Carbohydrate binders and materials made therewith.
Abstract
Se describe un aglutinante que comprende los productos de un reactivo de carbohidrato y poliamina. El aglutinante es útil para consolidar material libremente ensamblada, tal como fibras. Los productos fibrosos sin cura que comprenden fibras n contacto con un reactivo de carbohidrato y una poliamina también se describen. La composición aglutinante puede curarse para producir un producto fibroso que comprende fibras enlazadas por un polímero reticulado. Además se describen los métodos para enlazar fibras con el reactivo de carbohidrato y el aglutinante basado en poliamina.

Term
4.6 yearsleft in the term
Expires 7 May 2031.
- Priority
- Filed
- Granted
- Today
- Expires
9 claims: 7 independent, 2 dependent
- 1NOVEDAD DE LA INVENCIÓN Habiendo descrito la presente invención, novedad, y por lo tanto se reclama como propiedad lo contenido en las siguientes:REIVINDICACIONES 1. Un método de fabricación de un tablero de madera compuesto que comprende una colección de materia, que comprende fibras celulósicas unidas con un aglutinante polimérico termoestable curado, el método caracterizado porque comprende: preparar una solución de aglutinante acuoso que contiene reactivos para producir el aglutinante polimérico termoestable curado, en donde los reactivos incluyen una azúcar reductora y un nucleófilo R1-Q-R2, en donde: (a) Q es un alquilo, cicloalquilo, heteroalquilo, o cicloheteroalquilo, cada uno de los cuales es opcionalmente sustituido por un grupo seleccionado del grupo que consiste de hidroxilo, halo, tiol, alquilo, haloalquilo, heteroalquilo, arilo, arilalquilo, arilheteroalquilo, nitro, ácidos sulfónicos y derivados de los mismos, ácidos carboxílicos y derivados de los mismos;(b) Ri es una amina;y (c) R.2 se selecciona del grupo Instituto mexicano DE LA ITOHTOAD INDUSTRIAL amida, imina, nitro, nitrato, piridina, fosfato, fosfono, hidroxilo, sulfono, sulfo, sulfinilo, sulfhidrilo, azida, cianato, isocianato, tiol, disulfido, tiocianato, halógeno, haloformil, carboxil, carboxilato y alcoxido;disponer la solución de aglutinante acuoso sobre una colección de materia;secar la solución de aglutinante acuoso para formar un aglutinante no curado y curar térmicamente el producto no curado para formar el tablero de madera compuesto con el aglutinante polimérico termoestable curado.
- 2El método de conformidad con la reivindicación 1, en donde el aglutinante polimérico termoestable curado está libre de formaldehído.
- 3El método de conformidad con la reivindicación 1 o 2, en donde ninguno de formaldehído ni fenol es usado como reactivo.
- 4El método de conformidad con cualquiera de las reivindicaciones 1-3, en donde las fibras celulósicas comprenden materia seleccionada del grupo que consiste de virutas de madera, aserrín, pulpa de madera, madera terrestre, yute, lino, cáñamo, y paja. El método de conformidad con cu, DE LA FROFif PAD INDUSTRIAL reivindicaciones 1-4, en donde la relación de peso del azúcar reductor al nucleófilo está en el rango de 2:1 a 10:1.
- 56. El método de conformidad con cualquiera de las reivindicaciones 1-5, en donde el azúcar reductor se selecciona del grupo que consiste de dextrosa, xilosa, fructosa, dihidroxiacetona, y mezclas de los mismos.
- 67. El método de conformidad con cualquiera de las reivindicaciones 1-6, en donde Ri y R 2 forma enlaces covalentes con el azúcar reductor para formar un aglutinante polimérico.
- 78. El método de conformidad con cualquiera de las reivindicaciones 1-7, en donde Q es una alquilo, cicloalquilo, heteroalquilo, o cicloheteroalquilo, cada uno de los cuales es no sustituido.
- 89. El método de conformidad con cualquiera de las reivindicaciones 1-8, en donde R 2 se selecciona del grupo que consiste de amida, imina, nitro, fosfato, fosfono, hidroxilo, sulfo, sulfinilo, cianato, isocianato, tiol, halógeno, haloformil, carboxil, carboxilato y alcoxido.
- 910. El método de conformidad con cualquiera de las reivindicaciones 1-8, en donde R 2 se selecciona del grupo que consiste de amida, imina, fosfato, fosfono, hidroxilo, sulfo, sulfinilo, cianato, tiol, carboxil y carboxilato. 1/3 IMPI FlG. 1 INSTITUTO MEXICANO » DE LA PROPIEDAD INDUSTRIAL 2/3 V Fig. 2 IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL RNH I HC-1 I I (HCOH), O HC-1 I CHjOH Aldosilamina N-sustituido RNH RNH RNH -i-H* CH I HCOH (hÍoh), CHjOH Catión de baseSchiff CU CHj -H* II I -► COH .....S.....' C:O (H CHjOH (H CHjOH Forma enol Forma ceto, 1am¡no-1-deoxi-2cetosa, sustituida conN 3/3 Fig.3 Tiempo de molde
Independent claims9
434 paragraphs in 19 sections, as filed
(54) Title: CARBOHYDRATE BINDERS AND MATERIALS MADE WITH THEM. (54) Title: CARBOHYDRATE BINDERS AND MATERIALS MADE THEREWITH.
(57) Summary
A binder is described comprising the products of a carbohydrate and polyamine reagent. The binder is useful for consolidating freely assembled material, such as fibers. Uncured fibrous products comprising fibers in contact with a carbohydrate reagent and a polyamine are also described. The binder composition can be cured to produce a fibrous product comprising fibers bonded by a crosslinked polymer. In addition, methods for bonding fibers with the carbohydrate reagent and the polyamine-based binder are described.
(57) Abstract
A binder comprising a polymeric binder comprising the products of a carbohydrate reactant and nucleophile is disclosed. The binder is useful for consolidating loosely assembled matter, such as fibers. Fibrous products comprising fibers in contad with a carbohydrate reactant and a nucleophile are also disclosed. The binder composition may be cured to yield a fibrous product comprising fibers bound by a cross-linked polymer. Further disclosed are methods for binding fibers with the carbohydrate reactant and polyamine based binder.
Institute
Mexican Property
Industrial
<img file="MX339649B_D0001.tif" />
PATENT TITLE NO. 339649 μ!
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Owner (s): KNAUFINSULATION
Address: Rué de Maestricht 95, B-4600, Visé, BELGIUM
Name: CARBOHYDRATE BINDERS AND MATERIALS MADE WITH THEM.
Classification: lnt.CI.8: C08G12 / 00; C08G14 / 00; C08G16 / 00
Inventor (s): CHARLES APPLEY: CARL HAMPSON; GERT MUELLER; BÉNÉDICTE
PACOREL
REQUEST
Number: International filing date:
MX / a / 2012/012635 May 07, 2011
PRIORITY
Country: Date: Number:
US May 7, 2010 61 / 332,452
Affluence: Twenty years ifbcha Maturity: May 7, 2031
The reference patent is granted based on articles 1, 2nd section V, 6th section III, and 59 of the Industrial Property Law.
In accordance with article 23 of the Industrial Property Law, this patent has a validity of twenty non-extendable years, counted from the filing date of the international application and will be subject to the payment of the fee to keep the rights in force. . s
Whoever signs this title does so based on the provisions of articles 6 fractions III and 7 bis 2 of the Industrial Property Law (Official Gazette of the Federation (DOF) 06/27/1991, amended on 02 / 08/1994, 10/25/1996, 12/26/1997, 05/17/1999, 01/26/2004, 06/16/2005, 01/25/2006, 06/05/2009 / 06/01 / 2010, 06/18/2010, 06/28/2010, 01/27/2012 and 04/09/2012); Articles 1, 3 · fraction V, subsection a), sub subsection iii), 4th and 12th sections I and lll of the Regulations of the Mexican Institute of Industrial Property (DOF 14/12/1999, amended on 07/01/2002, 07/15/2004, 07/28/2004 and 09/07/2007); Articles 1, 3, 4, 5, section V, Section a), sub Section II), 16 sections I and lll and 30 of the Organic Statute of the InstitutB: Mexican of Industrial Property (DOF 12/27/1999, amended on 10/10/2002, 07/29/2004, 08/04/2004 and 09/13/2007); 1 °, 3 ° and 5Í »ímülBi8) ;; and the penultimate paragraph of the Agreement that delegates powers to the Deputy Directors General, Coordinator, Divisional Directors, Holders of the Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of the Industrial property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).
Issue Date: June 2, 2016
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CARBOHYDRATE BINDERS AND MATERIALS H £ C¡ £) & LQS,
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MEXICAN INSTITUTE F¿ ^ * ÍÍÍÍai '·'. · DS THE PROPERTY ---- “->»
INDUSTRIAL
SAME
FIELD OF THE INVENTION
The disclosure relates to a binder formulation and materials made therefrom comprising a carbohydrate-based binder and a method of preparing the same. In particular, a binder is described comprising the reaction products of a carbohydrate and a nucleophile and materials made therefrom.
BACKGROUND OF THE INVENTION
Binders are useful in manufacturing articles because they are capable of consolidating non-assembled or freely assembled material. For example, binders allow one or two surfaces to bond. In particular, the binders can be used to produce products comprising consolidated fibers. Thermoset binders can be characterized by being transformed into insoluble and infusible materials by means of either heat or catalytic action. Examples of thermoset binders include a variety of phenolaldehyde, urea-aldehyde, melamine-aldehyde, and other furan-type condensation-polymerization materials and
MEXICAN INSTITUTE rciWeeft
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polyurethane resins. The compositions contain phenol-aldehyde, phenol / aldehyde / urea, phenol / melamine / aldehyde-S3.m, all of which are used for bonding fibers, textiles, plastics, rubbers, and many other materials.
The mineral wool and agglomerate industries have historically used a phenol formaldehyde binder to bond fibers. Binders of the phenol formaldehyde type provide suitable properties for the final products; however, environmental considerations have motivated the development of alternative binders. One such alternative binder is a carbohydrate-based binder derived from a reaction carbohydrate and a multiprotic acid, for example, US Published Application.
No. 2007/0027283 and PCT Application Published W02009 / 019235.
Another alternative binder is the esterification products of the reaction of a carboxylic acid and a polyol, for example, US Published Application No.
2005/0202224. Because these binders do not use formaldehyde as a reagent, they have been collectively referred to as formaldehyde-free binders.
