TWI389996B - Binders and materials made therewith - Google Patents

Description

Adhesive and materials made thereof

The present invention relates to a binder that produces or promotes bonding in non-assembled or loosely assembled materials.

Adhesives can be used to make materials from non-assembled or loosely assembled materials. For example, a binder can bond two or more surfaces together. Adhesives can be broadly classified into two main categories: organic and inorganic binders, in which organic materials can be subdivided into animal, plant and synthetic sources. Another classification of binders is based on the chemical nature of the compounds: (1) protein or protein derivatives; (2) starch, cellulose or gums and their derivatives; (3) thermoplastic synthetic resins; (4) thermoset Synthetic resin; (5) natural resin and asphalt; (6) natural and synthetic rubber; and (7) inorganic binder. They can also be classified according to the purpose of the adhesive: (1) bonded rigid surfaces such as rigid plastics and metals; and (2) bonded flexible surfaces such as flexible plastics and thin metal sheets, among others.

Thermoplastic binders include a variety of polymeric materials such as polyvinyl acetate, polyvinyl butyral, polyvinyl alcohol and other polyethylene resins; polystyrene resins; acrylic and methacrylate resins; cyanoacrylates and various other Synthetic resins such as polyisobutylene polyamide, benzofuran-indene products and polyfluorene. These thermoplastic cements have long-lasting solubility and fusibility to soften under stress and upon heating. It can be used to make a variety of products, such as tapes.

Thermosetting binders include various phenol-aldehydes, urea-aldehydes, melamine-aldehydes, and other condensation-polymeric materials such as furan resins and polyurethane resins. Thermosetting binders can be characterized by their conversion to insoluble and infusible materials by means of heat or catalysis. A binder composition comprising phenol-, resorcinol-, urea-, melamine-formaldehyde, phenol furfural, and the like is used to bond fabrics, plastics, rubber, and many other materials.

As noted above, the binder is used to make materials from non-assembled or loosely assembled materials. Thus, we desire a composition that can be used as a binder.

The cured or uncured adhesive of the exemplary embodiments of the present invention may include one or more of the following features or a combination thereof. Furthermore, the materials of the present invention may include one or more of the following features or combinations thereof: First, it should be understood that the present adhesives can be used in a variety of manufacturing applications to create or promote bonding in a collection of non-assembled or loosely assembled materials. A collection includes two or more components. The binder creates or promotes bonding in at least two components of the collection. For example, the binder can bind the collection of materials together to cause the material to adhere together in a manner to resist separation. The binders described herein can be used in the manufacture of any material.

One of the potential features of the present invention is that it does not contain formaldehyde. Therefore, the material on which the binder is applied is also free of formaldehyde (e.g., fiberglass). Furthermore, the binder of the present invention may have a reduced trimethylamine content compared to other conventional binders.

With regard to the chemical composition of the binder of the present invention, it may include ester and/or polyester compounds. Such binders may include combinations of ester and/or polyester compounds with vegetable oils such as soybean oil. Additionally, the binders may include combinations of ester and/or polyester compounds with sodium salts of organic acids. These binders may include sodium salts of inorganic acids. These binders may also include potassium salts of organic acids. Additionally, the binders can include potassium salts of mineral acids. The binder may comprise a combination of an ester and/or polyester compound with a clay additive such as montmorillonite.

Furthermore, the binder of the present invention may comprise the product of a Maillard reaction. See, for example, Figure 2. As shown in Figure 2, the Maillard reaction produces a black matrix-like, high molecular weight furan-containing ring and nitrogen-containing polymer that varies depending on the structure of the reactants and their preparation conditions. Black-like concentrates exhibit a C:N ratio, degree of unsaturation, and chemical aromaticity as a function of temperature and heating time. (See Ames, J. M. in "The Maillard Browning Reaction-an update," Chemistry and Industry (Great Britain), 1988, 7, pp. 558-561, the disclosure of which is incorporated herein by reference. Thus, the binder can be prepared via a Maillard reaction and thus comprises a melanoid. It is to be understood that the binder may comprise melanoid-like or other Maillard reaction products which are produced by a separate process and which are then simply added to the composition comprising the binder. Black essence such as in the binder may be water insoluble. In addition, the binders can be thermoset binders.

The Maillard-derived Maillard reactant can include an amine reactant that reacts with a reducing sugar carbohydrate reactant. For example, an ammonium salt of a monomeric polycarboxylic acid can be reacted with (i) a monosaccharide in the form of its aldose or ketose or (ii) a polysaccharide or (iii) in combination therewith. In another variation, the ammonium salt of the polymeric polycarboxylic acid can be contacted with (i) a monosaccharide in the form of its aldose or ketose or (ii) a polysaccharide, or (iii) in combination therewith. In still another variation, the amino acid can be contacted with (i) a monosaccharide in the form of its aldose or ketose, or (ii) with a polysaccharide or (iii) in combination therewith. Further, the peptide may be contacted with (i) a monosaccharide in the form of its aldose or ketose or (ii) in combination with a polysaccharide or (iii). Alternatively, the protein may be contacted with (i) a monosaccharide in the form of its aldose or ketose or (ii) in combination with a polysaccharide or (iii).

It should also be understood that the binder of the present invention may include a melanoid produced in a non-sugar variant of the Maillard reaction. In such reactions, the amine reactant is contacted with a non-carbohydrate carbonyl reactant. In an exemplary variation, the ammonium salt of the monomeric polycarboxylic acid is contacted with a non-carbohydrate carbonyl reactant (eg, pyruvic aldehyde, acetaldehyde, crotonaldehyde, 2-furfural, hydrazine, ascorbic acid, or the like) Or in contact with it. In another variation, the ammonium salt of the polymeric polycarboxylic acid can be contacted with or with a non-carbohydrate carbonyl reactant (eg, pyruvic aldehyde, acetaldehyde, crotonaldehyde, 2-furfural, hydrazine, ascorbic acid, or the like) Combination contact. In yet another exemplary variation, the amino acid can be contacted with or in combination with a non-carbohydrate carbonyl reactant such as pyruvic aldehyde, acetaldehyde, crotonaldehyde, 2-furfural, hydrazine, ascorbic acid or the like. . In another exemplary variation, the peptide can be contacted with or in combination with a non-carbohydrate carbonyl reactant (eg, pyruvic aldehyde, acetaldehyde, crotonaldehyde, 2-furfural, hydrazine, ascorbic acid, or the like). In yet another exemplary variation, the protein can be contacted with or in combination with a non-carbohydrate carbonyl reactant (e.g., pyruvic aldehyde, acetaldehyde, crotonaldehyde, 2-furfural, hydrazine, ascorbic acid, and the like).

The black essence discussed herein can be produced from a melanin-like reactant compound. These reactant compounds are placed in an aqueous solution of alkaline pH and are therefore not corrosive. That is, the alkaline solution prevents or inhibits corrosion or abrasion of a substance (for example, metal) caused by chemical decomposition caused by, for example, an acid. The reactant compounds can include a reducing sugar carbohydrate reactant and an amine reactant. Additionally, the reactant compounds can include non-carbohydrate carbonyl reactants and amine reactants.

It should also be understood that the binders described herein can be made only from compounds of the melanin-like reactants. That is, after the Maillard reactant is mixed, the mixture can be used as the binder of the present invention. These binders can be used to make uncured, formaldehyde-free materials such as fibrous materials.

Alternatively, the binder made from the Maillard reaction can be cured. These binders can be used to make solidified formaldehyde-free materials, such as fiber compositions. The compositions are water resistant and include water insoluble melanin as described above.

It should be understood that the binders described herein can be manufactured from a collection of non-assembled or loosely assembled materials. For example, such binders can be used to make fiber products. These products can be made from woven or non-woven fabrics. The fibers may be heat resistant or heat resistant fibers or combinations thereof. In an exemplary embodiment, the binders are used to bond glass fibers to produce fiberglass. In another exemplary embodiment, the binders are used to prepare a cellulosic composition. With regard to cellulosic compositions, such binders can be used to bond cellulosic materials to make, for example, wood fiberboard having desirable physical properties, such as mechanical strength.

One embodiment of the present invention is directed to a method for making a product from a collection of non-assembled or loosely assembled materials. An example of the use of this method is the production of fiberglass. However, as described above, the method can be used to make any material as long as the method produces or promotes bonding when in use. The method can include contacting the fibers with a thermosetting aqueous binder. The binder can include (i) an ammonium salt of a polycarboxylic acid reactant and (ii) a reducing sugar carbohydrate reactant. The two reactants are melatonin-like reactants (i.e., when the reactants react under the conditions that initiate the Maillard reaction, they produce a melanoidin). The method can further include removing water from the binder in contact with the fibers (i.e., dehydrating the binder). The method can also include curing a binder that is in contact with the glass fibers (e.g., thermally curing the binder).

Another example of using this method is the manufacture of cellulosic materials. The method can include contacting a cellulosic material, such as a cellulosic fiber, with a thermally curable aqueous binder. The binder can include (i) an ammonium salt of a polycarboxylic acid reactant and (ii) a reducing sugar carbohydrate reactant. As mentioned above, the two reactants are based on the black essence reactant compound. The method can also include removing water from the binder in contact with the cellulosic material. As mentioned previously, the method can also include curing the binder (e.g., heat curing).

One of the methods of using these binders is to bond the glass fibers together to form a fiberglass sheet. The fiberglass sheet can be processed to form one of several fiberglass materials, such as fiberglass spacers. In one example, the fiberglass material can comprise glass fibers in a range from about 80% to about 99% by weight. An uncured binder can be used to bond the glass fibers together. Curing binders can be used to bond the glass fibers together.

Furthermore, the present invention describes a fibrous product comprising a binder in contact with cellulosic fibers, such as those in the form of wood chips or sawdust. The board can be processed to form one of several wood fiberboard products. In one variation, the binder is uncured. In this variation, the uncured binder can be used to bond the cellulosic fibers together. Alternatively, a curing binder can be used to bond the cellulosic fibers together.

Other features of the present invention will become apparent to those skilled in the art from a <RTIgt;

Although the invention is susceptible to various modifications and alternative forms, the specific embodiments are described herein. However, it is to be understood that the invention is not intended to be limited to the details of the invention.

As used herein, the phrase "non-formaldehyde-free" means that the binder or the material incorporated into the binder will only release less than about 1 ppm of formaldehyde due to drying and/or solidification. The 1 ppm is based on the weight of the sample from which the formaldehyde is released.

Curing means that the binder has been exposed to conditions that initiate chemical changes. Examples of such chemical changes include, but are not limited to, (i) covalent bonding, (ii) hydrogen bonding of the binder component, and chemical crosslinking of the polymer and/or oligomer in the binder. These changes increase the durability and solvent resistance of the binder compared to uncured binders. The curing binder forms a thermoset material. Additionally, curing can include the production of melanoid. These classes of melatonin can be produced by Maillard reaction from a melanin-like reactant compound. In addition, the curing binder can increase the adhesion between the materials in a collection compared to the uncured binder. Curing can be initiated by, for example, heating, electromagnetic radiation, or an electron beam.

In the case where chemical changes (e.g., polymerization and cross-linking) in the binder result in water release, curing can be determined by the amount of water released above that which occurs when dried alone. Techniques for measuring the amount of water released during drying and the amount of water released when the binder cures are well known in the art.

According to the above paragraph, the uncured adhesive is uncured.

The term "basic" as used herein means a solution having a pH greater than or equal to about 7. For example, the solution pH can be less than or equal to about 10. Additionally, the solution can have a pH of from about 7 to about 10, or from about 8 to about 10, or from about 9 to about 10.

The term "ammonium" include (but are not limited ^{to) +} NH ₄ with, ⁺ NH ₃ R ¹ and ⁺ NH ^₂ R ¹ R _2, where ⁺ NH ^₂ R ¹ R ₂ in the R ¹ and R ² independently selected And wherein R ¹ and R ^{2 are each} selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, heterocyclyl, aryl and heteroaryl.

The term "alkyl" refers to a saturated monovalent chain of carbon atoms, which may optionally be branched; the term "cycloalkyl" refers to a monovalent chain of carbon atoms in which a portion forms a ring; the term "alkenyl" is intended to include at least one A carbon atom unsaturated monovalent chain of a double bond, which may optionally have a branch; the term "cycloalkenyl" means an unsaturated monovalent chain of a carbon atom in which a part forms a ring; the term "heterocyclic group" means that it includes at least one One of the heteroatoms forms a ring of carbon and a monovalent chain of heteroatoms, wherein the heteroatoms are selected from the group consisting of nitrogen, oxygen and sulfur; the term "aryl" refers to an aromatic monocyclic or polycyclic ring of a carbon atom, such as phenyl. , naphthyl and the like; and the term "heteroaryl" refers to a carbon atom and at least one aromatic monocyclic or polycyclic ring selected from heteroatoms of nitrogen, oxygen and sulfur, such as pyridyl, pyrimidinyl, fluorenyl, Benzooxazolyl and the like. It is to be understood that each of the alkyl, cycloalkyl, alkenyl, cycloalkenyl and heterocyclic groups may optionally be substituted with a group independently selected from the group consisting of alkyl, haloalkyl, hydroxyalkyl, amine. Alkyl groups, carboxylic acids and derivatives thereof (including esters, decylamines and nitriles), hydroxyl groups, alkoxy groups, decyloxy groups, amine groups, alkyl and dialkylamino groups, decylamino groups, sulfur and the like and Its combination. It is further understood that each aryl and heteroaryl group may be optionally substituted with one or more substituents independently selected from the group consisting of halogen, hydroxy, amine, alkyl or dialkylamino, alkoxy, Alkylsulfonyl, cyano, nitro and the like.

