11-22|Hamed Othman A|Chemically Stiffened Fibers In Sheet Form|

---

US20070287018A1|2006-06-09|2007-12-13|Georgia-Pacific Resins, Inc.|Fibrous mats having reduced formaldehyde emissions|

---

US9169157B2|2006-06-16|2015-10-27|Georgia-Pacific Chemicals Llc|Formaldehyde free binder|

---

US7795354B2|2006-06-16|2010-09-14|Georgia-Pacific Chemicals Llc|Formaldehyde free binder|

---

US7803879B2|2006-06-16|2010-09-28|Georgia-Pacific Chemicals Llc|Formaldehyde free binder|

---

US7829611B2|2006-08-24|2010-11-09|Rohm And Haas Company|Curable composition|

---

US7749923B2|2006-09-07|2010-07-06|Johns Manville|Facing and faced insulation products|

---

ES2458965T5|2006-11-03|2018-06-27|Prefere Resins Holding Gmbh|Renewable binder for nonwoven materials|

---

US20080160302A1|2006-12-27|2008-07-03|Jawed Asrar|Modified fibers for use in the formation of thermoplastic fiber-reinforced composite articles and process|

---

JP2008163178A|2006-12-28|2008-07-17|Advics:Kk|Friction material for brake|

---

EP3795546A1|2007-01-25|2021-03-24|Knauf Insulation GmbH|Binders and materials made therewith|

---

WO2008089847A1|2007-01-25|2008-07-31|Knauf Insulation Limited|Composite wood board|

---

PL2124521T3|2007-01-25|2019-09-30|Knauf Insulation|Hydroponics growing medium|

---

SI2126179T1|2007-01-25|2014-12-31|Knauf Insulation|Formaldehyde-free mineral fibre insulation product|

---

EP2450493A3|2007-01-25|2015-07-29|Knauf Insulation SPRL|Mineral fibre board|

---

WO2008089848A1|2007-01-25|2008-07-31|Knauf Insulation Limited|Mineral fibre insulation|

---

EP1958975B1|2007-02-06|2011-07-20|nolax AG|Dual component glue|

---

US8552140B2|2007-04-13|2013-10-08|Knauf Insulation Gmbh|Composite maillard-resole binders|

---

JP2009102604A|2007-05-09|2009-05-14|Sekisui Chem Co Ltd|Tannin-base adhesive, woody composite material made by using the same, and method for producing the composite material|

---

WO2008141201A1|2007-05-10|2008-11-20|Fish Christopher N|Composite materials|

---

US20100320113A1|2007-07-05|2010-12-23|Knauf Insulation Gmbh|Hydroxymonocarboxylic acid-based maillard binder|

---

DE102007035334A1|2007-07-27|2009-01-29|Boehringer Ingelheim Pharma Gmbh & Co. Kg|Novel substituted arylsulfonylglycines, their preparation and their use as pharmaceuticals|

---

GB0715100D0|2007-08-03|2007-09-12|Knauf Insulation Ltd|Binders|

---

TW200925232A|2007-08-09|2009-06-16|Sumika Chemtex Company Ltd|Water system adhesive|

---

FR2924719B1|2007-12-05|2010-09-10|Saint Gobain Isover|SIZING COMPOSITION FOR MINERAL WOOL COMPRISING MONOSACCHARIDE AND / OR POLYSACCHARIDE AND POLYCARBOXYLIC ORGANIC ACID, AND INSULATING PRODUCTS OBTAINED|

---

US8580375B2|2008-11-24|2013-11-12|Rohm And Haas Company|Soy composite materials comprising a reducing sugar and methods of making the same|

---

JP4927066B2|2007-12-26|2012-05-09|ロームアンドハースカンパニー|Curable composition|

---

JP4789995B2|2007-12-26|2011-10-12|ロームアンドハースカンパニー|Composite material and manufacturing method thereof|

---

CA2720844C|2008-04-14|2016-06-14|Dow Global Technologies Inc.|Use of filler that undergoes endothermic phase transition to lower the reaction exotherm of epoxy based compositions|

---

PE20100438A1|2008-06-05|2010-07-14|Georgia Pacific Chemicals Llc|COMPOSITION OF AQUEOUS SUSPENSION WITH PARTICLES OF VALUABLE MATERIALS AND IMPURITIES|

---

JP5248954B2|2008-09-02|2013-07-31|スリーエムイノベイティブプロパティズカンパニー|Abrasive products containing inclusion compounds|

---

CA2742829C|2008-11-12|2017-02-07|Georgia-Pacific Chemicals Llc|Method for inhibiting ice formation and accumulation|

---

ES2704135T3|2009-02-27|2019-03-14|Rohm & Haas|Fast-curing carbohydrate composition|

---

DE102009021555B4|2009-05-15|2011-06-22|AGM Mader GmbH, 85221|Process for the preparation of a binder and use of such a binder for the production of a shaped body|