One area of current development is finding a replacement for phenol formaldehyde-type binders across the entire range of products in the construction sector and
<img file="MX339649B_D0005.tif" />
automotive (for example fib particle board insulation, office panels, and acoustic sound). In particular, the previously developed agglutirtáfttéS librés d'e formaldehyde may not possess all the desired properties for all products in this sector. For example, binders based on acrylic acid and poly (vinyl alcohol) have shown promising performance characteristics. However, these are relatively more expensive than phenol formaldehyde binders, and are essentially derived from petroleum-based resources, and have a tendency to exhibit lower reaction rates compared to phenol formaldehyde-based binder compositions (requiring either time long curves or increased cure temperatures). The carbohydrate-based binder compositions are made from relatively inexpensive precursors and are derived primarily from renewable resources; however, these binders may also require reaction conditions for cure that are substantially different from those conditions under which the traditional phenol formaldehyde binder system cures. Like tai, easy replacement of phenol formaldehyde-type binders with an existing alternative has not been easily achieved.
SUMMARY OF THE INVENTION í
According to the present description ^
<img file="MX339649B_D0006.tif" />
carbohydrate based binder. The binder composition has properties that make it useful for a variety of applications; particularly, the binder can be used to bond assembled material without much stiffness such as fibers.
In illustrative embodiments, the present disclosure relates to a binder comprising a polymeric product of a carbohydrate reagent and a polyamine. In one embodiment, the carbohydrate reagent is a polysaccharide. In one embodiment, the carbohydrate reagent is a monosaccharide or disaccharide. In another embodiment, the carbohydrate is a monosaccharide in its aldose or keto form.
In another embodiment, the carbohydrate reagent is selected from a group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In another embodiment, the polymeric product is a thermoset polymeric product.
In illustrative embodiments, the nucleophile is a difunctional. In one embodiment, the nucleophile is Ri-QR<sub>2</sub> wherein q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which is optionally substituted having a nucleophilic moiety and a stabilizing moiety, Ri is selected from the group jqj ^ jcp ^ -p ^ g ^ g ^. MEXICAN INSTITUTE / ¿**** 4 * an amine, an azide, a cyanate, an isocyanafσ> Γ ·<sup>Α</sup>, ^^ ΐθdisulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl, and an alkoxide, and R2 is selected from the group consisting of an amine, an amide, an imine, an imide, a nitro , a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulfone, a sulfo, a sulfinyl, and a sulfhydryl (thiol). In one embodiment, the nucleophile includes an amine functional group.
In illustrative embodiments, the molar ratio of the carbohydrate reagent to the polyamine is in a range of from about 1: 1 to about 30: 1. In another embodiment, the molar ratio of the carbohydrate reagent to the nucleophile is in a range from about 2: 1 to about 10: 1. In another embodiment, an aqueous extract of the polymeric product has a pH in the range of about 5 to about 9. In another embodiment, an aqueous extract of a polymeric product is essentially colorless. In yet another embodiment, the polymeric product is phenol-free and / or formaldehyde-free. In another embodiment, an aqueous extract of a polymeric product is capable of reducing the Benedict reagent. In another embodiment, the polymeric product absorbs light between 400 and 500 nm, for example, in one embodiment, at 420 nm.
In an illustrative modality, a method of making one to be born
MPI'G collecting matter linked with an agglutÍBaitóéMÉ) m «Kbii« W3 »© ancla<sup>:</sup>'. ^
FROM THE FRAMEWORK l ND 'J STR l AL * «».
it comprises preparing a solution containing reagents to produce the polymeric binder and a solvent, wherein the reagents include a carbohydrate reagent and a nucleophile; arranging the solution in the collection of matter; volatilizing the solvent to form an uncured product, and subjecting the uncured product to conditions that cause the carbohydrate reagent and polyamine to polymerize to form the polymeric binder. In one embodiment, the collection of matter comprises fibers selected from a group consisting of mineral fibers (slag wool, rock wool fiber, or glass fiber), aramid fibers, ceramic fibers, metal fibers, carbon, polyamide fibers, polyester fibers, rayon fibers and cellulosic fibers. In another embodiment, the collection of matter comprises particles such as coal or sand. In another embodiment, the collection of matter is glass fibers. In yet another embodiment, the glass fibers are present in a range of from about 70% to about 99% by weight. In another embodiment, the collection of matter comprises cellulosic fibers. For example, cellulosic fibers can be wood chips, sawdust pulp, wood, or chopped wood. In yet another embodiment, the f ib ^^^^^ i- ^ ó ^ ib.as may be other natural fibers such as goi ^ 'm ^^ íúS: INDUSTRIAL hemp, and straw. ________
In illustrative embodiments, the method of making a bound matter collection with a polymeric binder further includes preparing a solution by adding an amount of a carbohydrate reagent and an amount of a nucleophile such that the weight ratio is in the range of about 2 : 1 to about 10: 1, respectively. In one embodiment, preparing the solution includes adding the carbohydrate reagent and the nucleophile to an aqueous solution. In another embodiment, preparing the solution includes adjusting the pH of the solution to within the range of about 8 to about 13, for example, the range of about 8 to about 12.
In illustrative embodiments, the present disclosure relates to a composition comprising a collection of matter and a binder; the binder comprises the polymeric products of a reaction between a carbohydrate reagent and a nucleophile, the polymeric products being substantially insoluble in water. In one embodiment, the collection of matter includes mineral fibers (from slag wool, rock wool fibers, or glass fibers), aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyamide fibers, fib
.....- - ^ ííw- «S« j * ''<sup>Λ</sup> ,, JZ'-L. η Ί 'TA · INSTITUTO MEXICANO rayon fibers and cellulosic fibers. By ei emole / Rorla®<sup>JJ</sup> Cellulose-based INDUSTRIAL include wood chips, sawdust pulp, wood, or chopped wood. In one embodiment, the carbohydrate reagent is selected from a group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In another embodiment, the polyamine is selected from a group consisting of a diamine, triamine, tetramine, and pentamine. In one embodiment, the nucleophil is R1-Q-R2, where Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which is optionally substituted, Ri is a nucleophilic moiety, and R2 is a stabilization moiety. In one embodiment, Ri is selected from a group consisting of an amine, an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl, and an alkoxide. In another modality, R<sub>2</sub> is selected from a group consisting of an amine, an amide, an imine, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydroxyl, a hydrogen, a sulfone, a sulfo, a sulfinyl, and a sulfhydryl (thiol).
In another embodiment, the composition further comprises a silicon-containing compound. In one embodiment the silica-containing compound is a functionalized silylether or a functionalized alkylsilyl ether, such as "-Wi" S ·, industrial -— amino-functionalized alkylsilyl ether. For example, in one embodiment, the silicon-containing compound may be gammaaminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, or aminoethylaminopropyltrimethoxysilane, or a mixture thereof. In another embodiment, the silicon-containing compound may be an amino-functional oligomeric siloxane. In another embodiment, the composition comprises a corrosion inhibitor selected from a group consisting of dedusting oil, monoammonium phosphate, sodium metasilacate pentahydrate, melamine, tin (II) oxalate, and a methylhydrogen silicone fluid emulsion.
BRIEF DESCRIPTION OF THE FIGURES
Fig. 1 shows a schematic of a Maillard reaction, culminating in the production of melanoidins.
Fig. 2 shows a schematic of a rearrangement of a
Representative Amadori.
Fig. 3 shows the cure temperature profile (Y axis in ° C) of the center of a glass sphere sample for different binders during a heat molding cycle (X axis in minutes of mold time) using a pressure mold with a temperature stage controls binder 1 (♦ (Comparative Example 2); Binder —W4
INSTITUTO MEXICANO is a f®rmal binder<sup>D</sup>á ^ tO © AL f
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-ua ··· carbohydrate binder - inorganic acid (Comparative Example 3); and binder 3 (X) is a diamine dextrose-ammonia-hexamethylene binder (HMDA) (Example
5) .
DETAILED DESCRIPTION OF THE INVENTION
Although the invention is susceptible to various modifications and alternative forms, specific embodiments will be described in detail herein. It should be understood, however, that there is no attempt to limit the invention to the particular forms described, but rather, the intention is to cover all modifications, equivalents, and alternatives that fall within the spirit and scope of the invention.
The present description relates to a binder composition that has unexpected utility in consolidating non-assembled or freely assembled matter. The binder composition represents an unexpected advance in the current state of technology in the area of binder compositions. Specifically, the binder offers performance improvements and provides more simplified manufacturing methodologies that are advantageous, while
<img file="MX339649B_D0008.tif" />
INSTITUTO MtXlCANO DE LA PRO P! S DA D environmentally sound advantages that are- caractwi '& tí?
of a binder based on the carbohydrate system .--——
As used herein, the term "binder solution" is the chemical solution that can be substantially dehydrated to form an uncured binder. As used herein, the binder or binder composition may be cured, uncured, or partially cured. The uncured binder composition refers to an uncured binder composition. An uncured binder is a substantially dehydrated mixture of chemicals that can be cured to form a cured binder. Substantially dehydrated means that the solvent (usually water or a mixture thereof) used to make the binder solution is vaporized so that the viscosity of the remaining material (comprising the binder reagents and the solvent) is high enough to create cohesion inte the assembled material without much rigidity; thus, the remaining material is an uncured binder. In one embodiment, the solvent is less than 65% of the total weight of the remaining material. In another embodiment, a substantially dehydrated binder has a moisture content of between about 5% and about 65% water by weight of total binder. In another modality, the sojvé
Iii O '·':. .-4,
INSTITUTO MEXICANO ¡¡£ i less than 50% of the total weight of the material 'restáñ ^^^ SKíin ^ íS ^ jí ^ other modality, the solvent may be less qp.Q<sub>x</sub>.35% HaI — total passage of the remaining material. In another embodiment, a substantially dehydrated binder has between about 10% and about 35% water by weight of the total binder. In another embodiment, the solvent may comprise less than about 20% of the total weight of the remaining material.
In illustrative embodiments, an uncured binder can be colorless, white, off-white, ocher, or yellow to a brown sticky substance that is, at least partially, soluble in water. As used herein, the term "cured binder" describes the polymeric cure product of the uncured binder composition. The cured binder may have a characteristic brown to black color. Although described as brown or black, another feature is that the binder tends to absorb light over a wide range of wavelengths. In particular, there may be higher absorbance at 420nm. Although the polymer is extensively crosslinked, the cured binder is substantially insoluble. For example, the binder is predominantly insoluble in water. As described herein, the uncured binder provides sufficient binding capacity to consolidate fiber§; jsin _eiuba r qo e 1
ΙΜΡΓ «^ cured binder imparts durability fueiíístiewo ^ icd ©
OF THE INDUSTRIAL PFfcrtlVAD durability and physical properties commonly associated with crosslinked polymers.