The term "polycarboxylic acid" as used herein, refers to dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, pentacarboxylic acids, and similar monomeric polycarboxylic acids and anhydrides, and combinations thereof, as well as polymeric polycarboxylic acids, anhydrides, copolymers, and Its combination. In one aspect, the polycarboxylate ammonium salt reactant has sufficient non-volatility to maximize its ability to remain reacted with the Maillard-reacted carbohydrate reactant (discussed below). In another aspect, the polycarboxylic acid ammonium salt reactant can be substituted with other chemical functional groups.

For example, the monomeric polycarboxylic acid can be a dicarboxylic acid, including but not limited to: an unsaturated aliphatic dicarboxylic acid, a saturated aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, an unsaturated cyclic dicarboxylic acid. An acid, a saturated cyclic dicarboxylic acid, a hydroxy substituted derivative thereof, and the like. Or, by way of example, the (etc.) polycarboxylic acid itself may be a tricarboxylic acid, including but not limited to: an unsaturated aliphatic tricarboxylic acid, a saturated aliphatic tricarboxylic acid, an aromatic tricarboxylic acid, an unsaturated A cyclic tricarboxylic acid, a saturated cyclic tricarboxylic acid, a hydroxy substituted derivative thereof, and the like. It should be understood that any such polycarboxylic acid may be optionally substituted with, for example, a hydroxyl group, a halogen, an alkyl group, an alkoxy group, and the like. In a variation, the polycarboxylic acid is a saturated aliphatic tricarboxylic acid citric acid. Other suitable polycarboxylic acids are intended to include, but are not limited to, aconitic acid, adipic acid, sebacic acid, butane tetracarboxylic acid dihydride, butane tricarboxylic acid, chloric acid, citraconic acid, dicyclopentadiene- Maleic acid adduct, di-ethyltriamine pentaacetic acid, adduct of dipentene and maleic acid, ethylenediaminetetraacetic acid (EDTA), whole maleated rosin, maleated tart oil fatty acid , fumaric acid, glutaric acid, isophthalic acid, itaconic acid, oxidation with potassium peroxide to alcohol and then maleic acid rosin of carboxylic acid, maleic acid, malic acid, methyl fumaric acid, via KOLBE-Schmidt reaction with carbon dioxide to introduce 3-4 carboxyl groups of bisphenol A or bisphenol F, oxalic acid, phthalic acid, azelaic acid, succinic acid, tartaric acid, terephthalic acid, tetrabromophthalic acid , tetrachlorophthalic acid, tetrahydrophthalic acid, trimellitic acid, trimesic acid, and the like and anhydrides, and combinations thereof.

For example, the polymeric polycarboxylic acid can be an acid such as polyacrylic acid, polymethacrylic acid, polymaleic acid, and the like polymeric polycarboxylic acid, copolymers thereof, anhydrides thereof, and mixtures thereof. Examples of commercially available polyacrylic acids include AQUASET-529 (Rohm & Haas, Philadelphia, PA, USA), CRITERION 2000 (Kemira, Helsinki, Finland, Europe), NF1 (HBFuller, St. Paul, MN, USA), and SOKALAN ( BASF, Ludwigshafen, Germany, Europe). Regarding SOKALAN, it is a water-soluble polyacrylic acid copolymer of acrylic acid and maleic acid having a molecular weight of about 4,000. AQUASET-529 is a composition comprising polyacrylic acid crosslinked with glycerin and sodium hypophosphite as a catalyst. CRITERION 2000 is an acidic solution of polyacrylic acid sub-salt with a molecular weight of approximately 2,000. With regard to NF1, it is a copolymer comprising a carboxylic acid functional group and a hydroxyl functional group and a unit which does not contain both functional groups; NF1 also contains a chain transfer agent such as sodium hypophosphite or an organic phosphate ester catalyst.

In addition, compositions comprising a polymeric polycarboxylic acid are also intended to be used in the preparation of the binders described herein, for example, in U.S. Patent Nos. 5,318,990, 5,661,213, 6,136,916, and 6, 331,350, the disclosures of each of Their compositions in this article). In particular, aqueous solutions of polymeric polycarboxylic acids, polyols and catalysts are described in U.S. Patent Nos. 5,318,990 and 6,331,350.

Polymeric polycarboxylic acids include organic polymers or oligomers comprising more than one pendant carboxyl group, as described in U.S. Patent Nos. 5,318,990 and 6,331,350. The polymeric polycarboxylic acid can be a homopolymer or copolymer prepared from, but not necessarily limited to, the following unsaturated carboxylic acids: acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2 - methyl maleic acid, itaconic acid, 2-methyl itaconic acid, alpha, beta-methylene glutaric acid, and the like. Alternatively, the polymeric polycarboxylic acid can be prepared from, but not necessarily limited to, the following unsaturated anhydrides: maleic anhydride, itaconic anhydride, acrylic anhydride, methacrylic anhydride, and the like, and mixtures thereof. Methods of polymerizing such acids and anhydrides are well known in the chemical industry. The polymeric polycarboxylic acid may additionally comprise a copolymer of one or more of the foregoing unsaturated carboxylic acids or anhydrides with one or more vinyl compounds including, but not necessarily limited to, styrene, alpha-methyl styrene, propylene. Nitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidol methacrylate Base esters, vinyl methyl ethers, vinyl acetate and the like. Methods of preparing such copolymers are well known in the art. The polymeric polycarboxylic acids can include homopolymers and copolymers of polyacrylic acid. The polymeric polycarboxylic acid, and in particular the polyacrylic acid polymer, may have a molecular weight of less than 10,000, less than 5,000 or about 3,000 or less. For example, the molecular weight can be 2000.

The polyol (present in the composition comprising the polymeric polycarboxylic acid) comprises at least two hydroxyl groups as described in U.S. Patent Nos. 5,318,990 and 6,331,350. The polyol should have sufficient non-volatility during the heating or curing operation to render it substantially still reactive with the polymerization of the polycarboxylic acid in the composition. The polyol may be a compound having a molecular weight of less than about 1000 with at least two hydroxyl groups, such as ethylene glycol, glycerol, isovaerythritol, trimethylolpropane, sorbitol, sucrose, glucose, resorcinol, Catechol, pyrogallol, glycolated urea, 1,4-cyclohexanediol, diethanolamine, triethanolamine, and certain reactive polyols, such as beta-hydroxyalkylguanamine (for example, for example, Bis[ N , N -bis(β-hydroxyethyl)]hexanediamine), or it may be an addition polymer comprising at least two hydroxyl groups, such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate and Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and the like, homopolymers or copolymers.

The catalyst (present in the composition comprising the polymeric polycarboxylic acid) is a phosphorus-containing accelerator which can be a compound having a molecular weight of less than about 1000, such as an alkali metal poly, as described in U.S. Patent Nos. 5,318,990 and 6,331,350. a phosphate, an alkali metal dihydrogen phosphate, a polyphosphoric acid, and an alkylphosphonic acid, or it may be an oligomer or polymer having a phosphorus-containing group, for example, acrylic acid formed in the presence of sodium hypophosphite and/or An addition polymer of maleic acid, an addition polymer prepared from an ethylenically unsaturated monomer in the presence of a phosphite chain transfer agent or a terminator, and an addition polymer comprising an acid functional monomer residue, such as copolymerized methacrylic acid Ethyl phosphate and similar phosphonates and copolymerized vinyl sulfonic acid monomers and salts thereof. The phosphorus-containing accelerator may be used in an amount of from about 1% by weight to about 40% by weight based on the combined weight of the polymeric polycarboxylic acid and the polyol. The phosphorus-containing accelerator may be used in an amount of from about 2.5% by weight to about 10% by weight based on the combined weight of the polymeric polycarboxylic acid and the polyol. Examples of such catalysts include, but are not limited to, sodium hypophosphite, sodium phosphite, potassium phosphite, disodium pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium phosphate, polymetaphosphoric acid. Potassium, potassium polyphosphate, potassium tripolyphosphate, sodium trimetaphosphate and sodium tetrametaphosphate and mixtures thereof.

A composition comprising a polymeric polycarboxylic acid, which is intended to be used in the preparation of a binder as described herein, comprising an aqueous solution of a polymeric polycarboxylic acid, a polyol comprising at least two hydroxyl groups, and the like, as described in U.S. Patent Nos. 5,661,213 and 6,136,916. A phosphorus accelerator wherein the ratio of the number of equivalents of carboxylic acid groups to the number of equivalents of hydroxyl groups is from about 1:0.01 to about 1:3.

The polymeric polycarboxylic acid may be a polyester comprising at least two carboxylic acid groups or an addition or oligomer comprising at least two copolycarboxylic acid functional monomers, as disclosed in U.S. Patent Nos. 5,661,213 and 6,136,916. Things. The polymeric polycarboxylic acid is preferably an addition polymer formed from at least one ethylenically unsaturated monomer. The addition polymer may be in the form of an addition polymer solution in an aqueous medium (for example, an alkali-soluble resin which has been dissolved in an alkaline medium); in the form of an aqueous dispersion, such as an emulsion-polymerization dispersion; or In the form of an aqueous suspension. The addition polymer must comprise at least two carboxylic acid groups, anhydride groups or salts thereof. Ethylene-based unsaturated carboxylic acids (such as methacrylic acid, acrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methyl maleic acid, itaconic acid, 2-methyl itaconic acid, α, β-亚Methyl glutaric acid, monoalkyl maleate and monoalkyl fumarate), ethylenically unsaturated anhydride (for example, maleic anhydride, itaconic anhydride, acrylic anhydride, and methacrylic anhydride) and salts thereof The amount may be from about 1% by weight to 100% by weight based on the weight of the addition polymer. Further, the ethylenically unsaturated monomer may include an acrylate monomer including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, butyl methacrylate Ester, isodecyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; acrylamide or substituted acrylamide; styrene or substituted styrene Butadiene; vinyl acetate or other vinyl ester; acrylonitrile or methacrylonitrile and the like. An addition polymer comprising at least two carboxylic acid groups, anhydride groups or salts thereof can have a molecular weight of from about 300 to about 10,000,000. Molecular weights from about 1000 to about 250,000 can be used. When the addition polymer is an alkali-soluble resin having a carboxylic acid, an anhydride or a salt thereof, it may be used in an amount of from about 5% to about 30% by weight based on the total weight of the addition polymer, and may have a molecular weight of from about 10,000 to about 100,000. Methods of preparing such additional polymers are well known in the art.

Polyols (present in compositions comprising polymeric polycarboxylic acids) comprise at least two hydroxyl groups and should have sufficient non-volatileity during heating and curing operations, as described in U.S. Patent Nos. 5,661,213 and 6,136,916. It is made substantially still reactive with the polymeric polycarboxylic acid in the composition. The polyol may be a compound having a molecular weight of less than about 1000 with at least two hydroxyl groups, such as ethylene glycol, glycerol, isovaerythritol, trimethylolpropane, sorbitol, sucrose, glucose, resorcinol. , catechol, pyrogallol, glycolated urea, 1,4-cyclohexanediol, diethanolamine, triethanolamine, and certain reactive polyols, such as beta-hydroxyalkylguanamine (eg, bis-[ N , N -bis(β-hydroxyethyl)]hexanediamine, bis[ N , N -bis(β-hydroxypropyl)]decylamine, bis[ N - N -bis(β-hydroxypropyl) )] hexamethyleneamine, bis[ N - N -bis(β-hydroxypropyl)]pentamethyleneamine, bis[ N - N -bis(β-hydroxypropyl)] succinimide and bis[ N- Methyl- N- (β-hydroxyethyl)]glucamine, or it may be an addition polymer comprising at least two hydroxyl groups (for example polyvinyl alcohol, partially hydrolyzed polyvinyl acetate), and (a) A hydroxyethyl acrylate, a hydroxypropyl (meth) acrylate, and the like, or a homopolymer or copolymer thereof.

Phosphorus-containing accelerators (present in compositions comprising polymeric polycarboxylic acids) can be compounds having a molecular weight of less than about 1000, such as alkali metal hypophosphites, alkali metals, as described in U.S. Patent Nos. 5,661,213 and 6,136,916. a phosphite, an alkali metal polyphosphate, an alkali metal dihydrogen phosphate, a polyphosphoric acid, and an alkylphosphonic acid, or it may be an oligomer or polymer having a phosphorus-containing group, for example, in the presence of sodium hypophosphite An addition polymer of acrylic acid and/or maleic acid formed; an addition polymer prepared from an ethylenically unsaturated monomer in the presence of a phosphite chain transfer agent or a terminator; and an addition polymer comprising an acid functional monomer residue For example, copolymerized ethyl methacrylate phosphate and similar phosphonates and copolymerized vinyl sulfonic acid monomers and salts thereof. The phosphorus-containing accelerator may be used in an amount of from about 1% by weight to about 40% by weight based on the combined weight of the polybasic acid and the polyol. The phosphorus-containing accelerator can be used in an amount of from about 2.5% by weight to about 10% by weight based on the combined weight of the polybasic acid and the polyol.

The term "amine base" as used herein includes, but is not limited to, ammonia, a first amine (ie, NH ₂ R ¹ ), and a second amine (ie, NHR ¹ R ² ), wherein each of R ¹ and R ² in NHR ¹ R ² Independently selected, and wherein R ¹ and R ² are selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, heterocyclyl, aryl and heteroaryl groups as defined herein. For example, the amine base can be substantially volatilized or substantially non-volatile under conditions sufficient to promote formation of the thermoset binder during thermal curing. For example, the amine base can be a substantially volatile base such as ammonia, ethylamine, diethylamine, dimethylamine, and ethylpropylamine. Alternatively, the amine base can be a substantially nonvolatile base such as aniline, 1-naphthylamine, 2-naphthylamine and p-aminophenol.