---

FR2946352B1|2009-06-04|2012-11-09|Saint Gobain Isover|MINERAL WOOL SIZING COMPOSITION COMPRISING A SACCHARIDE, A POLYCARBOXYLIC ORGANIC ACID AND A REACTIVE SILICONE, AND INSULATING PRODUCTS OBTAINED|

---

EP2462169B1|2009-08-07|2019-02-27|Knauf Insulation|Molasses binder|

---

US9365963B2|2009-08-11|2016-06-14|Johns Manville|Curable fiberglass binder|

---

US20110040010A1|2009-08-11|2011-02-17|Kiarash Alavi Shooshtari|Curable fiberglass binder comprising salt of inorganic acid|

---

US9994482B2|2009-08-11|2018-06-12|Johns Manville|Curable fiberglass binder|

---

DK2464773T3|2009-08-11|2017-11-13|Johns Manville|Method of Bonding Fiberglass and Fiberglass Product|

---

US8377564B2|2009-08-19|2013-02-19|Johns Manville|Cellulosic composite|

---

US8372900B2|2009-08-19|2013-02-12|Johns Manville|Cellulosic composite with binder comprising salt of inorganic acid|

---

US8708162B2|2009-08-19|2014-04-29|Johns Manville|Polymeric fiber webs with binder comprising salt of inorganic acid|

---

US8680224B2|2010-02-01|2014-03-25|Johns Manville|Formaldehyde-free protein-containing binder compositions|

---

EP2553010B2|2010-03-31|2020-03-11|Knauf Insulation GmbH|Insulation products having a non-aqueous moisturizer|

---

JP5616277B2|2010-04-22|2014-10-29|ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ|Durable thermosetting binder composition from 5-carbon reducing sugar and use as wood binder|

---

EP2386605B1|2010-04-22|2017-08-23|Rohm and Haas Company|Durable thermosets from reducing sugars and primary polyamines|

---

MX339649B|2010-05-07|2016-06-02|Knauf Insulation |Carbohydrate binders and materials made therewith.|

---

CN105176460B|2010-05-07|2018-02-06|克瑙夫绝缘私人有限公司|The more amine bonding agents of carbohydrate and the material with its preparation|

---

CA2801546C|2010-06-07|2018-07-10|Knauf Insulation|Fiber products having temperature control additives|

---

JP5616291B2|2010-06-11|2014-10-29|ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ|Fast-curing thermosetting materials from 5- and 6-membered cyclic enamine compounds prepared from dialdehydes|

---

US20130174758A1|2010-09-17|2013-07-11|Knauf Insulation Gmbh|Organic acid carbohydrate binders and materials made therewith|

---

FR2978768B1|2011-08-05|2014-11-28|Saint Gobain Isover|SINKING COMPOSITION FOR MINERAL WOOL BASED ON SUCROSE REDUCER AND HYDROGEN SACCHARIDE, AND INSULATING PRODUCTS OBTAINED|

---

GB201120137D0|2011-11-22|2012-01-04|Dynea Oy|Modified binder compositions|

---

DE112012005805T5|2012-02-03|2014-10-16|Toyota Jidosha Kabushiki Kaisha|Electric storage system|

---

GB201206193D0|2012-04-05|2012-05-23|Knauf Insulation Ltd|Binders and associated products|

---

US10815593B2|2012-11-13|2020-10-27|Johns Manville|Viscosity modified formaldehyde-free binder compositions|EA019802B1|2005-07-26|2014-06-30|Кнауф Инзулацьон Гмбх|Formaldehyde-free uncured binder, composition comprising same and method for preparing fibers bound by a binder|

---

EP3795546A1|2007-01-25|2021-03-24|Knauf Insulation GmbH|Binders and materials made therewith|

---

EP2450493A3|2007-01-25|2015-07-29|Knauf Insulation SPRL|Mineral fibre board|

---

WO2008089847A1|2007-01-25|2008-07-31|Knauf Insulation Limited|Composite wood board|

---

US8552140B2|2007-04-13|2013-10-08|Knauf Insulation Gmbh|Composite maillard-resole binders|

---

GB0715100D0|2007-08-03|2007-09-12|Knauf Insulation Ltd|Binders|

---

EP2462169B1|2009-08-07|2019-02-27|Knauf Insulation|Molasses binder|

---

MX339649B|2010-05-07|2016-06-02|Knauf Insulation |Carbohydrate binders and materials made therewith.|

---

CA2834816C|2011-05-07|2020-05-12|Knauf Insulation|Liquid high solids binder composition|

---

CN105176460B|2010-05-07|2018-02-06|克瑙夫绝缘私人有限公司|The more amine bonding agents of carbohydrate and the material with its preparation|

---

JP5977015B2|2010-11-30|2016-08-24|ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ|Stable reactive thermosetting formulations of reducing sugars and amines|

---

FR2975689B1|2011-05-25|2014-02-28|Saint Gobain Isover|FORMALDEHYDE - FREE SIZING COMPOSITION FOR FIBERS, ESPECIALLY MINERAL, AND RESULTING PRODUCTS.|