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In illustrative embodiments, the binder reagents described herein are water soluble and the binder solution is a solution of the binder reagents in an aqueous solution. In one embodiment, a surfactant is included in the aqueous solution to increase the solubility or dispersibility of one or more binder reagents or additives. For example, a surfactant can be added to the aqueous binder solution to improve the dispersibility of a particulate additive. In one embodiment, a surfactant is used to create an emulsion with a nonpolar additive or binder reagent. In another embodiment, the binder solution comprises approximately
0.01% to about 5% surfactant by weight based on the weight of the binder solution.
In illustrative embodiments, the binder solutions described herein can be applied to mineral fibers (eg, spread over the mat or spread over the fibers as they enter the forming region), during the production of mineral fiber insulation products. Once the binder solution is in contact with the mineral fibers, the heat resj
INS mineral fibers (note that the example fibers are made of molten glass and contain residual heat) and air flow through and / or around the product will cause a portion of the water to evaporate from the binder solution. Removing the water leaves the remaining components of the binder on the fibers as a viscous or semi-viscous high solids blend coating. This viscose or semi viscose high solids blend coating works as a binder. At this point, the mat has not been cured. In other words, the cured binder works to bind the natural fibers in the mat.
Furthermore, it should be understood that the above-described uncured binders can be cured. For example, the manufacturing process for a cured insulation product may include a subsequent step in which heat is applied to cause a chemical reaction in the uncured binder composition. For example, in the case of manufacturing fiberglass insulation products or other mineral fiber insulation products, after the binder solution has been applied to the fibers and dehydrated, the uncured insulation product may transfer to a cure oven. In the cure oven the
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TITUTO í / Ea'CANO DF IA PFC.Pir
SOI · * · * ······ ** · · ΙΙ | Ι »Ι · · μ ·« ΙΛΛ »» 4 »ϊ. · '. ............
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uncured insulation product heats up ·
MEXICAN INSTITUTE approximately 150 ° C to approximately approximately 300 ° F to approximately 600— <sup>g</sup>-Pj-j7 — rrartserrek? · Let the binder heal. The cured binder is a formaldehyde-free, water-resistant binder that bonds the fibers of the insulation product together.
Note that drying and thermal cure can occur either sequentially, simultaneously, simultaneously, or concurrently.
In illustrative embodiments, an uncured fiber product comprises from about 3% to about 40% dry binder solids (total uncured solids by weight). In one embodiment, the uncured fiber product comprises about 5% to about 25% dry binder solids. In another embodiment, the uncured fiber product comprises about 50% to about 97% fibers by weight.
As mentioned herein with respect to a binder on mineral fibers, a cured binder is the product of cure binder reagents. The term cured indicates that the binder has been exposed to conditions to initiate a chemical change. Examples of these chemical changes include, but are not limited to, (i) covalent bond, (ii) component hydrogen bond
<img file="MX339649B_D0012.tif" />
binders, and (iii) the chemically crosslinked polymers in the binder can increase the durability of the binder and solvent resistance compared to the uncured binder.
The cure of a binder can result in the formation of a thermoset material. Furthermore, a cured binder can result in an increase in adhesion between the material in one harvest compared to an uncured binder. The cure can be initiated by, for example, heat, microwave radiation, and / or conditions that initiate one or more of the aforementioned chemical changes. Although not limited to any particular theory, curing can include the carbohydrate and nucleophile reaction in a nucleophilic addition reaction or nucleophilic addition-deletion reaction.
In a situation where the chemical change in the · binder results in the release of water, for example, polymerization and crosslinking, a cure can be determined by the amount of water released above that would occur from · drying alone. The methods used to measure the amount of water released during drying compared to when a binder cures are well known in the art.
In an illustrative embodiment, the nucleophile is a nitrogen-containing compound. In one embodiment, the cured binder composition comprises! '
MEXICAN INSTITUTE t & J nitrogen. In one embodiment, the polymer is brown to black in color. Although not limited to an onparticular, the cured binder composition comprises a blend of high molecular weight polymers. High molecular weight polymers can be characterized by being highly crosslinked. Furthermore, high molecular weight polymers can be characterized as brown and complex polymers containing furan rings and containing nitrogen. High molecular weight, as used herein, includes those polymers that have a molecular weight in excess of 100,000
Daltones. Being comprised of highly crosslinked polymer chains, the molecular weight of the melanoidins described herein approaches infinity. Consequently, the molecular weight of a melanoidin can be a function of the mass and physical dimensions of the polymer being analyzed. For example, a unit sample of melanoidins having a mass of 3 grams can be presumed to comprise a single polymer molecule due to extensive crosslinking. Consequently, the molecular weight of the polymer would be approximately 1.8 x IO<sup>24</sup> grams per mole (being the product of the sample mass and the number
Avogadro). As used herein, a high molecular weight polymer includes polymers with a molecular weight in the
<img file="MX339649B_D0013.tif" />
order of about 1 x 10<sup>5</sup> and i '· MEXICAN INSTITUTE' / 'AtfL / é'x'i
-, n24 η <sup>;</sup>· OF PROPERTY grams per mole. and industrial
Although it is not limited to a theory that high molecular weight polymers vary in structure according to the reagents and the conditions of the preparation. High molecular weight polymers are also known to have a carbon to nitrogen ratio that increases with temperature and heating time.
Furthermore, high molecular weight polymers possess saturated, unsaturated and aromatic characteristics. In one embodiment, the high molecular weight polymers possess a degree of unsaturation and aromaticity that increases with temperature (cure temperature) and heating time (cure time). High molecular weight polymers also contain the Cl of those sugars incorporated as reagents in a variety of structures within the polymer. High molecular weight polymers can also contain carbonyl, carboxyl, amine, amide, pyrrole, indole, azometin, ester, anhydride, ether, methyl and / or hydroxyl groups. Depending on the complexity of the structure, infrared spectroscopy can be useful in identifying one or more of these functional groups. Although not classified here, one skilled in the art would appreciate that the binder can also be classified according to the existence of a particular prepente_ Lal ^ .- bond as
^ο ^^ polyester, polyether, polyamide, etc. "^^ 'ίΑρΙοπΕΟΑη
Another way in which the binder is characterizable is through the analysis of gaseous compounds produced during the pyrolysis of the cured binder. Gas pyrolysis of a cured binder within the scope of the present disclosure can produce about 0.5 to about 15% (by relative peak area) of one or more of the following compounds: 2-cyclopenten-l-one, 2.5 -dimethylfuran, furan, 3-methyl-2,5-furandione, phenol, 2,3-dimethyl-2-cyclopenten-l-one, 2-methyl phenol, 4-methyl phenol, 2,4-dimethylphenol, dimethylphthalate, octadecanoic acid, or erucilamide. Fingerprinting on pyrolysis gas chromatography (Py GC-MS) spectrometry performed at
770 ° C of a binder sample prepared using hexamethylonediamine as the polyamine component shows pyridine and a number of components that are derivatives of pyrrole or pyridine (a methyl pyridine, a methyl pyrrole, dimethyl pyridine, a methyl pyrrole, and another pyrrole related to components that contain
N). Another way in which the binder can be identified is whether a solution containing the binder (or an extract solution) is capable of reducing the reagent from
Benedict. In one embodiment, a solution in contact with the binder or an aqueous extract thereof INSTITUTO MEXICANO
Benedict. ;<sup>of the</sup>, nous' ™ a?
One aspect of the present description e, s. .than<sup>1rvc;</sup> Binders described herein are environmentally friendly. Parallel to the advancement of government regulation, the present description describes a binder that can be made free of formaldehyde. Additionally, the chemistry described herein is essentially formaldehyde and phenol free. In this regard, neither formaldehyde nor phenol is used as a reagent within the scope of the present description. Although both can be added to obtain a binder with potentially useful properties, one aspect of the present description is a binder that can be made free of these two reagents. In another aspect, the binder composition present can be made without the use of volatile reagents. In one embodiment, the nucleophile and the carbohydrate are both non-volatile reagents. As used herein, a volatile reagent is one that has a vapor pressure greater than 10 kPa at 20 ° C. Similarly, as used herein, a non-volatile reagent has a vapor pressure of less than about 10 kPa at 20 ° C. Specifically and as an example, the binder present can be made without the addition of ammonia or an ammonia-releasing compound. In one embodiment, the nucleophile has_ ppfesuón ^
Vapor IMP of less than about 0.5 kPaNsaTugQtrjÁ ^ o
Another environmentally friendly aspect of the present disclosure is that the primary reagents for the binder are carbohydrates. Carbohydrates are considered a renewable resource. However, the current state of the art mainly uses petroleum-derived reagents for the manufacture of binder compositions. In another aspect, the binder is made through chemical reactions that can occur at lower temperatures than those of comparable systems described in the prior art. How
I tal, cure kilns and fabrication kilns can be operated at lower temperatures, saving valuable resources. In the alternative and in a related manner, the binder described herein cures faster than the currently comparable binders used when
<td>submit to</td><td>temperatures</td><td>of</td><td>cure</td><td>Similar.</td><td>In</td><td colspan="2">consequence,</td><td>to</td>
<td>through</td><td>anyone</td><td>of</td><td>the</td><td>approaches,</td><td>a</td><td>appearance</td><td>of</td><td>the</td>
<td>Present</td><td>description</td><td>is</td><td>than</td><td>the footprint</td><td>of the</td><td>carbon</td><td>of</td><td>a</td>
Product formed using the binder presently described can be substantially reduced compared to a comparable binder made according to the current state of the art, for example a phenol formaldehyde based product.
<img file="MX339649B_D0014.tif" />
In addition to the environmental benefits, the _joppfgpcjLó
MEXICAN INSTITUTE <sub>and</sub> OF THE NiORIECAO present binder and the compositions made mísrEio 'can be made having characteristics dfé <sup>l</sup>equivalent performance or exceeding those of comparable binder systems, for example phenol formaldehyde binders. In another aspect, a binder in accordance with the present disclosure provides articles made therefrom with sufficient tensile strength to allow for die cutting, fabrication, lamination, and installation in OEM applications. In one aspect, a binder according to the present disclosure has better holding capacity in water (weather resistance) compared to that of the phenol formaldehyde binder. Other performance characteristics that may be relevant to a particular application include product emissions, density, loss or ignition, thickness recovery, dust, tensile strength, breakout force, breakout force durability, bond strength, absorption water, hot surface performance, corrosivity on steel, bending stiffness, strength-stiffness, compressive strength, conditioned compressive strength, compression modules, conditioned understanding modules, and smoke development during ignition. One aspect of the present disclosure is that the cured binder extract is essentially pH neutral, for example 6 and 8. Another aspect of the present dedGrup ^ i ^ "; ^^
<img file="MX339649B_D0015.tif" />
The present binder enables the manufacture of products having relevant performance characteristics comparable to formaldehyde phenol binder compositions.