As used herein, "reducing sugar" refers to one or more sugars comprising an aldehyde group or isomerizable (ie, tautomeric) to comprise an aldehyde group, the groups being associated with an amine group under Maillard reaction conditions The reaction is carried out and the groups can be oxidized, for example, with Cu ^{+ 2} to give a carboxylic acid. It should also be understood that any such carbohydrate reactants may optionally be substituted with, for example, a hydroxyl group, a halogen, an alkyl group, an alkoxy group, and the like. It is further understood that in any of these carbohydrate reactants, one or more pairs of palm centers are present, and that two possible optical isomers at each center of the palm are intended to be encompassed within the invention described herein. In addition, it should be understood that any of the various optical isomers of this carbohydrate reactant, as well as various mixtures of various geometric isomers thereof, including racemic mixtures or other mixtures of diastereomers, may be used herein. In one or more embodiments described.

The term "fiber glass" as used herein refers to a heat resistant fiber suitable for withstanding high temperatures. Examples of such fibers include, but are not limited to, mineral fibers, aromatic polyamide fibers, ceramic fibers, metal fibers, carbon fibers, polyimine fibers, certain polyester fibers, rayon fibers, and glass fibers. For example, such fibers are substantially unaffected upon exposure to temperatures above about 120 °C.

Figure 1 shows an example of a reactant for the Maillard reaction. Examples of the amine reactant include a protein, a peptide, an amino acid, an ammonium salt of a polymeric polycarboxylic acid, and an ammonium salt of a monomeric polycarboxylic acid. As stated, "ammonium" can be [ ⁺ NH ₄ ] _x , [ ⁺ NH ₃ R ¹ ] _x and [ ⁺ NH ₂ R ¹ R ² ] _x , where X is at least about 1. With respect to ⁺ NH ₂ R ¹ R ² , R ¹ and R ² are each independently selected. Further, R ¹ and R ² are selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a heterocyclic group, an aryl group, and a heteroaryl group, as described above. Figure 1 also illustrates an example of a reducing sugar reactant used to produce a melanoid, including monosaccharides, polysaccharides, or combinations thereof in the form of their aldose or ketose. Exemplary non-carbohydrate carbonyl reactants for use in the production of melatonin are also shown in Figure 1 and include various aldehydes (e.g., pyruvaldehyde and furfural) as well as compounds such as ascorbic acid and guanidine.

Figure 2 shows a schematic diagram of the Maillard reaction capable of producing melanoidin. In its initial stage, the Maillard reaction includes a carbohydrate reactant, such as a reducing sugar (note that the carbohydrate reactant can be obtained from a substance that produces a reducing sugar under Maillard's reaction conditions). The reaction also includes condensing the carbohydrate reactant (e.g., reducing sugar) with an amine reactant (i.e., a compound having an amine group). In other words, the carbohydrate reactant and the amine reactant are melatonic reactants such as Maillard reaction. The condensation of the two components produces an N-substituted glycosidic amine. For a more detailed description of the Maillard reaction, see Hodge, JE Chemistry of Browning Reactions in Model Systems J. Agric. Food Chem. 1953, 1 , pages 928 to 943, the disclosure of which is incorporated herein by reference. The compound having a free amino group in the Maillard reaction may exist in the form of an amino acid. The free amine group can also be derived from a protein wherein the free amine group can, for example, be from the epsilon-amino group of the amine acid residue and/or the a-amino group of the terminal amino acid. The form is used.

Another aspect of carrying out the Maillard reaction as described herein is that the Maillard reactant aqueous solution (which is also a binder) as described above initially has an alkaline pH. However, once the solution is placed on a collection of non-assembled or loosely packed materials and curing is initiated, the pH drops (ie, the binder becomes acidic). We should understand that when manufacturing materials, the binder and mechanical components used in manufacturing before curing (ie when the binder solution is alkaline) and after curing (ie when the binder is acidic) The amount of contact between the two is greater. The alkaline composition is less corrosive than the acidic composition. Therefore, the corrosiveness of the manufacturing process is lowered.

It should be understood that by using the aqueous Maillard solution described herein, the machinery used to make the fiberglass is not exposed to excessive amounts of acidic solution because the pH of the Maillard reactant solution is alkaline as described above. . Furthermore, the acidic conditions occur only during the application of the binder to the glass fibers. The binder and the material incorporating the binder will have relatively infrequent contact with the mechanical component after application of the binder to the glass fibers as compared to the period prior to application of the binder to the glass fibers. As a result, the corrosiveness of fiberglass manufacturing (and the manufacture of other materials) is reduced.

Without being bound by theory, it is believed that the Maillard reaction of the polycarboxylic acid ammonium salt with the reducing sugar reactant covalently reacts (which occurs substantially during thermal curing as described herein to produce brown nitrogen polymerization of various structures). And the copolymerized melanin) comprises an initial Maillard reaction of ammonia with the aldehyde moiety of the reducing sugar carbohydrate reactant to give an N -substituted glycosidic amine, as shown in FIG. Consumption of ammonia in this manner, wherein ammonia and the reducing sugar carbohydrate reactant are used together as a latent acid catalyst, is expected to cause a pH drop which is believed to promote the esterification process and/or dehydration of the polycarboxylic acid to obtain it. Corresponding anhydride derivatives. At pH At 7 o'clock, the Amadori rearrangement product of the N -substituted glycosidic amine (ie 1-amino-1-deoxy-2-ketosaccharide) is expected to be predominantly subjected to 1,2-enolization and when included, for example, pentose When furfural is formed, or when, for example, hexose is included, hydroxymethylfurfural is formed, which is produced as a melanoid. At the same time, an esterification process involving melalinoids, polycarboxylic acids and/or their corresponding anhydride derivatives and residual carbohydrates may occur at the same time as or subsequent to the production of mereoids, which processes result in extensive crosslinking. Along with the sugar dehydration reaction, thereby producing a conjugated double bond capable of polymerization, a water-resistant thermosetting binder composed of a polyester adduct interconnected by a carbon-carbon single bond network is produced. Consistent with the above reaction scheme, strong absorbance values appear in the FT-IR spectrum of the cured binder described herein at around 1734 cm ^-1 , and for the ester carbonyl C-O vibration, the absorbance is expected to be in the range of 1750-1730 cm ^-1 . . The above spectrum is shown in Fig. 4.

The following discussion pertains to (i) examples of carbohydrate and amine reactants that can be used in the Maillard reaction and (ii) how the reactants are combined. First, we should understand that any carbohydrate and/or compound having a first or second amine group to be used as a reactant in the Maillard reaction can be used in the binder of the present invention. Those skilled in the art can determine and use such compounds in accordance with the teachings disclosed herein.

With regard to the exemplary reactants, it is also understood that an ammonium salt of a polycarboxylic acid is used as an effective reactant in the Maillard reaction of the amine reactant system. The ammonium salt of a polycarboxylic acid can be produced by neutralizing an acid group with an amine base to produce a polyvalent ammonium carboxylate group. Complete neutralization (i.e., about 100% calculated on an equivalent basis) eliminates any need to titrate or partially neutralize the acid groups in the (or other) polycarboxylic acid prior to the formation of the binder. However, we anticipate that incomplete neutralization will not inhibit the formation of binders. Note that the neutralization of the acid group of the (etc.) polycarboxylic acid can be carried out before or after the (poly)carboxylic acid is mixed with the (or) carbohydrate.

The carbohydrate reactant can include one or more reactants containing one or more reducing sugars. In one aspect, any carbohydrate reactant should have sufficient non-volatility to maximize its ability to react with the polycarboxylate ammonium salt reactant. The carbohydrate reactant can be a monosaccharide (including triose, butyrate, pentose, hexose or heptose) in the form of its aldose or ketose; or a polysaccharide or a combination thereof. The carbohydrate reactant can be a reducing sugar or a person who produces one or more reducing sugars in situ under heat curing conditions. For example, when triose is used as the carbohydrate reactant, or when used in combination with other reducing sugars and/or polysaccharides, propionaldehyde or syrup may be used, such as glyceraldehyde and dihydroxyacetone, respectively. When butyrate is used as a carbohydrate reactant, or in combination with other reducing sugars and/or polysaccharides, butyralose (such as erythrose and threose) and butanose (such as erythrulose) can be used. . When pentose is used as a carbohydrate reactant, or in combination with other reducing sugars and/or polysaccharides, valerose (eg, ribose, arabinose, xylose, and lyxose) and ketopentose (eg, nucleus) may be used. Ketosaccharide, arabinose, xylulose and lyxulose. When hexose is used as a carbohydrate reactant, or in combination with other reducing sugars and/or polysaccharides, aldohexose (eg, glucose (ie, dextrose), mannose, galactose, alo Sugar, altrose, talose, gulose and idose) and ketohexose (for example, sugar, allulose, sorbose and tagatose). When heptose is used as a carbohydrate reactant, or in combination with other reducing sugars and/or polysaccharides, heptanose, such as sedoheptulose, can be used. Other stereoisomers of such carbohydrate reactants which are not known to be naturally occurring are also intended to be used in the preparation of a binder composition as described herein. When the polysaccharide is used as a carbohydrate, or when used in combination with a monosaccharide, sucrose, lactose, maltose, starch, and cellulose can be used.

In addition, the carbohydrate reactant in the Maillard reaction can be used in combination with a non-carbohydrate polyhydroxy reactant. Examples of non-carbohydrate polyhydroxy reactants that can be used in combination with a carbohydrate reactant include, but are not limited to, trimethylolpropane, glycerin, isovaerythritol, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, complete Hydrolyzed polyvinyl acetate and mixtures thereof. In one aspect, the non-carbohydrate polyhydroxy reactant should have sufficient non-volatility to maximize its ability to react with monomeric or polymeric polycarboxylic acid reactants. It will be appreciated that the hydrophobicity of the non-carbohydrate polyhydroxy reactant can be a factor in determining the physical properties of the binder prepared as described herein.

When partially hydrolyzed polyvinyl acetate is used as the non-carbohydrate polyhydroxy reactant, a commercially available compound such as 87 to 89% hydrolyzed polyvinyl acetate such as DuPont ELVANOL 51-05 can be used. DuPont ELVANOL 51-05 has a molecular weight of from about 22,000 to 26,000 Da and a viscosity of from about 5.0 to 6.0 centipoise. Other partially hydrolyzed polyvinyl acetates which are intended to be used in the preparation of the cement compositions described herein include, but are not limited to, polyvinyl acetate having a molecular weight and viscosity different from 87 to 89% of ELVANOL 51-05, for example, For example, DuPont ELVANOL 51-04, ELVANOL 51-08, ELVANOL 50-14, ELVANOL 52-22, ELVANOL 50-26, ELVANOL 50-42; and molecular weight, viscosity and/or degree of hydrolysis are different from ELVANOL 51-05 Partially hydrolyzed polyvinyl acetate, such as DuPont ELVANOL 51-03 (86 to 89% hydrolysis), ELVANOL 70-14 (95.0 to 97.0% hydrolysis), ELVANOL 70-27 (95.5 to 96.5% hydrolysis), ELVANOL 60- 30 (90-93% hydrolysis). Other partially hydrolyzed polyvinyl acetates which are intended to be used in the preparation of the cement compositions described herein include, but are not limited to, Clariant MOWIOL 15-79, MOWIOL 3-83, MOWIOL 4-88, MOWIOL 5-88, MOWIOL 8 -88, MOWIOL 18-88, MOWIOL 23-88, MOWIOL 26-88, MOWIOL 40-88, MOWIOL 47-88 and MOWIOL 30-92 and Celanese CELVOL 203, CELVOL 205, CELVOL 502, CELVOL 504, CELVOL 513, CELVOL 523, CELVOL 523TV, CELVOL 530, CELVOL 540, CELVOL 540TV, CELVOL 418, CELVOL 425 and CELVOL 443. Also intended for use are similar or similar partially hydrolyzed polyvinyl acetates from other commercial suppliers.

When fully hydrolyzed polyvinyl acetate is used as the non-carbohydrate polyhydroxy reactant, Clariant MOWIOL 4-98 having a molecular weight of about 27,000 Da can be used. Other fully hydrolyzed polyvinyl acetates that are intended to be useful include, but are not limited to, DuPont ELVANOL 70-03 (98.0-98.8% hydrolysis), ELVANOL 70-04 (98.0-98.8% hydrolysis), ELVANOL 70-06 (98.5-99.2) % hydrolysis), ELVANOL 90-50 (99.0-99.8% hydrolysis), ELVANOL 70-20 (98.5-99.2% hydrolysis), ELVANOL 70-30 (98.5-99.2% hydrolysis), ELVANOL 71-30 (99.0-99.8% hydrolysis) ), ELVANOL 70-62 (98.4-99.8% hydrolysis), ELVANOL 70-63 (98.5-99.2% hydrolysis), ELVANOL 70-75 (98.5-99.2% hydrolysis), Clariant MOWIOL 3-98, MOWIOL 6-98, MOWIOL 10-98, MOWIOL 20-98, MOWIOL 56-98, MOWIOL 28-99 and Celanese CELVOL 103, CELVOL 107, CELVOL 305, CELVOL 310, CELVOL 325, CELVOL 325LA and CELVOL 350 and similar or similar from other commercial suppliers Similar to fully hydrolyzed polyvinyl acetate.