---

GB201115172D0|2011-09-02|2011-10-19|Knauf Insulation Ltd|Carbohydrate based binder system and method of its production|

---

BE1020570A3|2011-11-04|2014-01-07|Knauf Insulation|BINDERS AND MATERIALS THAT DIE.|

---

BE1020571A3|2011-11-04|2014-01-07|Knauf Insulation|BINDERS AND MATERIALS THAT DIE.|

---

GB201120137D0|2011-11-22|2012-01-04|Dynea Oy|Modified binder compositions|

---

GB201206193D0|2012-04-05|2012-05-23|Knauf Insulation Ltd|Binders and associated products|

---

EP2669349B1|2012-05-29|2014-06-04|Rohm and Haas Company|Aqueous amine-carbohydrate thermosets having reduced weight loss upon cure and improved early dry strength|

---

EP2669325B1|2012-05-29|2016-01-13|Rohm and Haas Company|Bio-based flame resistant thermosetting binders with improved wet resistance|

---

GB201214734D0|2012-08-17|2012-10-03|Knauf Insulation Ltd|Wood board and process for its production|

---

PL2928935T3|2012-12-05|2021-11-02|Knauf Insulation Sprl|Binders|

---

EP2928936A2|2012-12-05|2015-10-14|Knauf Insulation SPRL|Binder|

---

EP2969448B1|2013-03-13|2017-08-02|Knauf Insulation GmbH|Molding process for insulation product|

---

US10167226B2|2013-07-18|2019-01-01|Johns Manville|Anti-static agent for glass fiber insulation|

---

CA2926033C|2013-10-16|2021-06-15|Rockwool International A/S|Man-made vitreous fibres|

---

EP2884259A1|2013-12-11|2015-06-17|Rockwool International A/S|Method for detecting curing of the binder in a mineral fibre product|

---

EP2930195B1|2014-04-11|2017-02-01|SWISS KRONO Tec AG|Adhesive composition for panels containing fibres and a method for the production thereof|

---

EP2947117B1|2014-05-19|2018-07-11|Rockwool International A/S|Analytical binder for mineral wool products|

---

GB201408909D0|2014-05-20|2014-07-02|Knauf Insulation Ltd|Binders|

---

GB201412709D0|2014-07-17|2014-09-03|Knauf Insulation And Knauf Insulation Ltd|Improved binder compositions and uses thereof|

---

GB201413402D0|2014-07-29|2014-09-10|Knauf Insulation Ltd|Laminates|

---

PT3067402T|2015-03-09|2017-07-28|SWISS KRONO Tec AG|Binder composition and use of same in wooden boards|

---

GB201517867D0|2015-10-09|2015-11-25|Knauf Insulation Ltd|Wood particle boards|

---

GB201517882D0|2015-10-09|2015-11-25|Knauf Insulation Ltd|Wood particle boards|

---

LT3219756T|2016-03-17|2018-10-10|Sestec Sp. Z O.O.|Formaldehyde-free wood binder|

---

EP3455183B1|2016-05-13|2021-07-07|Rockwool International A/S|Binder composition for mineral fibers comprising at least one hydrocolloid.|

---

RU2753338C2|2017-05-11|2021-08-13|Роквул Интернэшнл А/С|Fire-fighting insulation product and application of such product|

---

GB201610063D0|2016-06-09|2016-07-27|Knauf Insulation Ltd|Binders|

---

GB201701569D0|2017-01-31|2017-03-15|Knauf Insulation Ltd|Improved binder compositions and uses thereof|

---

WO2019018384A2|2017-07-20|2019-01-24|Xinova, LLC|Stabilized biofiller particles and polymer compositions including the same|

---

AU2018348020A1|2017-10-09|2020-04-09|Owens Corning Intellectual Capital, Llc|Aqueous binder compositions|

---

US11111372B2|2017-10-09|2021-09-07|Owens Corning Intellectual Capital, Llc|Aqueous binder compositions|

---

EP3511353A1|2018-01-11|2019-07-17|SWISS KRONO Tec AG|Formaldehyde-free adhesive composition for panels containing lignocellulose and method for the production thereof|

---

GB201804907D0|2018-03-27|2018-05-09|Knauf Insulation Ltd|Composite products|

---

GB201804906D0|2018-03-27|2018-05-09|Knauf Insulation Ltd|Wood boards|

---

GB2574206A|2018-05-29|2019-12-04|Knauf Insulation Sprl|Briquettes|

---

WO2021158599A1|2020-02-04|2021-08-12|Cargill, Incorporated|Carbohydrate-based adhesives|

法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-04| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-08| 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 07/05/2011, 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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US33245810P| true| 2010-05-07|2010-05-07|

---

US61332458|2010-05-07|

---

PCT/EP2011/057363|WO2011138458A1|2010-05-07|2011-05-07|Carbohydrate polyamine binders and materials made therewith|

---