Illustratively, in one embodiment, a binder according to the present disclosure has the advantage of producing essentially colorless aqueous extracts. This feature of the present description makes the binder desirable in applications such as ceiling tiles, furniture, or office panels, where the finished product may come into contact with water. A cured well manufactured made with the present binder shows excellent resistance to discoloration or spillage after contact with moisture or water. Furthermore, in such an embodiment, the water that is contacted with the binder does not leave a residual color on other articles or parts that can be contacted subsequently to contact the binder. For example, in one embodiment, the binder can be used to bond glass fibers in an office panel application. The cover of the bonded fiberglass composition may be a light colored fabric. Advantageously, in one embodiment, the water that comes into contact with the fiberglass composition does not leave a
<img file="MX339649B_D0016.tif" />
color residue on the fabric after
MEXICAN INSTITUTE
DELA PROPERTY office panel. and industrial -
In addition to the performance features<sup>J</sup>The process and the manufacturing methods involving the binder presently described have a number of unexpected advantages over previously described binders. In one aspect, as previously described with respect to environmental benefits, the present binder can be manufactured without the use of highly volatile reagents. Consequently, manufacturing emission controls are under reduced load. Furthermore, the reaction efficiency is higher since the loss of the reagent due to vaporization is reduced. Accordingly, one aspect of the present disclosure is that the compounds used herein are substantially non-volatile, therefore the steps one must take to mitigate unwanted emissions are reduced.
According to another aspect, the reactants that react to form a binder are low enough to react so that a one-stage / can binder system can be used. According to this aspect, the reagent compounds are slow enough to react that they can be added to a simple reaction solution and stored for a reasonable amount of time during which binders can be applied to a product using
-ÍNSTIT'JTO MEX'GANQ
WjJ¡
This contrasts with those> ELAFK <siisteí— · * INDUSTRIAL that react to low temperatures;
in insoluble reaction products within binder solution delivery systems. As used herein, a reasonable amount of time for storage without substantial (> 5%) polymer precipitation is two weeks.
Another aspect of the present disclosure is that, although the binder is sufficiently non-reactive under ambient temperature conditions to facilitate a grouping approach, it is sufficiently reactive at elevated temperatures to cure at very low temperatures and / or residence times of cures very short. In one aspect, the decreased cure temperature reduces the risk of an insulation product experiencing flameless combustion and / or causing inline fires. As used here, very low temperatures are characterized as less than or equal to about 120 ° C. As used here, very short cure times are less than or equal to about 4 min.
In illustrative embodiments, the binder composition includes an acid or an acidic salt to increase the shelf life of the uncured binder or binder solution. Although this acid is not a reagent or catalyst, it can be included to delay or inhibit the reagents of the binder from forming the binder while sj ^ j.
binder or uncured binder is sieriwj ^ gfl ^ under storage conditions. For example, the volatile acid or acid salt can be included in the binder or uncured binder solution that delays or inhibits the cure reaction under ambient conditions. However, the acid can be removed by heating the binder solution or uncured solution so that the acid is volatilized and the pH of the uncured binder or binder solution is increased. In one embodiment, the binder composition includes a shelf life acid. In another embodiment, the binder composition includes a molar ratio of nucleophil shelf life extension acid of about 1:20 to about 1: 1.
Another aspect of the present disclosure is a binder that has a cure rate, cycle time, and cure temperature that meets or exceeds those cure rates that a comparable phenol and formaldehyde-type binder can exhibit within the scope of comparable use. In this regard, the present binder can be used as a direct replacement for formaldehyde phenol resins in applications without modification to the equipment. In addition, the present binder allows modification of temperature and cure times so that both reaction temperatures and cure times can reduce this.
IMPÍ / ¾ reduction has the effect of reducing consumption ^ <sup>D</sup> 'INDUSTRIAL of the total process and reduces the environmental impact of product manufacturing. Furthermore, lower cure temperatures have the additional effect of increasing the safety of the manufacturing process. Another effect of lower cure temperatures is a reduction in the risk of flameless or fire combustion.
In the manufacture of insulation products, the heat released by the exothermic cure reaction can result in self-heating of the product. Self-heating is typically not problematic as long as the heat dissipates from the product. However, if heat increases the temperature of the product to the point where the oxidation process begins, self-heating can cause significant damage to the product. For example, flameless combustion or oxidation can occur when the temperature of the isolated product exceeds approximately 210 ° C (425 ° F). At these temperatures, the exothermic combustion or oxidation processes also promote self-heating and the binder can be destroyed. Furthermore, the temperature can increase to a level where melting or devitrification of the glass fibers is possible. Not only does this damage the structure and value of the insulation product ^, - ^ also 'LMnfe
M EX'CANO INSTITUTE *
FROM INDUSTRIAL IROHEPAD can create a fire hazard.
Another aspect of the present disclosure is that the binder system is essentially non-corrosive with or without the addition of corrosion inhibitors. Furthermore, the binder system does not require the addition of any organic or inorganic acid or salts thereof as a catalyst or active ingredient. Accordingly, one aspect of the present binder is that it can be made essentially acid free. Furthermore, the binder can be manufactured under entirely alkaline conditions. As used herein, the term "acid" includes those compounds that are primarily characterized by their acidic characteristic such as multiprotic organic and inorganic acids (eg, sulfuric acid and citric acid). This aspect reduces the use and maintenance requirements of manufacturing equipment and improves worker safety.
In illustrative embodiments, a binder comprises a polymeric product of a carbohydrate reagent and a nucleophile. As used herein, the term "carbohydrate reagent" refers to a monosaccharide, a disaccharide, a polysaccharide, or a reaction product thereof. In one embodiment, the carbohydrate reagent can be a reducing sugar. As used herein, sugar from
Ϊ ϊ reduction indicates one or more sugars than; co:
MEXICAN INSTITUTE OF PROPERTY
<img file="MX339649B_D0017.tif" />
aldehyde, or that can be isomerized, that is, taúí? óWtiz? r7 to contain aldehyde groups, whose group5 '<sup>1</sup> pusdén 'SET rusted with, for example, Cu<sup>+2</sup> to achieve carboxylic acids. It is also appreciated that any carbohydrate reagent can be optionally substituted, such as with hydroxy, halo, alkyl, alkoxy, and the like. Furthermore it is also appreciated that in any carbohydrate reagent, one or more chiral centers are present, and that both possible optical isomers in each chiral center are contemplated to be included in the invention described herein.
Furthermore, it should also be understood that various mixtures, including racemic mixtures, or other diasteromeric mixtures of the various optical isomers of any carbohydrate reagent, as well as various geometric isomers thereof, may be used in one or more embodiments of the invention described in the present. Although non-reducing sugars, for example sucrose, may not be preferable, they may nonetheless be useful within the scope of the present description by in situ conversion to a reducing sugar (i.e. the conversion of sucrose to invert sugar is a method known in the art). Furthermore, it is also understood that a monosaccharide, disaccharide, or polysaccharide may be partially reacted with a precursor to form a reaction product.
DELA EROF *:<sup>r</sup>MT
INDUSTRIAL
To the extent that the reaction product '/ carbohydrate is derived from a monosaccharide, a disaccharide, or a polysaccharide and maintains similar reactivity with the nucleophile to form reaction products similar to those of a monosaccharide, a disaccharide, or a polysaccharide with a nucleophile, the carbohydrate reaction product is within the term carbohydrate reagent approach.
In one aspect, any carbohydrate reagent must be nonvolatile enough to maximize its ability to remain available for reaction with the nucleophile. The carbohydrate reagent can be a monosaccharide in its aldose or keto form, including a triose, a tetrose, a pentose, a hexose, or a heptosose;
or a polysaccharide; or combinations thereof. For example, when a triose serves as the carbohydrate reagent, or is used in combination with other reducing sugars and / or a polysaccharide, an aldotriose sugar or a quetotriose sugar can be used, such as glyceraldehyde and dihydroxyacetone, respectively. When a tetrose serves as the carbohydrate reagent, or is used with other reducing sugars and / or a polysaccharide, aldotetrose sugars, such as erythro and treose; and quetotetrose sugars, such as erythrulose, can be used. When a pentose serves as the carbohydrate reagent, or is used with or
INSTITUTO MEXICANO reduction and / or a polysaccharide, sugars · -aldS ^ ié ^ SSa, '* such as ribose, arabinose, xylose, and lizase ,; and - aaúcare & kentopentosa, such as ribulose, arabulose, cylulose, and lixulose, can be used. When a hexose serves as the carbohydrate reagent, or is used with other reducing sugars and / or a polysaccharide, aldohexose sugars, such as glucose (i.e., dextrose), mannose, galactose, allose, altrose, talose, gulose, and idosa; and ketohexose sugars, such as fructose, psychosa, sorbose, and tagatose, can be used. When a heptosose serves as the carbohydrate reagent, or is used with other reducing sugars and / or a polysaccharide, a ketoheptose sugar such as sedoheptulose can be used. Other carbohydrate reagent stereoisomers not known to occur naturally are also contemplated to be useful in the preparation of binder compositions as described herein.
In one embodiment, the carbohydrate reagent is high fructose corn syrup.
In illustrative embodiments, the carbohydrate reagent is a polysaccharide. In one embodiment, the carbohydrate reagent is a polysaccharide with a low degree of polymerization. In one embodiment, the polysaccharide is molasses, starch, cellulose hydrolysates, or mixtures thereof. In "
IMPI
<img file="MX339649B_D0018.tif" />
one modality, the carbohydrate reagent ββιτιιππΝΕΦΕΑ'βΓ • Ϊ OF THE PROPÍLCAn
INDUSTRIAL starch, a maltodextrin, or a mixture thereof.
Although carbohydrates of higher degrees of polymerization may not be preferable, they may nonetheless be useful within the scope of the present disclosure by depolymerization in situ (i.e. depolymerization by ammonium formation at elevated temperatures is a method known in the art).