The Maillard reactants described above can be combined to prepare an aqueous composition comprising a carbohydrate reactant and an amine reactant. These aqueous binders represent examples of uncured binders. As discussed below, such aqueous compositions can be used as the binder of the present invention. The binders are free of formaldehyde, curable, alkaline, aqueous binder compositions. Additionally, as noted above, the Carahydrate reactant carbohydrate reactant can be used in combination with a non-carbohydrate polyhydroxy reactant. Therefore, whenever a carbohydrate reactant is mentioned, it should be understood that it can be used in combination with a non-carbohydrate polyhydroxy reactant.

In an exemplary embodiment, the aqueous solution of Maillard reactants can include (i) an ammonium salt of one or more polycarboxylic acid reactants and (ii) one or more carbohydrate reactants comprising a reducing sugar. The pH of the solution may be greater than or equal to about 7 prior to contacting the solution with the material to be bonded. Additionally, the solution can have a pH of less than or equal to about 10. The ratio of the molar number of the (and other) polycarboxylic acid reactant to the molar number of the (or equivalent) carbohydrate reactant may range from about 1:4 to about 1:15. In one example, the ratio of the molar number of the (and other) polycarboxylic acid reactants to the molar number of the (or equivalent) carbohydrate reactant in the binder composition is about 1:5. In another example, the ratio of the molar number of the (and other) polycarboxylic acid reactant to the molar number of the (or equivalent) carbohydrate reactant is about 1:6. In still another example, the ratio of the molar number of the (equivalent) polycarboxylic acid reactant to the molar number of the (or equivalent) carbohydrate reactant is about 1:7.

As noted above, the aqueous binder composition includes (i) an ammonium salt of one or more polycarboxylic acid reactants and (ii) one or more carbohydrate reactants comprising a reducing sugar. It will be appreciated that when an ammonium salt of a monomeric or polymeric polycarboxylic acid is used as the amine reactant, the molar equivalent of the ammonium ion may or may not be equal to the molar equivalent of the acid salt group present on the polycarboxylic acid. In an illustrative example, when a tricarboxylic acid is used as the polycarboxylic acid reactant, the ammonium salt can be mono-, di- or ternary. Thus, the molar equivalent of the ammonium ion can be present in an amount less than or about equal to the molar equivalent of the acid salt group present in the polycarboxylic acid. Thus, when the polycarboxylic acid reactant is a dicarboxylic acid, the salt can be monobasic or binary. Additionally, the molar equivalents of ammonium ions may be present in an amount less than or equal to the molar equivalents of the acid salt groups present in the polymeric polycarboxylic acid and such amounts as such. When a unit salt of a dicarboxylic acid is used, or when a binary salt of a tricarboxylic acid is used, or when the molar equivalent of the ammonium ion is lower than the molar equivalent of the acid salt group present in the polymeric polycarboxylic acid When present, the pH of the cement composition may need to be adjusted to achieve alkalinity.

Uncured, formaldehyde-free, heat curable, alkaline, aqueous binder compositions can be used to make a variety of different materials. In particular, the bonding agents can be used to create or promote bonding in non-assembled or loosely assembled materials by contacting the bonding agent with the substance to be bonded. Any number of conventional techniques can be used to contact the aqueous binder with the material to be bonded. For example, the aqueous binder can be sprayed (eg, during bonding of the glass fibers) or applied via a roll coating device.

The aqueous binder may be applied to a fiberglass board (e.g., sprayed onto the board) during the production of the fiberglass insulation product. Once the aqueous binder is in contact with the glass fibers, the residual heat from the glass fibers (note that the glass fibers are made of molten glass and therefore contain residual heat) and the flow of air through the fiberboard will cause water to adhere thereto. The agent evaporates (ie, removes). Removal of water allows the remaining components of the binder to remain on the fibers as a viscous or semi-viscous, high solids liquid coating. The viscous or semi-viscous high solid liquid coating is used as a binder. At this point, the board has not yet been cured. In other words, the uncured binder is used to bond the glass fibers in the panel.

In addition, it should be understood that the aqueous binder described above can be cured. For example, any of the aqueous binders described above can be disposed (e.g., sprayed) onto the material to be bonded and subsequently heated. For example, in the case of preparing a fiberglass insulation product, after application of the aqueous binder to the board, the sheet coated with the binder is transferred to a curing oven. In the curing oven, the plate is heated (e.g., from about 300 °F to about 600 °F) and the binder is cured. The curing adhesive is a formaldehyde-free, water-resistant thermosetting bonding agent that bonds the glass fibers of the board together. It should be noted that the drying and thermal curing can occur sequentially, simultaneously or in parallel.

With regard to the preparation of a binder which is water-insoluble when cured, we should know the number of mole equivalents of the acid salt groups present on the (etc.) polycarboxylic acid reactant and the hydroxyl groups present on the (etc.) carbohydrate reactant. The ratio of the molar equivalents of the mass may range from about 0.04:1 to about 0.15:1. After curing, the formulations produce a water resistant thermoset binder. In a variation, the number of mole equivalents of the hydroxyl groups present on the (etc.) carbohydrate reactant is about 25 higher than the number of mole equivalents of the acid salt groups present on the (etc.) polycarboxylic acid reactant. Times. In another variation, the number of mole equivalents of the hydroxyl groups present on the (etc.) carbohydrate reactant is greater than the number of mole equivalents of the acid salt groups present on the (etc.) polycarboxylic acid reactant. 10 times. In still another variation, the number of mole equivalents of the hydroxyl groups present on the (etc.) carbohydrate reactant is greater than the number of mole equivalents of the acid salt groups present on the (etc.) polycarboxylic acid reactant. 6 times.

In other embodiments of the invention, the cured adhesive can be disposed on the material to be bonded. As noted above, most curing adhesives will typically contain water insoluble melanin. Therefore, the binders are also water-resistant thermosetting binders.

Various additives can be included in the binder composition as described below. These additives can impart additional desirable characteristics to the adhesives of the present invention. For example, the binder may include a cerium-containing coupling agent. Many bismuth-containing coupling agents are available from Dow-Corning, Petrarch Systems and General Electric. For example, ruthenium-containing coupling agents include compounds such as decyl ethers and alkyl decyl ethers, each of which may be optionally substituted with, for example, a halogen, an alkoxy group, an amine group, and the like. In a variation, the ruthenium containing compound is an amine substituted decane such as gamma-aminopropyl triethoxy decane (General Electric Silicones, SILQUEST A-1101; Wilton, CT; USA). In another variation, the ruthenium containing compound is an amine substituted decane, for example, aminoethylaminopropyltrimethoxydecane (Dow Z-6020; Dow Chemical, Midland, MI; USA). In another variation, the ruthenium containing compound is gamma-glycidoxypropyltrimethoxydecane (General Electric Silicones, SILQUEST A-187). In another variation, the ruthenium containing compound is n-propylamine decane (Creanova (formerly Huls America) HYDROSIL 2627; Creanova; Somerset, N.J.; U.S.A.).

The ruthenium-containing coupling agents are typically present in the binder in an amount ranging from about 0.1% to about 1% by weight of the dissolved cement solids (i.e., from about 0.1% to about 1% by weight of the solids added to the aqueous solution) ). In one application, one or more of the ruthenium containing compounds can be added to the aqueous uncured binder. The binder is then applied to the material to be bonded. The binder can then be cured if desired. The cerium-containing compounds enhance the ability of the binder to adhere to materials (e.g., glass fibers) to which the binder is applied. The ability to enhance the adhesion of the binder can improve, for example, its ability to create or promote bonding in non-assembled or loosely packed materials.

The binder comprising the ruthenium-containing coupling agent may be formulated by blending 10 to about 50% by weight of one or more aqueous solutions of the polycarboxylic acid reactant neutralized or neutralized in situ with an amine base and about 10 to 50% by weight. Or an aqueous solution of a plurality of reducing sugar-containing carbohydrate reactants and an effective amount of a ruthenium-containing coupling agent. In a variation, one or more polycarboxylic acid reactants and one or more carbohydrate reactants (the latter containing a reducing sugar) may be combined in solid form, mixed with water, and subsequently treated with an aqueous amine base (to neutralize such The mixture is treated with one or more polycarboxylic acid reactants and a rhodium-containing coupling agent to produce an aqueous solution of various polycarboxylic acid reactants and various carbohydrate reactants in an amount of from 10 to 50% by weight.

In another exemplary embodiment, the present adhesives can include one or more corrosion inhibitors. These corrosion inhibitors prevent or inhibit corrosion or abrasion of substances (such as metals) caused by chemical decomposition by acid. When a corrosion inhibitor is incorporated into the binder of the present invention, the corrosiveness of the binder is reduced compared to the corrosivity of the binder without the inhibitor. In one embodiment, the corrosion inhibitors can be used to reduce the corrosivity of the glass fiber-containing compositions described herein. For example, the corrosion inhibitor includes one or more of the following: dusting oil or ammonium dihydrogen phosphate, sodium metasilicate pentahydrate, melamine, tin (II) oxalate, and/or methyl hydrogen polyoxygen fluid emulsion. When a corrosion inhibitor is incorporated into the cement of the present invention, it is typically present in the binder in an amount ranging from about 0.5% to about 2% by weight of the dissolved cement solids.

In accordance with the disclosed guidelines, those skilled in the art will be able to modify the concentration of the reactants of the aqueous binder to produce a variety of binder compositions. In particular, the aqueous binder composition can be formulated to have an alkaline pH. For example, the pH can be between greater than or equal to about 7 to less than or equal to about 10. Examples of steerable binder reactants include (i) a polycarboxylic acid reactant, (ii) an amine base, (iii) a carbohydrate reactant, (iv) a ruthenium containing coupling agent, and (v) a corrosion inhibitor compound. The aqueous binders of the present invention (e.g., uncured binders) have a pH in the alkaline range that inhibits corrosion of materials that are in contact with the binder, such as those used in manufacturing processes, such as in the manufacture of fiberglass. Note: This is especially true when the corrosive nature of the acid binder is compared to the binder of the present invention. As a result, the "life" of the machine has increased while the cost of maintaining such machines has decreased. In addition, standard equipment can be used with the present invention, rather than having to use a relatively corrosion resistant machine component, such as a stainless steel component, in contact with an acidic binder. Thus, the binders disclosed herein reduce the cost of making bonding materials.

The following examples further illustrate specific embodiments of the invention in detail. The examples are provided for illustrative purposes only and are not to be construed as limiting the invention or the inventive concept to any particular physical configuration in any manner. For example, although an aqueous binder of 25% by weight of each of triammonium citrate and dextrose monohydrate is blended in Example 1, it will be understood that in variations of the embodiments described herein The weight % of the aqueous solution of the polycarboxylic acid ammonium salt reactant and the weight % of the aqueous solution of the reducing sugar carbohydrate reactant can be varied without affecting the properties of the invention as described. For example, an aqueous solution of a polycarboxylic acid ammonium salt reactant and a reducing sugar carbohydrate reactant in a weight range of from about 10 to 50% by weight is blended. In addition, although in Examples 8 to 12, a binder/glass fiber composition was prepared by dissolving a 10-50% by weight aqueous solution of solids using triammonium citrate and dextrose monohydrate, it is understood that the changeable plural The weight percent of the aqueous solution of the ammonium carboxylate reactant/aqueous solution containing the reducing sugar carbohydrate reactant does not affect the properties of the invention as described. For example, an aqueous solution is prepared in which a polycarboxylic acid ammonium salt reactant and a reducing sugar carbohydrate reactant are included in a weight percentage in excess of about 10-50% by weight. Further, although the following Examples of polycarboxylic acids include the ammonium (i.e. ⁺ NH ₄₎ salts of polycarboxylic acid ammonium salt as a reactant, but it should be understood that alternative may be used without affecting the properties of the amine reactant of the present invention include, for example polyhydric a first amine salt or a second amine salt of a carboxylic acid.

Example 1

Preparation of aqueous triammonium citrate-dextrose binder Preparation of aqueous triammonium citrate-dextrose binder according to the following procedure: aqueous solution of triammonium citrate (25%) (81.9 g of citric acid, 203.7 g of water and 114.4)克 19% ammonia solution) and aqueous dextrose monohydrate solution (25%) (50.0 g of dextrose monohydrate in 150.0 g of water) were combined at room temperature in the following volume ratios: 1:24, 1:12 1,8, 1:6, 1:5, 1:4, and 1:3, wherein the relative volume of triammonium citrate is listed as "1". For example, 10 ml of an aqueous solution of triammonium citrate is mixed with 50 ml of an aqueous solution of dextrose monohydrate to obtain a "1:5" solution, wherein the mass ratio of triammonium citrate to dextrose monohydrate is about 1:5. , the molar ratio of triammonium citrate to dextrose monohydrate is about 1:6, and the molar equivalent number of the acid salt group present on the triammonium citrate and the hydroxyl group present on the dextrose monohydrate The ratio of the molar equivalents of the groups is about 0.10:1. The resulting solution was stirred for several minutes at room temperature, at which time 2 grams of sample was taken and thermally cured as described in Example 2.

Example 2

Preparation of a cured triammonium citrate-dextrose binder sample from aqueous triammonium citrate-dextrose binder A 2 gram sample of each of the binders prepared as in Example 1 was placed in three separate 1 gram aluminum baking trays. On each of the plates. Each of the binders was then subjected to the following three conventional baking/curing conditions in a preheated thermostat convection oven to produce the corresponding cured binder samples: 15 minutes at 400 °F, 30 minutes at 350 °F and 30 at 300 °F. minute.

Example 3

Test/Evaluation of Solidified Triammonium Citrate-Dextrose Adhesive Samples Produced by Aqueous Triammonium Citrate-Dextrose Adhesive for Each of the Cured Triammonium Citrate-Dextrose Bonds Prepared as in Example 2 The wet strength of the sample was such that the cured cement sample appeared to remain intact and resistant to dissolution, and then water was added to the aluminum baking tray and then allowed to stand at room temperature. Wet strength is recorded as dissolved (no wet strength), partially dissolved (minimum wet strength), softened (intermediate wet strength) or impermeable (high wet strength, water insoluble). The color of the water produced by contact with the solidified ammonium citrate-dextrose binder sample was also determined. Table 1 below shows illustrative examples of the triammonium citrate-dextrose binder prepared according to Example 1, the curing conditions used according to Example 2, and the test and evaluation results according to Example 3.

Example 4

Elemental analysis of cured triammonium citrate-dextrose (1:6) binder sample 15% triammonium citrate-dextrose (1:6) prepared as described in Example 1 and cured as described below Elemental analysis of carbon, hydrogen and nitrogen (ie C, H, N) was carried out on 5 g of the binder, and the 0.75 g of the cured sample was incorporated with triammonium citrate and dextrose monohydrate at a molar ratio of about 1:6. . The binder samples were cured according to the following temperatures and times: 300 °F for 1 hour, 350 °F for 0.5 hours, and 400 °F for 0.33 hours. Elemental analysis was performed at Galbraith Laboratories (Knoxville, TN). As shown in Table 2, elemental analysis revealed that the C:N ratio increased with increasing temperature from 300 °F to 350 °F, which is consistent with the preparation of the binder containing the melanoid. In addition, Table 2 also shows that the C:H ratio increases with increasing temperature, which is consistent with the dehydration that occurs during curing of the binder (a known process that occurs during the formation of melanoids).

Example 5

Preparation of aqueous ammonium carboxylate-sugar binder for glass bead shell, glass fiber board and wood fiber board composition aqueous triammonium citrate-dextrose (1:6) binder (the binder) Used to construct glass bead shells and glass fiber-containing boards) by the following general procedure: powdered dextrose monohydrate (915 g) and powdered anhydrous citric acid (152.5 g) in 1 gallon The reaction vessel was combined, and 880 g of distilled water was added thereto. To the mixture was added 265 g of 19% aqueous ammonia with stirring, and stirring was continued for several minutes to completely dissolve the solid. To the resulting solution was added 3.3 grams of SILQUEST A-1101 decane to produce a solution having a pH of about 8 to 9 (by means of a pH test paper) containing about 50% dissolved dextrose monohydrate and dissolved ammonium citrate solids ( % of the total weight of the solution), 2 g of this solution sample was thermally cured at 400 °F for 30 minutes to give 30% solids (this weight loss is attributed to the dehydration during the formation of the thermosetting binder). Among them, decane instead of SILQUEST A-1101 was incorporated into the triammonium citrate-dextrose (1:6) binder and replaced with SILQUEST A-187 decane, HYDROSIL 2627 decane or Z-6020 decane. When an additive was incorporated into the triammonium citrate-dextrose (1:6) binder to produce a binder variant, the standard solution was dispensed into a bottle in 300 gram aliquots, and then each additive was added thereto.

Figure 3 shows the FT-IR spectrum of a dry (uncured) triammonium citrate-dextrose (1:6) binder which is dried in a vacuum by 30% (dissolved binder solid) binder. A 10 gram sample was obtained in the form of a microscopic film. Figure 4 shows the FT-IR spectrum of a cured triammonium citrate-dextrose (1:6) Maillard binder, which is obtained by 30% binder (dissolved binder solid) after curing. The sample was obtained in the form of a microscopic film.

When an aqueous polycarboxylic acid ammonium-sugar binder variant is prepared using a polycarboxylic acid instead of citric acid, sugar rather than dextrose and/or an additive, the same general procedure as described above is used to prepare aqueous citric acid. Triammonium-dextrose (1:6) binder. For polycarboxylate ammonium-sugar binder variants, adjustments may be made as needed to suit, for example, a dicarboxylic acid or a polymeric polycarboxylic acid in place of citric acid, or may be incorporated, for example, as a triose, instead of dextrose, Or suitable for inclusion in, for example, one or more additives. Such adjustments include, for example, adjusting the volume of aqueous ammonia required to produce an ammonium salt, adjusting the grams of the desired reactant to achieve the desired molar ratio of ammonium polycarboxylate to sugar, and/or incorporating it in the desired weight percent. additive.

Example 6

Preparation/weathering/testing of glass bead shell compositions prepared with a polycarboxylate ammonium-sugar binder When evaluating the dry and "weathered" tensile strength of a glass bead containing bone composition prepared with a given binder Providing similar tensile strength and similar durability readings for fiberglass spacers prepared with the particular binder, respectively. The predicted durability is based on the weathering tensile strength of the shell bone: the ratio of the dry tensile strength. The shell bone was prepared and weathered and tested as follows: the preparation procedure of the shell bone: the Dieter Foundry Testing Equipment (Heated Shell Curing Accessory; Model 366, and Shell Mold Accessory) was set to a desired temperature, usually 425 °F, And allowed to heat for at least 1 hour. When the shell mold was heated, about 100 grams of an aqueous polycarboxylic acid ammonium-sugar binder (typically 30% binder solids) was prepared as described in Example 5. 727.5 g of glass beads (Quality Ballotini Impact Beads, Spec. AD, US Sieve 70-140, 106-212 μm - #7, available from Potters Industries) were weighed by means of a large glass beaker. The glass beads were poured into a clean and dry mixing bowl and the crucible was placed on an electric mixer rack. About 75 grams of an aqueous polycarboxylic acid ammonium-sugar binder was obtained, and the binder was then slowly poured into the glass beads in the mixed bowl. The electric mixer was then turned on and the glass beads/polycarboxylate ammonium-sugar binder mixture was stirred for 1 minute. The side of the agitator (mixer) is scraped off with a large spatula to remove any of the cement blocks while also scraping the edges, wherein the glass beads are located at the bottom of the crucible. The mixer was then turned on for a further few minutes, then the stirrer (mixer) was removed from the apparatus, and then the mixed crucible containing the glass bead/polycarboxylate ammonium-sugar binder mixture was removed. With a large spatula, remove as much of the binder and glass beads as possible from the stirrer (mixer) and then stir it into the glass bead/polycarboxylate ammonium-sugar binder mixture in the mixing bowl. . The sides of the crucible are then scraped off to incorporate any excess binder that may have accumulated on the sides. At this time, the glass bead/polycarboxylate ammonium-sugar binder mixture is prepared to be molded in a shell bone mold.

It is determined that the slide rails of the shell mold are aligned within the bottom mold platen. The glass bead/polycarboxylate ammonium-sugar binder mixture is then rapidly added to the three mold cavities in the shell mold by means of a large spatula. The surface of the mixture in each cavity is flattened while the excess mixture is scraped off to impart a uniform surface area to the shell bone. Any inconsistencies or gaps present in any of the cavities are filled with additional glass beads/polycarboxylate ammonium-sugar binder mixture and subsequently flattened. Once the glass bead/polycarboxylate ammonium-sugar binder mixture is placed in the cranial cavity, the mixture is exposed to heat and curing begins. Since the operating time can affect the test results, for example, a shell bone having two differentially cured layers can be produced, the shell bone should be prepared consistently and rapidly. After filling the shell mold, the top platen is quickly placed on the bottom platen. Simultaneously or thereafter, the curing time is initially measured by means of a stopwatch during which the bottom platen temperature is between about 400 °F and about 430 °F, while the top platen temperature is between about 440 °F and about 470 °F. . After 7 minutes, the top platen was removed and the slides were pushed out to allow all three shell bones to be removed. The freshly prepared shell bone was then placed on a wire shelf adjacent to the shell mold plate and allowed to cool to room temperature. Thereafter, each shell bone is marked and placed separately in a suitably labeled plastic storage bag. If the shell bone is not tested on the day of preparation, the plastic bag containing the shell bone is placed in the dryer unit.

Shell Bone Adjustment (Weathering) Procedure: Turn on the Blue M Wet Chamber and then set it to provide weathering conditions of 90 °F and 90% relative humidity (ie 90 °F / 90% rH). Check the water tank on the side of the wet chamber and add water regularly, usually every time it is turned on. The wet chamber is allowed to reach a specified weathering condition over a period of at least 4 hours and typically a period of up to 1 day. Each time the open wet chamber door is quickly loaded with the shell bone to be weathered (because both humidity and temperature are lowered when the door is opened) on the upper shelf of the wet chamber. The time during which the shell bones were placed in the wet chamber was recorded and weathered for a period of 24 hours. Thereafter, the wet chamber doors are opened and a set of shell bones are quickly removed each time and placed separately in each fully sealed plastic storage bag. In general, one to four sets of shell bones are weathered each time as described above. The weathered crust was immediately placed in the Instron chamber and tested.

Test procedure for fractured shell bone: In the Instron chamber, the shell bone test method was loaded onto a 5500 R Instron machine while ensuring that the appropriate load sensor (ie, a static load sensor of 5 kN) was installed and the machine was installed Warm up for 15 minutes. During this time period, it is verified that the shell bone test fixture has been installed on the machine. The load cell was zeroed and equilibrated, and each time a set of shell bones was tested as follows: the shell bone was removed from its plastic storage bag and subsequently weighed. This weight (in grams) is then entered into a computer connected to the Instron machine. The thickness of the shell bone (in inches) was then entered as the sample thickness three times into the computer connected to the Instron machine. The shell bone sample was then placed in a fixture on the Instron machine and the test was started on the Instron machine via a keyboard. After taking the shell bone sample, the measured break point is entered into the computer connected to the Intron machine and testing continues until all of the shell bones in the set are tested.

The test results are shown in Tables 3 through 6, which are the average dry tensile strength (psi), average weathering tensile strength (psi), and weathering: dry tensile strength ratio.

Example 7

Preparation/weathering/testing of glass-containing sheets prepared with a polycarboxylate ammonium-sugar (1:6) binder When evaluating the dry and "weathered" tensile strength of a glass fiber-containing board prepared with a given binder, They provide similar tensile strength and similar durability readings for fiberglass spacers prepared with the particular binder, respectively. The predicted durability is based on the "weathered" tensile strength of the fiberglass sheet: the dry tensile strength ratio. The fiberglass board was prepared and weathered and tested as follows: Preparation procedure containing glass fiber board: 13 inches high x 13 inches wide x 14 inches deep "Deckel box" is made of pure acrylic resin sheet and attached To splicing the metal frame. A perforated plate and a coarse metal screen system were installed under the Dick box as a transition from the tank to the 3 inch drain. An interwoven plastic strip (referred to as "screen") is clamped under the Dick box. For mixing purposes, a 5 gallon bucket equipped with internal vertical ribs and a high shear air motor mixer was used. Typically, 4 gallons of water and E glass (i.e., high temperature glass) fibers (11 grams, 22 grams, or 33 grams) are mixed for 2 minutes. A typical E glass contains the following composition by weight: SiO ₂ , 52.5%; Na ₂ O, 0.3%; CaO, 22.5%; MgO, 1.2%; Al ₂ O ₃ , 14.5%; FeO/Fe ₂ O ₃ , 0.2% ; K ₂ O, 0.2% and B ₂ O ₃ , 8.6%. The drain and the under-net transition device have been pre-filled with water to wet the bottom of the Dick box. The aqueous glass fiber mixture was poured into the Dick box and stirred vertically with a plate containing forty-nine (49) 1 inch bores. Quickly open the slide valve at the bottom of the drain line and collect the glass fibers on the screen. A screen covered frame placed under the net facilitates transfer of the fiberglass sample. Water is removed by passing the sample through an extractor tank having a 25 to 40 inch water pipe string suction. One pass was used for 11 grams of sample, two passes for 22 grams of sample, and three passes for 33 grams of sample. The sample was transferred to a second screen covered frame and removed to form a screen. The sample is then dried and allowed to exit the screen. Subsequently, the sample was passed through a 3-inch diameter applicator roll in a bath containing an aqueous polycarboxylic acid ammonium-sugar binder (containing 15% dissolved binder solids prepared as described in Example 5). Medium rotation in which the glass fibers are saturated with a binder. Excess binder was again drawn through the extractor slot to produce a fiberglass-containing panel which was cured in an oven with upward flow of forced convection air at 375 °F for 30 minutes.

Adjustment of the fiberglass board (weathering) procedure: A sample of the glass fiber-containing board to be adjusted is placed on a TEFLON coated thick braid and pressed downward to prevent floating. A pair of sample plates were prepared for each of the polycarboxylate ammonium-sugar binders evaluated. The panels are allowed to be conditioned for at least 1 day in an air-conditioned but humidity-free room at ambient temperature and humidity. Seven test samples were cut from each plate by means of a die having a suitable profile; that is, six samples were cut in one direction and one sample was cut in the vertical direction, and each sample remained separated. Each sample was 2 inches wide and narrowed to a middle portion of 1 inch wide while being approximately 12 inches long. Three samples from each plate were placed in a "weathered" chamber at 37 to 38 ° C and 90% relative humidity for 24 hours. The weathered samples were removed from the chamber and stored in a sealable plastic bag, each containing a wet tissue until it was opened prior to testing.

Test procedure for broken fiberglass panels: Set the crosshead speed of the tensile tester to 0.5 inch per minute. The clamp is 2 inches wide and has a clamp of approximately 1.5 inches. Three dry samples from each plate and three weathered samples were tested. These dried samples are used for the determination of the binder content, as determined by the loss on ignition (LOI).