Furthermore, the carbohydrate reagent can be used in combination with a non-carbohydrate polyhydroxy reagent.
Examples of non-carbohydrate polyhydroxy reagents that can be used in combination with the carbohydrate reagent include, but are not limited to, trimethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, fully hydrolyzed polyvinyl acetate, and mixtures of the themselves. In one aspect, the non-carbohydrate polyhydroxy reagent is sufficiently non-volatile to maximize its ability to remain available for reaction with a monomeric or polymeric polyamine. It is appreciated that the hydrophobicity of the non-carbohydrate polyhydroxy reagent can be a factor in determining the physical properties of a binder prepared as described herein.
As used herein, a nucleophilic b
<img file="MX339649B_D0019.tif" />
INDUSTRIAL that forms a link to your partner<sup>;></sup> reaction (the electrophile) by donating both bonding electrons. As used herein, an electrophile is a reagent that bonds to its reaction partner (the nucleophile) by accepting both bond electrons from that reaction partner.
Illustratively, the electrophile is the carbohydrate described herein. Specifically, the electrophile group is the carbon associated with the aldose or keto form of the carbohydrate. For example, glucose Cl is electropositive due to aldose functionality and reacts with a nucleophile of the present disclosure. In another example, C-2 fructose is electropositive due to keto functionality and reacts with a nucleophile of the present disclosure. While described as an electrophile in its initial interaction with the nucleophile, one of skill in the art will appreciate that the carbohydrate is not limited to acting only as an electrophile within the focus of any reactions that may occur. For example, the hydroxyl groups of the carbohydrate can act as a nucleophile depending on the presence of a reactive nucleophile.
Furthermore, while the initial reaction between the nucleophile and the carbohydrate can correctly classify the carbohydrate as ur. electrophile, the product of that reaction
INDUSTRIAL
<img file="MX339649B_D0020.tif" />
It can exhibit both nucleophilic functionality - «- oítio ^ e ^ e_.
; MEXICAN INSTITUTE in additional reactions.
In illustrative embodiments, the nucleophile is nucleophilic enough to react with a carbohydrate in its aldose or keto form in a solution having a pH as described herein and at a temperature described herein. In one embodiment, the nucleophile includes a cationic stabilization moiety. As used herein, a cationic stabilization moiety is a chemical group on the nucleophile that stabilizes the cation that is formed on nucleophilic attack. For example, a nucleophile within the scope of the present disclosure is a diamine. Under the nucleophilic attack of a carbonium by a primary amine, a cation of a base
Schiff forms. While the first amine on the diamine acts on the function of a nucleophile, the second amine acts on the function of a cationic stabilization moiety while stabilizing the cation of the Schiff base. Further readjustment of the Schiff base cation to the enol or keto form is known to proceed spontaneously. The cation that is formed under nucleophilic attack is similarly stabilized (as is a Schiff base) by the structure of the nucleophile.
In another aspect, the nucleophile structure accelerates readjustment by stabilizing the positive charge that is acquired while the compound is in the cat '' '' 'form under nucleophilic attack.
<img file="MX339649B_D0021.tif" />
This sporadic reaction was found to be<sup>1</sup> also — e ^ · facilitated by dehydration, since the rate increased in dehydrated samples. The importance of the stabilization moiety is believed to have not been discussed in prior art within the scope of the present application since the improved effect of using a nucleophile of the present disclosure has not previously been described. Accordingly, one aspect of the present disclosure is that the nucleophile is of a type that provides stability to a cation of a nucleophilic base during subsequent readjustment. In another aspect, the nucleophile is of a type that provides stability to a cation of a nucleophilic base during subsequent readjustment while in a substantially dry state.
In illustrative embodiments, the nucleophile is R1-Q-R2 / where Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which is optionally substituted, Rl is a nucleophilic residue, and R2 is the stabilization residue. In an Rl embodiment it is selected from the group consisting of an amine, an azide, a cyate, an isocyte, a thiol, a disulfide, a thiocyte, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl, and an alkoxide . In another embodiment, R2 is selected
MEXICAN INSTITUTE. DELA PROPINAD consists of an amide, an amine, a bound unwwiTpter07 ^ -0 ^^ nitrate, a pyridine, a phosphate, a phosphorous * a hydroxyl; · - a hydrogen, a sulfone, a sulfinyl, and a sulfhydryl (thiol) .
In one embodiment, the nucleophile is a primary amine.
As used herein, a primary amine is an organic compound that has one or more primary amine groups. Within the focus of the term primary amine are those compounds that can be modified in situ or isomerized to generate a compound that has one or more primary amine groups. In one embodiment, the primary amine can be a molecule that has the formula of H<sub>2</sub>-NQR, where Q is an alkyl, cycloalkyl, heteroalkyl or cycloheteroalkyl, each of which can be optionally substituted and R includes a cationic stabilization moiety selected from the group consisting of an amine, an amide, an imine, an imide , a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulfone, a sulfo, a sulfinyl, and a sulfhydryl (thiol).
In one embodiment, Q is an alkyl selected from the group consisting of C2-C24. In another embodiment, Q is an alkyl selected from the group consisting of C<sub>2</sub>-Cs. In other
<img file="MX339649B_D0022.tif" />
modality, Q is a selected alkyl TMPí
MEXICAN INSTITUTE consists of C3-C7. In yet another modality, Q is' ÜK'iíaSíqu.i 1
In another embodiment, Q is selected from a cyclohexyl, cyclopentyl, or cyclobutyl · gxupe. In another embodiment, Q is a benzyl. In another embodiment, R1-Q-R2 is 2 [(2-aminoethyl) amino] ethanol. In another form of R1-Q-R2 each
RI and R<sub>2</sub> it's thiol.
In one embodiment, RI is an amine. In a further embodiment of the foregoing, R2 is an amine, an amide, an imine, or an imide. In a further embodiment of the above, R2 is an amine.
As used herein, the term "alkyl" includes a chain of carbon atoms, which is optionally branched. As used herein, the term "alkenyl and alkynyl" includes a chain of carbon atoms, which is optionally branched, and includes at least one double bond or one triple bond, respectively. It is also understood that the alkynyl may also include one or more double bonds. Furthermore it should be understood that the alkyl is advantageously of limited length, including Ci-C<sub>24</sub>, C1-C12,
CiC<sub>8</sub>, Ci-Cs, and C1-C4. Furthermore it should be understood that the alkenyl and / or alkynyl may each be advantageously of limited length, including C2-C24 / C2-C12, C<sub>2</sub>-C<sub>8</sub>, C2-C<sub>6</sub>, and C2-C4. It is appreciated herein that shorter alkyl, alkenyl, and / or alkynyl groups can add less
INSTITUTO MEXICANO composed and consequently will have a different er ^ ^ - g ^ c ts ^ gWzSr towards the carbohydrate reagent and solubility nna— binder solution.
As used herein, the term cycloalkyl includes a chain of carbon atoms, which is optionally branched, where at least a portion of the chain is cyclic. It should be understood that cycloalkylalkyl is a subset of cycloalkyl. It should be understood that cycloalkyl can be polycyclic. Illustrative cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, 2-methylcyclopropyl, cyclopentyl-2-yl, adamantyl, and the like. As used herein, the term cycloalkenyl includes a carbon atom chain, which is optionally branched, and includes at least one double bond, where at least a portion of the chain is cyclic. It should be understood that one or more of the double bonds may be in the cyclic alkenyl portion and / or the non-cyclic alkenyl portion. It should be understood that cycloalkenylalkyl and cycloalkylalkenyl are each subsets of cycloalkenyl. It should be understood that cycloalkyl can be polycyclic. Illustrative cycloalkenyl includes, but is not limited to, cyclopentenyl, cyclohexyl ethene-2-yl,
<img file="MX339649B_D0023.tif" />
cycloheptenylpropenyl, and the like. Furthermore · d that the chain that forms cycloalkyl and / or cyc _ advantageously of limited length, including · ..... Cj Cg Cá /, ”
C3-C8, C3-C6, and C5-C6. It is appreciated herein that the shorter alkyl and / or alkenyl chains that form cycloalkyl and / or cycloalkenyl, respectively, may add less lipophilicity to the compound and will accordingly have different behavior.
As used herein, the term "heteroalkyl" includes an atom chain that includes both carbon and at least one heteroatom, and is optionally branched. Illustrative heteroatoms include nitrogen, oxygen, and sulfur. In certain variations, illustrative heteroatoms also include phosphorous, and selenium. In one embodiment, a heteroalkyl is a polyether. As used herein, the term cycloheteroalkyl including heterocyclyl and heterocyclic, includes an atom chain that includes both carbon and at least one heteroatom, such as heteroalkyl, and is optionally branched, where at least a portion of the chain is cyclic. Illustrative heteroatoms include nitrogen, oxygen, and sulfur. In certain variations, illustrative heteroatoms also include phosphorous, and selenium. Illustrative cycloheteroalkyl includes, but is not limited to tetrahydrofuryl pyrrolidinyl, tetrahydropyranyl, piperidinyl morpholinyl.
<img file="MX339649B_D0024.tif" />
FROM INDUSTRIAL PROPERTY homopiperazinyl, quinuclidinyl, and the like.
The term optionally substituted as used herein includes the replacement of hydrogen atoms with other functional groups on the radical that is optionally substituted. Other illustrative functional groups include, but are not limited to, amino, hydroxyl, halo, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, nitro, sulfonic acids and derivatives thereof, carboxylic acids and derivatives thereof, and the like. Illustratively, any amino, hydroxyl, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, and / or sulfonic acid is optionally substituted.
In illustrative embodiments, the nucleophile is a diamine, triamine, tetraamine, or pentamine. In one embodiment, the polyamine is a triamine selected from diethylenetriamine, 1-piperazine ethanamine, or bis (hexamethylene) triamine. In another embodiment, the polyamine is a tetramine, for example triethiotramine. In another embodiment, the polyamine is a pentamine, for example tetraethylenepentamine.
One aspect of nucleophile is that low steric hindrance. For example, if Q. is linear and at least three rays long, the nucleophilic rir-d'i.i and the stabilizing moiety are spaced far enough so that the nucleophile is capable of reacting with the electrophile.
While not limited to a particular theory, the stabilization moiety is so named because it stabilizes a reaction intermediate as described herein. However, in another aspect of the present disclosure, the stabilization moiety may also serve as a reagent within the scope of the present disclosure. As such, the readjustment products that exist after the reaction between the nucleophilic moiety and the carbohydrate can convert or return the stabilizing moiety to a group that reacts or is capable of reacting with another carbohydrate. Consequently, the stabilizing moiety can convert or return to the nucleophilic moiety form and react with the carbohydrate accordingly.