The test results are shown in Table 7, which are the average % LOI, the average dry tensile strength (pound force), the average weathered tensile strength (pound force), and the weathering: dry tensile strength ratio.

Example 8

Triammonium citrate-dextrose (1:6) binder/glass fiber composition: preparation of uncured blanket and curing blanket to make powdered dextrose monohydrate (300 lbs) and powdered anhydrous citric acid (50 Pounds) combined in a 260 gallon container. Soft water was then added to reach a volume of 235 gallons. To the mixture was added 9.5 gallons of 19% aqueous ammonia, and the resulting mixture was stirred to completely dissolve the solid. 0.56 lbs of SILQUEST A-1101 decane was added to the resulting solution to produce a dissolved dextran monohydrate and a 15.5% solution of dissolved ammonium citrate solids (expressed as a percentage of the total weight of the solution); 2 grams of this solution sample After heat curing at 400 °F for 30 minutes, 9.3% solids were obtained (this weight loss was attributed to dehydration during the formation of the thermosetting binder). The solution is stirred for a few minutes before being sent to the binder pump, where the solution is used to make a fiberglass spacer, specifically for forming a "wet blanket" or uncured blanket and " Amber blanket or the material of the curing blanket.

The uncured and cured carpets are prepared using conventional fiberglass manufacturing procedures; such procedures are outlined below and in U.S. Patent No. 5,318,990, the disclosure of which is incorporated herein by reference. Typically, when the binder is produced, it is applied to the glass fibers and forms a sheet from which water can be volatilized, and the fiberglass sheet coated with the high solid binder is heated to cure the binder and thereby produce the final fibers. A glass sheet that can be used, for example, as a heat insulating or sound insulating product, as a reinforcement for a composite that is subsequently produced, and the like.

A porous sheet of fiberglass is produced by fiberizing molten glass and immediately forming a fiberglass sheet on a moving conveyor. The glass is melted in a can and supplied to a fiber forming device, such as a rotator or bushing. The glass fibers are drawn from the device and then typically blown down in the forming chamber. The glass fibers typically have a diameter of from about 2 to about 9 microns and have a length of from about 0.25 inches to about 3 inches. Typically, the glass fibers have a diameter of between about 3 and about 6 microns and have a length of from about 0.5 inches to about 1.5 inches. The glass fibers are deposited on a perforated, endless forming conveyor. When the glass fibers are formed, a binder is applied thereto by means of a suitable spray applicator to distribute the binder throughout the formed fiberglass panel. The glass fibers to which the uncured binder is adhered are gathered together and formed in a forming chamber by vacuum stretching from the underside of the forming conveyor to the endless conveyor. The residual heat contained in the glass fibers and the flow of air through the plates cause most of the water to evaporate therefrom before the plates exit the forming chamber. (The water is removed to the extent that the uncured binder can be used as a binder; for any particular use, the amount of water to be removed can be determined by one of ordinary skill in the art based on routine experimentation).

When the fiberglass sheet coated with the high solid binder emerges from the forming chamber, it will expand vertically due to the elasticity of the glass fibers. The expanded plate is then transferred to a curing oven and passed through a curing oven through which hot air passes to cure the binder. The squeegee above and below the panel slightly compresses the panel to provide a final product of predetermined thickness and finish. Typically, the curing oven operates at a temperature between about 350 °F and about 600 °F. Generally, the plate is allowed to stand in the oven for a period of from about 0.5 minutes to about 3 minutes. For the manufacture of conventional thermal or acoustic insulation products, the time is between about 0.75 minutes and about 1.5 minutes. When fiberglass having a cured rigid binder matrix emerges from the furnace in the form of a sheet, the sheet can be compressed for packaging and shipping and when subsequently decompressed it will generally substantially recover its vertical dimension at the time of preparation. For example, when a fiberglass sheet having a thickness of about 1.25 inches exits the forming chamber, it will expand to a vertical thickness of about 9 inches in the transfer zone and will be slightly compressed to a vertical thickness of about 6 inches in the curing oven. Inches.

The cured carpet product prepared as described above has a nominal specification of about 0.09 lbs. per square foot, a density of about 0.7 lbs. per cubic foot, a thickness of about 1.5 inches, and a fiber diameter of about 22 parts per million (5.6 microns). The content of the binder after curing is about 11% and the content of the mineral oil (dusting oil) used for dust removal is about 0.7%. The curing oven temperature was set at about 460 °F. The uncured blanket leaving the forming chamber has a white to off-white appearance, and the cured carpet leaving the oven has a dark brown appearance and good adhesion. After collecting several rolls of curing blanket, the board was broken in front of the furnace and an uncured blanket was also collected for the experiment.

Example 9

Triammonium citrate-dextrose (1:6) binder/glass fiber composition: The preparation of air duct plates allows powdered dextrose monohydrate (1800 lbs) and powdered anhydrous citric acid (300 lbs) at Combined in a 2000 gallon mixing tank containing 743.2 gallons of soft water. To the mixture was added 52.9 gallons of 19% aqueous ammonia with stirring, and stirring was continued for about 30 minutes to completely dissolve the solid. 9 pounds of SILQUEST A-1101 decane was added to the resulting solution to produce a solution having a pH of about 8 (by means of a pH test paper) containing about 25% dissolved dextrose monohydrate and dissolved ammonium citrate solid (in solution) The percentage of total weight is expressed as follows; 2 grams of this solution sample is thermally cured at 400 °F for 30 minutes to produce 15% solids (this weight loss is attributed to dehydration during the formation of the thermosetting binder). The solution is stirred for a few minutes before it is transferred to the binder storage tank, where it can be used to make fiberglass spacers, specifically a product known as an "air duct plate."

Air duct panels were prepared using conventional fiberglass manufacturing procedures; such procedures are summarized in Example 8. The air duct plate product has a nominal specification of about 0.4 lbs. per square foot, a density of about 4.5 pounds per cubic foot, a thickness of 1 inch, and a fiber diameter of about 32 parts per million (8.1 microns), and a binder. The mineral oil (dusting oil) having a content of about 14.3% and used for dust removal was 0.7%. The curing oven temperature was set at about 550 °F. The product leaving the furnace has a dark brown appearance and good adhesion.

Example 10

Triammonium citrate-dextrose (1:6) binder/glass fiber composition: R30 household carpet was prepared by powdered dextrose monohydrate (1200 lbs) and powdered anhydrous citric acid (200 lbs) at Combined in a 2000 gallon mixing tank containing 1104 gallons of soft water. To the mixture was added 42.3 gallons of 19% aqueous ammonia with stirring, and stirring was continued for about 30 minutes to completely dissolve the solid. 6 pounds of SILQUEST A-1101 decane was added to the resulting solution to produce a solution having a pH of about 8 (by means of a pH test paper) containing about 13.4% dissolved dextrose monohydrate and dissolved ammonium citrate solid (in solution) The percentage of total weight is expressed; 2 grams of this solution sample is thermally cured at 400 °F for 30 minutes to yield 8% solids (this weight loss is due to dehydration during thermosetting binder formation). The solution is stirred for a few minutes before it is transferred to the binder storage tank, where it can be used to make fiberglass spacers, specifically a product known as the "R30 Household Blanket."

R30 household carpets were prepared using conventional fiberglass manufacturing procedures; such procedures are summarized in Example 8. The nominal specification for the R30 household carpet product is: a weight of about 0.4 psi, a 10-inch thick end of the line, and a fiber diameter of 18 inches (4.6 microns) and a binder content of 3.8. % and the mineral oil (dusting oil) used for dust removal is 0.7%. The curing oven temperature was set at about 570 °F. The product leaving the furnace has a brownish appearance and good adhesion.

Example 11

Triammonium citrate-dextrose (1:6) binder/glass fiber composition: Preparation of R19 household carpet A-1: powdered dextrose monohydrate (1200 lbs) and powdered anhydrous lemon The acid (200 lbs) was combined in a 2000 gallon mixing tank containing 1104 gallons of soft water. 35.3 gallons of 19% aqueous ammonia was added to the mixture with stirring, and stirring was continued for about 30 minutes to completely dissolve the solid. 6 pounds of SILQUEST A-1101 decane was added to the resulting solution to produce a solution having a pH of about 8 (by means of a pH test paper) containing about 13.3% dissolved dextrose monohydrate and ammonium citrate solids (to the total weight of the solution) The percentage is expressed as follows; 2 g of the sample of this solution is thermally cured at 400 °F for 30 minutes to yield 8% solids (this weight loss is attributed to the dehydration during the formation of the thermosetting binder). The solution is stirred for a few minutes before it is transferred to the binder storage tank, where it is used to make a fiberglass spacer, specifically a product known as the "R19 Household Blanket."

The R19 household carpet (batch A-1) was prepared using a conventional fiberglass manufacturing procedure; these procedures are summarized in Example 8. The nominal specifications for the R19 home blanket product are: a weight of approximately 0.2 psi, a density of 0.2 lbs/ft3, a 6.5-inch thick end of the line, and a fiber diameter of 18 inches per 100,000 (4.6 Micron), binder content 3.8% and mineral oil (for dust removal) content 0.7%. The curing oven temperature was set at about 570 °F. The product leaving the furnace has a brownish appearance and good adhesion.

Batch A-2: Powdered dextrose monohydrate (1200 lbs) and powdered anhydrous citric acid (200 lbs) were combined in a 2000 gallon mixing tank containing 558 gallons of soft water. To the mixture was added 35.3 gallons of 19% ammonia with stirring and stirring was continued for about 30 minutes to completely dissolve the solids. Five pounds of SILQUEST A-1101 decane was added to the resulting solution to produce a solution having a pH of about 8 (by means of a pH test paper) containing about 20.5% dissolved dextrose monohydrate and ammonium citrate solids (by total solution weight) The percentage is expressed as follows; 2 g of this solution sample was thermally cured at 400 °F for 30 minutes to yield 12% solids (this weight loss is attributed to dehydration during thermosetting binder formation). The solution is stirred for a few minutes before it is transferred to the binder storage tank, where it can be used to make a fiberglass spacer, specifically a product known as the "R19 Household Blanket."

The R19 household carpet (batch A-2) was prepared using a conventional fiberglass manufacturing procedure; these procedures are summarized in Example 8. The nominal specification for the R19 household carpet product is: a weight of approximately 0.2 lbs. per square foot, a density of approximately 0.4 lbs. per cubic foot, a 6.5 inch thick end of the line, and a fiber diameter of 18 inches per 100,000 feet ( 4.6 μm), binder content 3.8% and mineral oil (for dust removal) content 0.7%. The curing oven temperature was set at about 570 °F. The product leaving the furnace has a brownish appearance and good adhesion.

Batch B: Powdered dextrose monohydrate (300 lbs) was combined with powdered anhydrous citric acid (50 lbs) in a 260 gallon International Bulk Container (IBC) containing 167 gallons of distilled water. 10.6 gallons of 19% ammonia was added to the mixture with stirring, and stirring was continued for about 30 minutes to completely dissolve the solid. 1.5 lbs of SILQUEST A-1101 decane was added to the resulting solution to produce a solution having a pH of about 8 (by means of a pH test paper) containing about 20.1% dissolved dextrose monohydrate and ammonium citrate solids (by total solution weight) The percentage is expressed as follows; 2 g of this solution sample was thermally cured at 400 °F for 30 minutes to yield 12% solids (this weight loss is attributed to dehydration during thermosetting binder formation). Transferring the IBC containing the aqueous binder to an area where the binder is pumped into a binder spray ring in a forming hood where it is diluted with distilled water and subsequently used to make a fiberglass spacer, In this case, a product called "R19 Household Blanket" is formed.

The R19 household carpet (batch B) was prepared using a conventional fiberglass manufacturing procedure; these procedures are summarized in Example 8. The nominal specifications of the R19 household carpet product are: a weight of about 0.2 lbs. per square foot, a density of about 0.4 lbs/ft3, a 6.5 inch thick end of the line, and a fiber diameter of 18 parts per 100,000. The inch (4.6 micron), the binder content of 3.8% and the mineral oil (for dust removal) content of 0.7%. The curing oven temperature was set at about 570 °F. The product leaving the furnace has a brownish appearance and good adhesion.

Batch C: Powdered dextrose monohydrate (300 lbs) was combined with powdered anhydrous citric acid (50 lbs) in a 260 gallon International Bulk Container (IBC) containing 167 gallons of distilled water. 10.6 gallons of 19% ammonia was added to the mixture with stirring, and stirring was continued for about 30 minutes to completely dissolve the solid. To the resulting solution was added 1.5 pounds of SILQUEST A-1101 decane followed by 1.80 gallons of methyl hydrogen emulsion BS 1040 (manufactured by Wacker Chemical Co., Ltd.) to produce a solution having a pH of about 8 (by means of a pH test paper) containing about 20.2% dissolved. Dextrose monohydrate and ammonium citrate solids (expressed as a percentage of the total weight of the solution); 2 grams of this solution is thermally cured at 400 °F for 30 minutes to yield 12% solids (this weight loss is attributed to Dehydration during the formation of thermosetting binders). Transferring the IBC containing the aqueous binder to an area where the binder is pumped into a binder spray ring in a forming hood where it is diluted with distilled water and subsequently used to make a fiberglass spacer, specifically In this case, a product called "R19 Household Blanket" is formed.