In illustrative embodiments, the Q group, as described herein, can serve to isolate the two groups so that Ri and R2 are essentially unaffected by chemistry occurring at the other position. As such, the
<img file="MX339649B_D0025.tif" />
DELA INDUSTRIAL PROPERTY group Q may or may not serve in stabilization capacity. According to this theory, the advantages that are gained during the use of a si-functional nucleophile are mainly attributable to the fact that a single di-functional compound can form a crosslink between two carbohydrate compounds. Since two functional groups are linked by a Q group, under the reaction of both Ri and R<sub>2</sub>, the result is a product of higher molecular weight than if Ri and R<sub>2</sub> were not linked by group Q.
As such, the Ri and R<sub>2</sub> can be selected from the group consisting of an amine, an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl, an alkoxide, an amide, a imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulfone, a sulfo, a sulfinyl, and a sulfhydryl (thiol).
In illustrative embodiments, group Q is of the type that enables chemical communication between R1 and R2. For example, Q can allow chemical communication by allowing the resonance and polarity variations of R1 and R2. In other embodiments, Q can be of a length that reacts to both R1 and R2 and causes changes to the electron distribution in the other group (Ri or R<sub>2</sub>). In one embodiment, it includes a stabilization moiety and a nuoféÉr ^ laS® ^ moiety. - In one embodiment, the nucleophilic moiety is —eeeeeeio «q — del · - group consisting of an amine, an azide, a cyanate, an isocyanate , a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl, an alkoxide. In another embodiment, the cationic stabilization moiety is selected from the group consisting of an amide, an amine, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulfone, a sulfo, a sulfinyl, and a sulfhydryl (thiol).
In one embodiment, the nucleophile can include a polymeric polyamine. For example, polymeric polyamines within the scope of the present disclosure include chitosan, polylysine, polyethyleneimine, poly (N-vinyl-N-methyl amine), polyaminostyrene, and polyvinylamines. In one embodiment, the polyamine comprises a polyvinyl amine.
As used herein, the polyvinyl amine can be a homopolymer or a copolymer.
Although not limited to a particular theory, one aspect of the present disclosure is that the primary polyamine and the carbohydrate reagent are Maillard reagents that
<img file="MX339649B_D0026.tif" />
.. I saw, ► JA
OF INDUSTRIAL PROPERTY react to form a melanoidi product "* '
Λ.
shows a schematic of a Maillard reaction; culminating in the production of melanoidins. In its initial phase, a Maillard reaction involves a carbohydrate reagent, for example, a reducing sugar (note that the carbohydrate reagent can come from a substance capable of producing a reducing sugar under reaction conditions
Maillard). The reaction also involves condensing the carbohydrate reagent (eg, reducing sugar) with an amine reagent, i.e., a compound that has an amino group. In other words, the carbohydrate reagent and the amine reagent are the melanoidin reagents for a Maillard reaction. Condensation of these two constituents produces an N-substituted gysosilamine.
For a more detailed description of the Maillard reaction see, Hodge, JE Chemistry of Browning Reactions in Model
Systems J. Agrie. Food Chem. 1953, 1, 928-943, the disclosure of which is incorporated herein by reference in its entirety. The literature on Maillard reactions focuses on melanoidins produced from amino acids. The present description can be distinguished from these references in that not all amino acids are polyamines. Common amino acids that are considered polyamines within the scope of the present disclosure include histidine, lysine, and arginine.
asparagin tXJC'TT'ri ΙΤΓ »ΜΛΪΊΓΑΨΊ r ^ - **** M £ eiF * .xl
MEXICAN INSTITUTE OF THE INDUSTRIAL PRCUcOAD
Without being bound by theory, the covalent reaction between the polyamine and the carbohydrate reagent will be described in greater specificity. As described herein, the path of the present reaction is to distinguish from those taught in the prior art for the following reasons:
(1) the present reaction can occur entirely at basic pH, (2) the polyamine is di-functional in its reactivity towards the carbohydrate reagent, (3) the polyamine, through its di-functional reactivity or other unrecognized phenomena, exhibits a lower activation energy within the focus of the reaction resulting in an unexpected increase in the reaction rate and / or a decrease in the temperature at which the reaction will proceed.
In illustrative embodiments, the first step in the formation of high molecular weight polymers of a nucleophile and a carbohydrate reagent is the condensation of the carbohydrate reagent and the nucleophile. Evidence indicates that the conditions described herein are especially well suited to drive this reaction to completion. First, the alkalinity of the binder solution is believed to lead to condensation. For example, IMP sugars and nucleophiles have been shown
MEXICAN INSTITUTE undergo coloration in aqueous solution in p £ tit¡ ^ fe'éi <^ or? '^ -' Mai '<sup>i</sup>'* basic strength of the amines used or the pp Hp i? nniήη-In this example, N-substituted glycosylamines are believed to remain dissociated in aqueous solutions to appreciable extents. Thus, the irreversible transformations that disassociated molecules undergo must be considered. While the condensation reaction is known to be reversible, we found that this reaction can furthermore lead to termination, according to Le Chatelier's principle by concurrent dehydration of the binder solution. As such, it was established that initially a primary constituent of the uncured binder composition was the condensation products of the nucleophile and the carbohydrate.
The second step in converting the binding reagents to the high molecular weight products can be a readjustment. An exemplification reset is shown as an outline of the Amadori reset in Fig. 2. Referring to Fig. 2, the N-glycosyl derivatives of representative amines are in equilibrium with the cation of a base
Schiff. While this balance favors Nglycosylamine, the further re-adjustment of the cation of a base
Schiff to the enol way
or keto I know J
IN * spontaneously. This reaction was also found to be facilitated by dehydration, since the f increased in dehydrated samples. One aspect of the present disclosure is that the structure of a nucleophile specifically accelerates this re-adjustment by stabilizing the positive charge that is acquired while the compound is in the form of a Schiff base cation. This stabilizing effect is believed to have not been discussed in the prior art or the literature since the enhanced effect of using a nucleophile as such within the scope of the present disclosure has not previously been described. Accordingly, one aspect of the present disclosure is that the nucleophile is of a type that provides stability to a Schiff base cation during an Amodori reset. In another aspect, the nucleophile is of a type that provides stability to a Schiff base cation during an Amadori reset while in a substantially dry state.
Another aspect of the present disclosure is that the carbohydrate structure is believed to also influence the kinetics of the reset. Specifically, it is known that when the C-2 hydroxy of an N-substituted glycosylamine was unsubstituted, the compound was
slowly transformed during storage
MEXICAN INSTITUTE adjustment product. However, if the hydre ^^^ TRjS-;
replaced, then the reset was .qn-ql-anni alinQni-.a ...
inhibited. Accordingly, one aspect of the present disclosure is that a carbohydrate of the present disclosure is unsubstituted in the hydroxyl adjacent to the ketone or aldehyde.
In illustrative embodiments, the weight ratio of the carbohydrate reagent to the nucleophile is in a range from about 1: 1 to about 30: 1. In another embodiment, the weight ratio of the carbohydrate reagent to the nucleophile is in a range from about 2: 1 to about 10: 1. In yet another embodiment, the weight ratio of the carbohydrate reagent to the nucleophile is in a range from about 3: 1 to about 6: 1. According to one aspect, the cure rate is a function of the weight ratio of the carbohydrate reagent to the primary polyamine. According to this function, it was established that while the ratio decreased, the cure rate increased;
in this way the healing time decreased. Accordingly, one aspect of the present disclosure is that cure time is directly related to the weight ratio of the carbohydrate reagent to the nucleophile as long as other parameters remain equivalent. In another aspect, the ¿η · * .. n a.7 / /. JL'l. ϊ. »« ι. ImíLl, * · ... ,, t'9 << ..
cure time of the binder is reduced to tlé:
INSTITUTO MEXICAW EJ.A PAQmtlS.
<sup>{</sup>Jt Λ
<img file="MX339649B_D0027.tif" />
a formaldehyde binder composition. fen8<sup>AND</sup>When the weight ratio of the reagent of arlaftfaAdgato to the primary polyamine is equal to approximately 6: 1. Accordingly, in one embodiment, a binder according to the present disclosure has a cure rate that exceeds a comparable phenol formaldehyde binder system when the weight ratio of the carbohydrate to nucleophile reagent is in a range of about 2: 1 to about
6:1.
Another aspect of the reaction as described herein is that, initially, the aqueous reagent solution (which can be dehydrated and used as a binder), as described above, has an alkaline pH. One aspect of the present disclosure is that the alkaline binder solution is less corrosive to metal than the acidic solution. Accordingly, a feature of the present disclosure that fights a substantial barrier to industry is that the binder described herein has less corrosiveness to manufacturing equipment that can be used to produce materials including the present binder due to the alkaline binder composition. . A distinguishing feature of the present disclosure over other recent carbohydrate binding systems
<img file="MX339649B_D0028.tif" />
described (for example Request published
MEXICAN INSTITUTE A _ λ-,, λ -λ. τ · .DE LA fROHEPAP
2007/0027283), is that the reaction is not necessary<sup>IAL</sup>prroeQ € r through an acidic path. Rather, —ü »—ttgpec.'to — de — la<sup>1</sup>The present disclosure is that the uncured binder can have an alkaline pH throughout the course of the chemical reaction leading to the formation of a cured binder. As such, the uncured binder throughout its use and storage does not present a risk of corrosion. In illustrative embodiments, an aqueous extract of the cured binder has a pH in the range of about 5 to about 9. Furthermore, an aqueous extract of a polymeric product is essentially colorless.
In illustrative embodiments, a method of making a binding binding of matter with a polymeric binder comprises preparing a solution containing reagents to produce the polymeric binder and a solvent, wherein the reagents include a carbohydrate reagent and a nucleophile; arranging the solution on the matter collection; volatilizing the solvent to form a product without cure, and subjecting the product without cure to conditions that cause the carbohydrate reagent and nucleophile to polymerize to form the polymeric binder.
In illustrative modalities, the collection ^^ Jp «INSTITUTO MEXICANO
PROPERTY includes insulating fibers. In one modality,<sup>li</sup>®éS'dtib ^ ~ iJTr fiber insulation product that— • rnci-cryy · insulating fibers and a binder. As used herein, the term "insulating fiber" indicates heat resistant fibers suitable for withstanding high temperatures. Examples of such fibers include, but are not limited to, mineral fibers (glass fibers, slag fibers, and rock wool fibers), aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyamide fibers, fibers of certain polyesters, and rayon fibers. Illustratively, such fibers are substantially unaffected by exposure to temperatures above about 120 ° C. In one embodiment, the insulating fibers are glass fibers. In yet another embodiment, the mineral fibers are present in the range of from about 70% to about 99% by weight.
In illustrative modalities, the collection of matter includes cellulosic fibers. For example, cellulosic fibers can be wood chips, sawdust pulp, wood, or chopped wood. In yet another embodiment, the cellulosic fibers may be other natural fibers such as jute, flax, hemp, and straw. The binder described herein can be used in place of the binder described in published PCT application WO 2008/089847, id. MEXICAN INSTITUTE<sup>J</sup> hereby for reference in your tdtali ^ í ^ ousTi ^ l
In this way, a wooden board is described that includes wood particles and a binder. In another embodiment, the plywood board is formaldehyde-free. In one embodiment, the plywood board has a nominal thickness range greater than 6mm to 13mm, and has a modulus of elasticity (MOE) of at least about 1050 N / irnn<sup>2</sup>, a bending force (MOR) of at least about 7 N / mm<sup>2</sup>, and an internal bond strength (IB) of at least 0.20 N / mm<sup>2</sup>. In another embodiment, the plywood board has a nominal thickness range greater than 6mm to 13mm, and has a bending force (MOR) of at least about
12.5 N / mm<sup>2</sup> and an internal bond strength (IB) of at least 0.2 8 N / mm<sup>2</sup>. In another embodiment, the plywood board has a nominal thickness range greater than 6mm to 13mm, and has a modulus of elasticity (MOE) of at least about 1800 N / mm<sup>2</sup> a bending force (MOR) of at least about 13 N / mm<sup>2</sup> and an internal bond strength (IB) of at least 0.40 N / mm<sup>2</sup>. In another embodiment, the plywood board has a modulus of elasticity (MOE) of at least about 1800 N / mm<sup>2</sup>. In another embodiment, the plywood board has a modulus of elasticity (MOE) of at least<sub>T</sub> Mexican institute / χ · '*' * - ® '
2500 N / mm<sup>2</sup>. In another modality, the tab.lero<sup>OF THE</sup>i ^ ísTÍu ^ ia
<img file="MX339649B_D0029.tif" />
plywood has a bending force (mor,) · ¡pl na <, nn «» approximately 14 N / mm<sup>2</sup>. In yet another embodiment, the plywood board has a bending force (MOR) that is at least about 18 N / mm<sup>2</sup>. In one embodiment, the plywood board has an internal bond strength (IB) of at least 0.28 N / mm<sup>2</sup>. In yet another embodiment, the plywood board has an internal bond strength (IB) of at least 0.4 N / mm<sup>2</sup>. In yet another embodiment, the plywood board swells less than or equal to about 12%, as measured by a change in thickness, after 24 hours in water at 20 ° C. In another embodiment, the plywood board has a water absorption after 24 hours in water at 20 ° C of less than or equal to approximately 40%.
In illustrative embodiments, the plywood board is a wood chipboard, oriented fiberboard, or medium density fiberboard. In one embodiment, the binder comprises from about 8% to about 18% by weight (the weight of dry resin to the weight of wet wood particles) of the composite wood board. In another embodiment, the plywood board further comprises a wax. In yet another embodiment, the plywood board, approximately 0.1% to approximately 2% cer ^<sup>ST</sup>^ S £ re ^^ s composite wood board. In illustrative embodiments, the method of making a binding binding of matter with a polymeric binder may further include preparing a solution by adding an amount of carbohydrate reagent and an amount of nucleophile so a weight ratio is in the range of about 2: 1 at about 10: 1.
In one embodiment, preparing the solution includes adding the carbohydrate reagent and the polyamine to an aqueous solution. In another embodiment, preparing the solution includes adjusting the pH of the solution within the range of about 8 to about 12. In yet another embodiment, the method of making a binding bond of material with a polymeric binder may further comprise packaging the product without It cures in a packaging of suitable material for its storage.
In illustrative embodiments, the present disclosure relates to a composition comprising a collection of matter and a binder, the binder comprising polymeric products of a reaction between a carbohydrate reagent and a nucleophile, the polymeric products being substantially insoluble in water. In one embodiment, the collection of matter includes mineral fibers, aramid fibers, ceramic fibers, carbon fibers, polymide fibers,
<img file="MX339649B_D0030.tif" />
rayon, glass fibers, ce 1 or 1 or more fibers ”· -<sup>1</sup> ττ ros · particulates. For example, cellulosic fibers can include wood chips, sawdust pulp, and / or chopped wood. In one embodiment, the collection of matter includes sand or other inorganic particulate matter. In one embodiment, the collection of matter is carbon particles. In one embodiment, the carbohydrate reagent is selected from a group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In one embodiment, the nucleophile is Rl-QR<sub>2</sub>, where Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which is optionally substituted, Rl is a nucleophilic moiety, and R2 is a stabilization moiety.
In another embodiment, the composition further comprises a silica-containing compound. In one embodiment, the silica-containing compound is a functionalized silyl ether or a functionalized alkylsilyl ether, such as, for example, an amino-functionalized alkylsilyl ether. For example, in one embodiment, the silica-containing compound can be gammaaminopropyltriethoxysilane, gammaglycidoxypropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, or a - ^> 6, · t
MEXICAN INSTITUTE ·. » . 1 isms. In another embodiment, the compound that j. contTew & sTB ^ liS ^ t ^ '<sup>7</sup> mi may be an aminofunούοττιτΗ oligomeric siloxane '' - end · - otr-a · modality, the composition comprises a corrosion inhibitor selected from a group consisting of oil dust removal, monoammonium phosphate, sodium methylamine pentahydrate, melamine, tin (II) oxalate, and a silicone methylhydrogen fluid emulsion.
In further illustrative embodiments, the binder may be arranged on a collection of fibers, substantially dehydrated, packed, and then stored or sold elsewhere. An uncured product sold elsewhere for use in an additional manufacturing process may be referred to as an uncured shipment. A stored uncured product for use in additional manufacturing processes may be referred to as an uncured plant. In the sale or storage of this type of product, it is packed in suitable bags or containers.
In illustrative embodiments, a packaged uncured fiber product comprises an uncured binder composition and a fiber collection, wherein (i) the uncured binder composition is in contact with the fiber collection that consolidates the fiber collection and ( ii) the composition of the uncured binder in: cijn ^ jtjp ^ ο, τγ. The fiber collection is packed in a suitable matena. In one embodiment, the amount of moisture gp _ 1 to ____ uncured binder composition can be in the range of about 1% to about 15% by weight based on the total weight of a product. In yet another embodiment, the suitable packaging material may be able to maintain the amount of moisture in the uncured binder composition to be within approximately 2 0% of an original moisture level for a period of one week at room temperature and at ambient pressure. In one embodiment, the packaged uncured fiber product comprises from about 3% to about 30% by weight of the uncured binder composition based on the weight of the packaged uncured fiber product regardless of the weight of the suitable packaging material. In one embodiment, the packaged uncured fiber product comprises from about 60 to about 97% by weight fibers based on the weight of the packaged uncured fiber insulation product regardless of the weight of suitable packaging material.
One aspect of the present disclosure is that the binder described herein is unexpectedly useful in uncured shipping and uncured plant applications.
Specifically, uncured shipping products and uncured plant products were proposed as ^ ^ and X ^ n ^^^> - <,<sub>:<</sub>.
uncured binder so that the cure<sup>THE</sup>^^ j £ ir <aSLJí ^ a later time and in a place pn ^ tprinr ,. IN uncured de-boarding, cure temperature and time are properties of the product that are of great importance to customers. Specifically, cure temperatures must be low enough that the product can be cured using your existing equipment. Also, the cure time should be short enough so that the cycle time to cure the products is kept low. Within this industry, acceptable manufacturing equipment and cycle times have been established for uncured products comprising phenol formaldehyde type resins. Therefore, sufficiently low cure temperatures are those cure temperatures suitable for curing a comparable phenol formaldehyde type product. Similarly, sufficiently low cycle times are those cycle times that would be routine to cure a comparable phenol formaldehyde type product. One of ordinary skill in the art will appreciate that neither cure time nor cure temperature can be set as defined amounts since specific applications can dramatically have different parameters. However, it is well understood that the cure time and cure temperatures of a model system provide the information that represents
MEXICAN INSTITUTE xV *
CE LA r RO? IFt AD INDUSTRIAL regarding the kinetics of the underlying chemical cure reaction so that reliable predictions of binder performance can be made in various applications.
In illustrative embodiments, the cure time and cure temperature of the binder is equal to or less than a comparable phenol formaldehyde binder composition. In one embodiment, the cure time of the binder is less than the cure time of a comparable phenol formaldehyde binder composition. In another embodiment, the cure temperature of the binder is less than the cure time of a comparable phenol formaldehyde binder composition. As used herein, a comparable phenol formaldehyde binder composition is as described according to US Patent No. 6,638,882, the patent of which is incorporated herein by reference in its entirety.
As discussed below, various additives can be incorporated into the binder composition. These additives give the binders of the present invention additional desirable characteristics. For example, the binder may include a silica-containing coupling agent. Many coupling agents containing
OF INDUSTRIAL PROPERTY
<img file="MX339649B_D0031.tif" />
silica are commercially available
<img file="MX339649B_D0032.tif" />
Corporation, Evonik Industries, and Momenti've Performance
Materials. Illustratively, the silica-containing coupling agent includes compounds such as silyl ethers and alkylosyl ethers, each of which can be optionally substituted, such as halogen, alkoxy, amino, and the like. In one variation, the silica-containing compound is an amino-substituted silane, such as gammaaminopropyltriethoxy silane (SILQUEST A-1101; Momentive Performance
Materials, Corporate Headquarters: 22 Corporate Woods
Boulevard, Albany, NY 12211 USA). In another variation, the silica-containing compound is an amino-substituted silane, for example, silane aminoethylaminopropyltrimethoxy (Dow
Z-6020; Dow Chemical, Midland, MI; USA). In another variation, the silica-containing compound is gammaglycidoxypropyltrimethoxysilane (SILQUEST A-187; Momentive).
In yet another variation, the silica-containing compound is an amino-functional oligomeric siloxane (HYDROSIL 2627, Evonik
Industries, 379 Interpace Pkwy, Parsippany, NJ 07054).