R19 Household Blankets (Batch C) were prepared using conventional fiberglass manufacturing procedures; such procedures are summarized in Example 8. The nominal specifications for the R19 household carpet product are: a weight of about 0.2 lbs. per square foot, a density of about 0.4 lbs/ft3, a 6.5 inch thick end of the line, and a fiber diameter of 18 parts per 100,000.吋 (4.6 μm), binder content 3.8% and mineral oil (for dust removal) content 0.7%. The curing oven temperature was set at about 570 °F. The product leaving the furnace has a brownish appearance and good adhesion.

Batch D: Powdered dextrose monohydrate (300 lbs) was combined with powdered anhydrous citric acid (50 lbs) in a 260 gallon International Bulk Container (IBC) containing 167 gallons of distilled water. 10.6 gallons of 19% ammonia was added to the mixture with stirring, and stirring was continued for about 30 minutes to completely dissolve the solid. To the resulting solution was added 1.5 pounds of SILQUEST A-1101 decane followed by 22 pounds of clay product Bentalite L10 (manufactured by Southern Clay Products) to produce a solution having a pH of about 8 (by means of a pH test paper) containing about 21.0% dissolved right. Rotose monohydrate and ammonium citrate solids (expressed as a percentage of the total weight of the solution); 2 grams of this solution was thermally cured at 400 °F for 30 minutes to yield 12.6% solids (this weight loss is attributed to thermoset bonding) Dehydration during the formation of the agent). Transferring the IBC containing the aqueous Maillard binder to a zone where the binder is pumped into a binder spray ring in a forming hood where it is diluted with distilled water and subsequently used to make a fiberglass spacer Specifically, a product called "R19 Household Blanket" is formed.

The R19 household carpet (batch D) was prepared using a conventional fiberglass manufacturing procedure; these procedures are summarized in Example 8. The R19 home blanket product produced the nominal specifications for the day: a weight of approximately 0.2 lbs. per square foot, a density of approximately 0.4 lbs/ft3, a line end recovery of 6.5 inches, and a fiber diameter of 18 parts per 100,000. The inch (4.6 micron), the binder content of 3.8% and the mineral oil (for dust removal) content of 0.7%. The curing oven temperature was set at about 570 °F. The product leaving the furnace has a brownish appearance and good adhesion.

Example 12

Triammonium citrate-dextrose (1:6) binder/glass fiber composition: Preparation of uncured tube separators to make powdered dextrose monohydrate (1200 lbs) with powdered anhydrous citric acid (200 lbs) ) Combined in a 2000 gallon mixing tank containing 215 gallons of soft water. To the mixture was added 42.3 gallons of 19% aqueous ammonia with stirring, and stirring was continued for about 30 minutes to completely dissolve the solid. 6 pounds of SILQUEST A-1101 decane was added to the resulting solution to produce a solution having a pH of about 8 (by means of a pH test paper) containing about 41.7% dissolved dextrose monohydrate and dissolved ammonium citrate solid (in solution) The percentage of total weight is expressed; 2 grams of this solution sample is thermally cured at 400 °F for 30 minutes to produce 25% solids (this weight loss is due to dehydration during thermosetting binder formation). The solution is allowed to stir for a few minutes before it is transferred to the binder storage tank, where it is used to make a fiberglass spacer, specifically a product known as an "uncured tube separator."

The uncured tube spacers were prepared using conventional fiberglass manufacturing procedures; such procedures are summarized in Example 8. The uncured tube separator product has a nominal specification of about 0.07 lbs. per square foot, a density of about 0.85 lbs. per cubic foot, a predicted thickness of 1 inch, and a fiber diameter of 30 inches (7.6 microns) per 100,000, And when curing, the binder content is 7%. The uncured tube spacer is transferred to a tube spacer forming region where it is cast into a cylindrical housing having a 6 inch wall and a 3 inch diameter hole and a density of 4 pounds per cubic foot for use as a tube spacer . The shells were cured with a curing oven set at about 450 °F to produce a dark brown and well bonded tube insulation product. Shells that cure at higher temperatures perform poorly and cannot be used for further testing.

Example 13

Triammonium citrate-dextrose (1:6) binder/cellulosic fiber composition: preparation of wood fiberboard There are several methods used in the industry for the production of binders with triammonium citrate-dextrose (1:6) binder. Wood fiberboard / sheet. A representative method (which produces a strong and uniform sample) is as follows: Wood in the form of various pine chips and sawdust is purchased from a local agricultural supply store. Wood fiberboard samples were made from "receiving" wood and materials that were also separated into shavings and sawdust components. The wood is first dried overnight in an oven at about 200 °F, which causes the moisture removal of the wood chips to be 14 to 15% and the moisture removal of the sawdust to be about 11%. Thereafter, the dried wood was placed in a plastic container (approximate size) of 8 inches high x 12 inches wide by 10.5 inches deep. A triammonium citrate-dextrose (1:6) binder (36% binder solids) was prepared as described in Example 5, and then 160 grams of the binder was sprayed onto the 400 grams of wood in the plastic container via a hydraulic nozzle. On the sample, the container was simultaneously tilted 30 to 40 degrees from the vertical and rotated slowly (about 5 to 15 rpm). During this treatment, the wood was gently turned over while it was evenly coated.

The resin treated wood samples were placed in a collapsible frame and compressed between hot plates under the following conditions: resin treated wood chips, 300 psi; resin treated sawdust, 600 psi. For each resin treated sample, the curing conditions were maintained at 350 °F for 25 to 30 minutes. The resulting sample plate was about 10 inches long x 10 inches wide and was about 0.4 inches thick before trimming, had good internal bonding, a smooth surface, and achieved clean cuts when trimmed on a band saw. The density of the trimmed sample and the size of each trimmed sample plate produced are as follows: a sample plate from wood chips having a density of about 54 pcf and a size of about 8.3 inches long by 9 inches wide by 0.36 inches thick; obtained from sawdust The sample plate has a density of approximately 44 pcf and a size of approximately 8.7 inches long x 8.8 inches wide x 0.41 inches thick. The predicted binder content of each sample plate was about 12.6%.

Example 14

Testing/Evaluation of Triammonium Citrate-Dextrose (1:6) Adhesive/Glass Fiber Compositions The lemons from Examples 8 to 12 were tested against the corresponding phenol-formaldehyde (PF) binder/glass fiber composition. One or more of the following: triammonium-dextrose (1:6) binder/glass fiber composition (ie, curing blanket, air duct panel, R30 household carpet, R19 household carpet, and uncured tube separator): product Dispersion, density, ignition loss, thickness recovery, dust, tensile strength, separation strength, separation strength durability, bond strength, water absorption, hot surface properties, corrosion to steel, bending stiffness, stiffness-stiffness, Compressive strength, adjusted compressive strength, compressive modulus, adjusted compression modulus, and amount of smoke generated during burning. The results of these tests are shown in Tables 8 to 13. The gaseous compounds produced during the curing blanket of the pyrolysis Example 8 and the gaseous compounds produced during the heat curing of the uncured tube separator of Example 12 were also determined; the results of these tests are shown in Tables 14-15. The thermal surface properties of the cured tube separator are shown in Figures 5 and 6. The conditions for carrying out the specific tests and carrying out the tests were as follows: Product Emissions Test The product emissions from the cured blanket of Example 8 and the air line panels from Example 9 were determined according to the AQS Greenguard Testing procedure. According to ASTM D5116 ("Standard Guide for Small-Scale Environmental Chamber Determinations of Organic Emissions from Indoor Materials/Products"), United States Environmental Protection Agency (US Environmental Protection Agency: USEPA) and the State of Washington IAQ Specification (1994 1 Month) Monitoring the amount of total volatile organic compounds (TVOC), formaldehyde, and total selected aldehydes of the separator products. The amount of emission data was collected after 1 week of exposure and the resulting air concentration of each of the foregoing materials was determined. Computer monitoring of air concentration predictions is performed according to Washington State requirements, including standard room loads and ASHRAE Standard 62-1999 ventilation conditions. The product is based on loading of 32 m ³ chamber wall using the standard of 28.1 m ^2.

Emission of the test - the selected aldehyde in a small volume of 0.0855 m ³ environmental chamber testing of the isolation and analysis of the product for distributing measured amounts of chemicals. The amount of the selected aldehyde, including formaldehyde, is measured by high performance liquid chromatography (HPLC) according to ASTM D5197 ("Standard Test Method for Determination of Formaldehyde and Other Carbonyl Compounds in Air (Active Sampler Methodology)". a solid absorbent column of 2,4-dinitrophenylhydrazine (DNPH) to collect formaldehyde and other low molecular weight carbonyl compounds in the air of the chamber. The DNPH reagent in the column reacts with the collected carbonyl compound to form a tube. The column is entrapped in a stable hydrazine derivative. The hydrazine derivative is eluted from the column with HPLC grade acetonitrile. Low molecular weight aldoxime derivatization of aliquots by UV detection by reversed-phase high performance liquid chromatography (HPLC) The absorbance of the derivatives was measured at 360 nm. The mass response of the resulting peaks was determined using a multi-point calibration curve drawn from the standard solutions of the indole derivatives. Based on a standard air volume collection report of 45 litres The measured value is a quantifiable value of 0.2 micrograms.

Dispersion Test - Volatile Organic Compound (VOC) VOC measurements were performed using gas chromatography and mass spectrometry (GC/MS). The chamber air is collected on a solid absorbent and then the solid absorbent is thermally desorbed in the GC/MS. The absorbent collection technology, separation and detection analysis methods have been modified according to the techniques proposed by USEPA and other researchers. This technology meets USEPA Method 1P-1B and is generally applicable to a boiling point range between the 35 ℃ C to 250 ℃ ₅ to C ₁₆ organic chemicals. The record is based on a standard air volume collection of 18 liters. The measured value is a quantifiable value of 0.4 micrograms. Each VOC was separated and detected by GC/MS. The total VOC measurement is performed by adding all individual VOC responses obtained by the mass spectrometer and calibrating the total mass relative to toluene.

Dispersion Test - Air Concentration The emission rate of formaldehyde, total aldehyde and TVOC is used in a computer exposure model to determine the potential air concentration of such materials. The computer model uses the measured spatter rate over a one-week period to determine the corresponding change in air concentration. The model measurements are based on the assumption that the air in the open office area of the building mixes well in the area of respiration of the occupied space; the environmental conditions are maintained at 50% relative humidity and 73°F (23°C); Additional sources of matter exist; and there are no heat sinks or potential sources of re-emergence in the space of such materials. The USEPA's Indoor Air Exposure Model (Version 2.0) is specifically modified to suit the product and the chemicals of interest. Ventilation and occupancy parameters are provided in ASHRAE Standard 62-1999.

Density The density of the cured blanket of Example 8 was determined according to the internal test method PTL-1 "Test Method for Density and Thickness of Blanket or Batt Thermal Insulation", which is substantially the same as ASTM C 167. The density of the air duct plate of Example 9 was determined according to the internal test method PTL-3 "Test Procedure for Density Preformed Block-Type Thermal Insulation", which is substantially the same as ASTM C 303.

The amount of ignition loss (LOI) of the curing blanket of Example 8 and the amount of ignition loss of the air piping plate of Example 9 were determined according to the internal test method K-157 "Ignition Loss of Cured Blanket (LOI)". The test was carried out on a sample in a wire pan placed in a 1000 °F +/- 50 °F oven for 15 to 20 minutes to ensure complete oxidation, and the resulting sample was weighed after the treatment.

The separation strength of the solidification blanket of the separation strength example 8, the R30 household blanket of Example 10, and the R19 household blanket of the example 11 was determined according to the internal test method KRD-161, which is substantially in accordance with ASTM C686 "Parting Strength of Mineral Fiber Batt". Same as Blanket-Type Insulation.

Durability of Separation Strength The durability of the separation strength of the R30 household carpet of Example 10 and the R19 household carpet of Example 11 was adjusted at 90 °F and 95% relative humidity for 1 week according to ASTM C 686 "Parting Strength of Mineral Fiber Batt and Measured by Blanket-Type Insulation.

Tensile Strength The tensile strength of the cured carpet of Example 8 and the R19 household carpet of Example 11 were measured according to the internal test method KRD-161 "Tensile Strength Test Procedure". The test was carried out on samples that were die cut in both the machine direction and the transverse direction. The samples were conditioned for 24 hours at 75 °F and 50% relative humidity. Ten samples were tested in each longitudinal direction in a test environment of 75 °F, 50% relative humidity. Dog bone samples are as specified in ASTM D638 "Standard Test Method for Tensile Properties of Plastics". A crosshead speed of 2 inches per minute was used for all tests.

Bonding Strength The internal lamination bond strength of the cured carpet of Example 8, the R30 household carpet of Example 10, and the R19 household carpet of Example 11 was determined using the internal test method KRD-159 "Bond Strength of Fiberglass Board and Blanket Products". A molded sample having a cross-sectional area of 6 inches x 6 inches was bonded to a 6 inch x 7 inch sample mounting plate and placed in a fixture that applied force perpendicularly to the surface of the sample. A crosshead speed of 12 inches per minute was used for all tests.

Thickness recovery was carried out on the curing blanket of Example 8 using the internal test method K-123 "Recovered Thickness-End of Line Dead Pin Method-Roll Products" and K-109 "Test Procedure for Recovered Thickness of Roll Products-Rollover Method". And tumbling thickness test. The recovered thickness is measured by the following measurement: 15 minutes or later after packaging, the needle gauge is forced to pass through the cured blanket sample from a roll of product until the needle contacts the flat hard surface under the sample, and then the steel ruler is used. Measure the thickness recovered. Use the internal test method K-120 "Test Procedure for Determining End-of-Line Dead-Pin Thickness-Batts" and K-128 "Test Procedure for Recovered Thickness of Batt Products-Drop Method" (both test methods are used with ASTM C 167 "Standard Test Methods for Thickness and Density of Blanket or Batt Thermal Insulations" was similarly tested on the R30 household carpet of Example 10 and the R19 household carpet of Example 11.

Dust test A dust test was carried out on the curing blanket of Example 8, the R30 household carpet of Example 10, and the R19 household carpet of Example 11 using the internal test procedure K-102 "Packaged Fiber Glass Dust Test, Batt Method". The dust released by the randomly selected sample (bath) of the curing blanket, the R30 household carpet, and the R19 household carpet dropped into the dust collection box was collected on the filter and the amount of dust was measured by the differential method.

Water Absorption Rate The water absorption rate (% by weight) test was carried out on the cured carpet of Example 8 and the R19 household carpet of Example 11 using ASTM C 1104 "Test Method for Determining the Water Vapor Absorption of Unfaced Mineral Fiber Insulation".

Bending Stiffness (EI) The bending stiffness of the air duct plate of Example 9 (which is the force required to bend the rigid air duct plate (ie, the product of the elastic modulus E and the inertia moment I)) is based on NAIMA AHS 100- 74 "Test Method for Flexural Rigidity of Rectangular Rigid Duct Materials".

Rigidity-Stiffness A stiffness-stiffness test was performed on the R19 household carpet of Example 11 using the internal test procedure K-117 "Test Procedure for Rigidity of Building Insulation". A sample of R19 household carpet having a length of about 47.5 inches (± 0.5 inch) was placed on a central support rod of a rigid test apparatus that included a protractor positioned directly behind the central support rod. The ends of the sample are free to hang, and the angle (in degrees) of each end of the sample is recorded by reading the protractor while viewing along the bottom edge of the sample.

Compressive Strength The compressive strength of the air duct plate of Example 9 was measured in accordance with ASTM C 165 "Standard Test Method for Measuring Compressive Properties of Thermal Insulations".

Adjusted Compressive Strength The adjusted compressive strength of the air duct panels of Example 9 was determined according to ASTM C 165 "Standard Test Method for Measuring Compressive Properties of Thermal Insulations" after one week at 90 °F and 95% relative humidity.

Compression modulus The compression modulus of the air duct plate of Example 9 was determined in accordance with ASTM C 165 "Standard Test Method for Measuring Compressive Properties of Thermal Insulations".

The adjusted compression modulus of the air duct plate of the modified compression modulus example 9 is after 90 weeks at 90 °F and 95% relative humidity according to ASTM C 165 "Standard Test Method for Measuring Compres Sive Properties of Thermal Insulations". Determination.

Hot surface properties using ASTM C 411 "Test Method for Hot Surface Performance of High Temperature Thermal Insulation " hot surfaces embodiment performance tests on the examples of the curing blanket 8, Example 10 of household carpets and R30 R19 household carpet of Example 11. The hot surface performance test was carried out at 650 °F and 1000 °F using ASTM C 411 "Test Method for Hot Surface Performance of High Temperature Thermal Insulation" on a 3 x 6 inch cross section of the cured tube insulation product of Example 12. The internal temperature of the separator was not measured to rise above the hot surface temperature of the tube.

Corrosion to steel Corrosion tests were carried out with respect to steel specimens on the R30 household carpet of Example 10 and the R19 household carpet of Example 11 using an internal test procedure Knauf PTL-14 substantially identical to ASTM C 665.

Smoke generation during ignition Example 8: The amount of smoke generated during the burning of the cured blanket (using the calculated area of the extinction area (SEA)) is based on ASTM E 1354 "Test Method for Heat and Visible Smoke Release Rates for Materials and Products Using an Oxygen The Consumption Calorimeter is measured by cone calorimetry.

The gaseous compound produced during the pyrolysis gas compound produced during the curing blanket of Pyrolysis Example 8 was determined as follows: Approximately 10 grams of the cured blanket was placed in a test tube, and then the tube was heated to 1000 °F for 2.5 minutes, at which time the top The space was sampled and analyzed by gas chromatography/mass spectrometry (GC/MS) under the following conditions: furnace, at 50 ° C for 1 minute - at 10 ° C / minute to 300 ° C and held for 10 minutes; inlet, 280 ° C No splitting; column, HP-5 30 mm x 0.32 mm x 0.25 μm; column flow rate, 1.11 ml/min helium; detector, MSD 280 ° C; injection volume, 1 ml; detector mode, scan 34-700 Amu; threshold, 50; and sampling rate, 22 scans/second. A computer study of the mass spectrum of the sample chromatographic peak was performed against a Wiley mass spectrometer library. Record the best match. Produces a quality index between 0 and 99 (proximity to match the library spectrum). Only features with a quality index greater than or equal to 90 are recorded.

The gaseous compound produced during the thermal curing of the gas compound produced during the heat curing of the uncured tube separator of Example 12 was determined as follows: About 0.6 grams of the uncured tube separator was placed in a test tube, and then the tube was heated to 540 °F for 2.5 minutes. At this time, the head space was sampled and analyzed by gas chromatography/mass spectrometry under the following conditions: furnace, 1 minute at 50 ° C - 10 ° C / minute to 300 ° C for 10 minutes; inlet, 280 ° C without Split; column, HP-5 30 mm x 0.32 mm x 0.25 μm; column flow rate, 1.11 ml/min helium; detector, MSD 280 ° C; injection volume, 1 ml; detector mode, scan 34-700 amu ; threshold, 50; and sampling rate, 22 scans / sec. A computer study of the mass spectrum of the sample chromatographic peak was performed against a Wiley mass spectrometer library. Record the best match. Produces a quality index between 0 and 99 (matching proximity to the library spectrum). Only features with a quality index greater than or equal to 90 are recorded.

^a obtained from Example 1 ^b MW = 243 g / mol; 25% (% by weight) solution ^c MW = 198 g / mol; 25% (% by weight) solution ^d approximation ^e accompanied by significant ammonia

^a from example 4

^a obtained from Example 6 ^b from Example 5 ^c 9 shell bone sample average ^d prepared 7 batches of different triammonium citrate-dextrose (1:6) binder batches over a period of 5 months The average value of 7 different batches of triammonium citrate-dextrose (1:6) binder prepared by post- ^e after 5 months

^a obtained from Example 6 ^b from the average value ^d of 9 ^c 9 shell samples obtained from the average ^d of 7 different triammonium citrate-dextrose (1:6) binder batches after 5 months the value of ^e Silres BS 1042 polyethylene-based polymethyl hydrogen silicone emulsion of 50% solids alumoxane ^{f g} sample of replication replicate samples ^h LE 46 35% solids emulsion based ^I polydimethylsiloxane of TPX5688 / AQUA-TRETE BSM40 homologous alkanes 40% emulsion of decane. ^j PGN is a clay grade montmorillonite from Nanocor. ^k Cloisite NA+ is a clay sodium salt ¹ foamed soymilk (25%) from Southern Clay Products. Soybean oil and PEG 400 dioleate. (4% solids) and guar gum (1% solids) 25% solid emulsion ^m Bentolite L-10 is obtained from Southern Clay Products clay ⁿ Michem 45745 PE emulsion (50%) is 25% solids of low molecular weight polyethylene Emulsion ^o bone cement solution 30% solid solution ^p Axel INT-26-LF95 fat-based release agent / emulsion ^q ISO Chill Whey 9010 ^r uncalculated ^s unmeasured

^a obtained from Example 6 ^b obtained from the average value ^d of 9 ^c shell samples of Example 5 ^c . The average of 7 different triammonium citrate-dextrose (1:6) binder batches after 5 months. Value ^e 200 g AQUAsET-529+87 g 19% ammonia + 301 g dextrose + 301 g 30% solution of water ^f 300 ml from the solution of the binder ^e + 0.32 g SILQUEST A-1101 ^g 200 g AQUASET-529 + 87 g 19% Ammonia + 101 grams of water + 0.6 grams of SILQUEST A-1101 ^h AQUASET-529 + SILQUEST A-1101 (0.5% binder solids), diluted to 30% solids ^I 136 grams of pentaerythritol + 98 grams of maleic anhydride + 130 grams of water, reflux for 30 minutes 232 g of the obtained solution was mixed with 170 g of water and 0.6 g of SILQUEST A-1101, ^j 136 g of isoptoerythritol + 98 g of maleic anhydride + 130 g of water + 1.5 ml of 66% p-toluenesulfonic acid, refluxed for 30 minutes; 232 g of the obtained solution Mix with 170 g of water and 0.6 g of SILQUEST A-1101 ^k 220 g of binder ⁱ +39 g of 19% ammonia + 135 g of dextrose + 97 g of water + 0.65 g of SILQUEST A-1101 ^l 128 g of citric acid + 45 g of pentaerythritol +125 g water, reflux for 20 minutes; dilute the resulting mixture to 30% solids and add SILQUEST A-1101 ^m 200 g Kemira to 0.5% solids CRITERION 2000+23g glycerin+123g water+0.5g SILQUEST A-1101 ⁿ 200g Kemira CRITERION 2000+30g glycerin+164g water+0.6g SILQUEST A-1101 ^o 100g BASF SOKALAN CP 10 S+57g 19% ammonia +198g right-handed Sugar + 180 g water + 0.8 g SILQUEST A-1101 ^p 211 g HBFuller NF1 + 93 g 19% ammonia + 321 g dextrose + 222 g water + 1.33 g SILQUEST A-1101

a obtained from Example 6 b from Example 5 c Average of 9 shell bone samples d Average of 7 batches of material e DHA = dihydroxyacetone f monocarboxylate g non-carboxylic acid h pH 7

^a obtained from Example 7 ^b from Example 5 ^c average of 3 glass fiber boards ^d Dex = dextrose ^e Fruc = fructose ^f DHA = dihydroxyacetone ^g glycerol instead of 25% by weight DHA ^h PETol = isovalerol replacement 25 Weight % DHA ^I PVOH = polyvinyl alcohol (86 to 89% hydrolyzed polyvinyl acetate, MW about 22K to 26K) instead of 20% by weight DHA ^j Ductliner binder

^a SEA = specific extinction area

^a class of black fine bonding agent; nominal machine conditions to produce 5% of the loss of burning ^b- type black fine bonding agent; adjust the machine to increase the burning loss to 6.3% ^c- class black fine bonding agent; adjust the machine to rise High ignition loss to 6.6% ^d not measured

Although certain embodiments of the invention have been illustrated and/or illustrated, the invention is intended to cover numerous variations and modifications. Therefore, the invention is not limited to the specific embodiments described and/or illustrated herein.

Figure 1 shows various exemplary reactants for the production of melanoid; Figure 2 illustrates a schematic of the Maillard reaction when the reducing sugar is reacted with an amine compound; Figure 3 shows the FT- of an exemplary embodiment of the dry binder of the present invention. IR spectrum; Figure 4 shows the FT-IR spectrum of an exemplary embodiment of the cured binder of the present invention; Figure 5 shows the 650 °F hot surface properties of a fiberglass tube insulation made using an exemplary embodiment of the present invention; 6 shows the 1000 °F hot surface properties of a fiberglass tube insulation made with an exemplary embodiment of the present invention.

Claims (19)

A composition comprising a collection of materials and a binder comprising a black-like product of substantially dehydration of a carbohydrate with an amine base, the black essence being crosslinked with a polycarboxylic acid. The composition of claim 1, wherein the collection of materials comprises a material selected from the group consisting of mineral fibers, aromatic polyamide fibers, ceramic fibers, metal fibers, carbon fibers, polyimine fibers, polyester fibers, rayon fibers. a group of fibers composed of glass fibers and cellulose fibers. The composition of claim 1, wherein the composition further comprises a ruthenium containing compound. The composition of claim 3, wherein the cerium-containing compound is selected from the group consisting of γ-aminopropyltriethoxydecane, γ-glycidyloxypropyltrimethoxynonane, and aminoethylaminopropyltrimethyl a group consisting of oxoxane, n-propylamine decane, and mixtures thereof. The composition of claim 4, wherein the ruthenium containing compound is γ-aminopropyltriethoxydecane. The composition of claim 1 wherein the collection of materials comprises glass fibers. The composition of claim 6, wherein the composition further comprises a corrosion inhibitor, wherein the corrosion inhibitor reduces corrosion of the glass fiber. The composition of claim 7, wherein the corrosion inhibitor is selected from the group consisting of dusting oil, ammonium dihydrogen phosphate, sodium metasilicate pentahydrate, melamine, tin (II) oxalate, and methyl hydrogen polyoxyl fluid emulsion. a group of people. The composition of claim 1 wherein the collection of materials comprises cellulosic fibers. The composition of claim 9, wherein the cellulosic fibers are present in a cellulosic substrate selected from the group consisting of wood chips and sawdust. The composition of claim 1 wherein the carbohydrate is a monosaccharide in the form of an aldose or ketose. The composition of claim 1, wherein the carbohydrate is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. The composition of claim 1 wherein the carbohydrate is dextrose. The composition of claim 1, wherein the polycarboxylic acid is a monomeric polycarboxylic acid. The composition of claim 14, wherein the ratio of the molar number of the monomeric polycarboxylic acid to the molar number of the carbohydrate is between 1:4 and 1:15. The composition of claim 14, wherein the monomeric polycarboxylic acid is selected from the group consisting of citric acid, maleic acid, tartaric acid, malic acid, succinic acid, and mixtures thereof. The composition of claim 14, wherein the polycarboxylic acid is citric acid. The composition of claim 1 wherein the black essence product is formed during curing of the dehydrated alkaline solution. The composition of claim 1, wherein the black essence product is crosslinked by an ester chain.