Silica-containing coupling agents are typically present in the binder in the range of about 0.1 percent to about 1 percent by weight based on the binder-based solids (i.e., about 0.05% to about 3% based on the weight of solids added to the solution INSTITUTO MEXICANO aU
INSTITUT ', 1 * 1 IA · ν, Α' * ·. ...
OF THE rsOPIEDAO an application, one or more of these compounds qií<sup>r</sup>and<sup>w</sup>'<sup>s</sup>bó'nti? ~ silica can be added to the solution agluti'nanLü ACUÓSá. The binder is then applied to the material to be bonded.
After that, the binder can be cured if desired.
This silicone containing compounds improves the ability of the binder to adhere the binder in which it is available, such as glass fibers, to the material. By enhancing the binder's ability to matter improves, for example, its ability to produce or promote cohesion in substance (s) not or assembled without much rigidity).
In another illustrative embodiment, a binder of the present invention may include one or more corrosion inhibitors. These corrosion inhibitors prevent or inhibit the decay or wear of the substance, such as, metal caused by chemical decomposition presented by an acid.
When a corrosion inhibitor is included in a binder of the present invention, the corrosivity of the binder decreases compared to the corrosivity of the binder without the inhibitor present. In one embodiment, these corrosion inhibitors can be used to decrease the corrosivity of the mineral fiber-containing compositions described herein. Illustratively, corrosion inhibitors include one or more of the following, oil dust removal, monoammonium phosphate, pentahydrate
INSTITUTO MEXICANO sodium, melamine, tin (II) oxalate, and a ™ ^ ®ίεί ^ όι> 53ϊ £ ΐί ^ 'silicone methylhydrogen fluid. When semi-luyen, or a binder of the present invention, is produced, the corrosion inhibitors are typically present in the binder in the range of about 0.5 percent to about percent by weight based on the dissolved binder solids. One aspect of the present disclosure is that the need for corrosion inhibiting additives is greatly reduced by the reachability of the binder solution and the substantially dehydrated uncured binder. In one embodiment, the binder is free of corrosion inhibitors and the corrosivity of the binder solution is within an acceptable range.
In illustrative embodiments, the binder may further include a non-aqueous humectant. The nonaqueous humectant can include one or more polyethers. For example, the nonaqueous humectant may include ethylene oxide or propylene oxide condensates having straight and / or branched alkaryl and alkyl groups. In one embodiment, the nonaqueous humectant includes a polyethylene glycol, a polypropylene glycol ether, a thioether, a polyoxyalkylene glycol (eg, Jeffox TP400®), a dipropylene glycol, and / or a polypropylene glycol (eg, Pluriol P425® or Pluriol
<img file="MX339649B_D0033.tif" />
MEXICAN INSTITUTE OF THE PkOFltOAP
000®). In one embodiment, the humectant does not a'cuj ^ sj
1NSTI * L _ a polyoxyalkylene glycol or a polypropylene glycol l<sup>ND</sup>E? Í<sup>1A</sup>btrc modality, the nonaqueous humectant includes<sup>one ι,</sup>·<sup>,</sup>ΐΐη<sup>, ι</sup>··<sup>,</sup>'υυΐ [ΐρΐΙΰΰΐΤΓ based on a polyhydroxy compound (eg, a partially or fully esterified polyhydroxy compound). In another embodiment, the nonaccusing humectant includes a polyhydroxy based on a glycerin, a propylene glycol, an ethylene glycol, a glycerin acetate, a sorbitol, a xylitol or a maltitol.
In another embodiment, the aqueous humectant includes other compounds having tetrahydrofuran-based multiple hydroxyl groups, a caprolactone, and / or alkylphenoxypoly (ethyleneoxy) ethanes having alkyl groups containing from about 7 to about carbon atoms and having from about 4 to about 240 ethylenoxy units. For example, the nonaqueous may include and / or a humectant heptylphenoxypoly (ethyleneoxy) ethanol nonylphenoxypoly (ethylenoxy) ethanol. In another embodiment, the nonaqueous humectant includes a hexitol-derived polyoxyalkylene such as a sorbitan, sorbide, mannitan, and / or a mannide. In yet another embodiment, the nonaqueous humectant may include a partial long chain fatty acid ester, such as a polyoxyalkylene derived from monolaurate sorbitan, monopalmitate sorbitan, monosterjtj ^^ triesterato sorbitan, monooleate sorbitan, /.
sip. -___
In illustrative embodiments, the nonaqueous humectant includes an ethylene oxide condensate with a hydrophobic base, the base being formed by condensing propylene oxide with propylene glycol. In one embodiment, the nonaqueous humectant includes a condensate-containing sulfur, such as those prepared by condensing ethylene oxide with a higher alkyl mercaptan (eg, nonyl, dodecyl, tetradecyl mercaptan, or alkyl pilotophenols having about 6 to about 15 atoms of carbon in the alkyl group). In another embodiment, the nonaqueous humectant includes an ethylene oxide derived from a long-chain carboxylic acid, such as lauric, myristic, palmitic, or oleic acids. In yet another embodiment, the nonaqueous humectant includes an ethylene oxide derived from a long-chain alcohol such as alcohols
<td>octyl, decile,</td><td>lauryl,</td><td>or cetyl.</td><td colspan="2">In another modality,</td><td>the</td>
<td>moisturizer no</td><td>aqueous</td><td>includes a</td><td>copolymer</td><td>oxide</td><td>of</td>
<td colspan="2">ethylene / tetrahydrofuran</td><td>or a</td><td>copolymer</td><td>oxide</td><td>of</td>
ethylene / propylene oxide.
The following examples illustrate specific modalities in additional detail. These examples are provided for illustrative purposes only and should not be con JeρΪΒκ ^ Ι; '- fe.
• MEXICAN INSTITUTE fc
PROPERTY LIMITATIONS OF THE INVENTION OR THE INVENT'ÍW CONCEPT<sup>ESTUARY,</sup>para-— any particular physical configuration —de —— crraiTjater '' way.
E TEMPLES
Example 1: A solution of 50 g of dextrose (0.278 mol), g of hexamethylenediamine (0.431 mol) dissolved in 566.6 g of deionized water (15% solids solution, pH 11.9) was heated to the boiling point of the solution. A brownish water insoluble polymer was observed as a precipitate in the reaction vessel.
Example 2: From the above solution of 50 g of dextrose (0.278 mol), 50 g of hexamethylenediamine (0.431 mol) dissolved in 566.6 g of deionized water (15% solids solution, pH 11.9), 2 g of the binder solution were applied over a pad filter that was placed in a Balance of
Humidity and heated for 15 min at 120 ° C. A brownish water insoluble polymer was formed on the filter pad. An extraction from the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of 6.8.
Example 3: A solution of 85 g of dextrose (0.472 mol), g of hexamethylenediamine (0.129 mol) dissolved in 566.6 g of deionized water (15% solids solution, 'INSTITUTO MEXlCAN' ** prepared. 2 g of the solution binder applied n & ^ jae pad filter which was placed on a Balaneg ·<sup>1</sup> '- Ufemederd and heated for 15 min at 140 ° C. A brownish water insoluble polymer was formed on the filter pad. An extraction from the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of
6.8.
Example 4: A solution of 95 g of dextrose (0.528 mol), g of hexamethylenediamine (0.043 mol) dissolved in 566.6 g of deionized water (15% solids solution) was prepared. 2 g of the binder solution was applied to a pad filter which was placed on a Moisture Balance and heated for 15 min at 180 ° C. A brownish water insoluble polymer was formed on the filter pad. An extraction from the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of
6.8 .
Comparative Example 1: A solution of 180 g dextrose (1 mol) dissolved in 1020 g of deionized water (15% solids solution) was prepared. 2 g of the binder solution was applied to a pad filter which was placed on a Moisture Balance and heated for 15 min at 180 ° C. A water insoluble polymer did not form on the pad
<img file="MX339649B_D0034.tif" />
square glass (33.02 x 33.02 cm [13 x 13]) with a weight of 44 g (corresponding to 34.5 g / ft<sup>2</sup>) were impregnated with a binder containing 15% solids. Excess binder is removed by vacuum suction, and the wet mat dries for at least 12 hours at 32.2 ° C (90 ° F) in an oven (recirculation).
The dry mat is cut into four squares of the same dimension. The boxes are stacked on top of each other, and at least one thermoelectric pair connected to a recorder (i.e. tunnel oven) is placed in the middle of the stack between the 2<sup>to</sup> and 3<sup>to</sup> cap.
A temperature controlled platen press mold is heated to 204 ° C (400 ° F). The sample with the prepared thermoelectric pair is placed in the middle of the stage, and pressed to a thickness of 1.59 cm (5/8) for a predefined time (i.e. 3.5 min, 4.0 min, 5.0 min, 6.0 min, 15 min ).
Each molded sample was evaluated for its degree of cure by testing the uniformity of the surfaces, water robbery, and extract. A sample was considered to cure when the surfaces are smooth without some bumps, the sample was not noticeably weakened when immersed
INSTITUTO MEXICANO formed an important extract color when it shows in water. The temperature profile d ^ l ... ^^. A.txQ .... da ..., 1a ,,, sample was measured during the molding cycle and is shown in Fig. 3.
Comparative Example 2: Phenol formaldehyde binder.
Composition based on dry solids:
2.41 part ammonium sulfate
1.08 part ammonia
- 0.21 parts of Silane A1101
96.3% formaldehyde phenol -Resin: Urea Premix (70:30)
Comparative Example 2 is referred to as Binder 1 within Fig. 3.
Comparative Example 3: Carbohydrate-Inorganic Acid Binder.
Composition based on dry solids:
81.59 parts of Dextrose
17.09 parts ammonium sulfate
- 1 part ammonia
0.3 parts Silane A1101
Comparative Example 3 is referred to as the Binder within Fig. 3.
Example 5:
Composition based only on dry olives? IMPI 0 ^ 1
i. MEXICAN INSTITUTE
DF. THE FAOPIDITY 0.94 parts of Dextrose solution and<sup>WE</sup>áffibttia5 (an aqueous solution containing 2 mol / liter · - · * · —Dextrose and 2 mol / liter Ammonia)
19.06 parts Hexamethylenediamine
Example 5 is referred to as binder 4 within Fig. 3.
The time required to achieve complete cure of a binder within the scope of the present disclosure was determined to be less than that of the binder systems of Comparative Example 3 having various chemistries. This model system illustrates that the cure time, as long as other variables remain constant, depends on the chemistry of the binder system. The chemistry of an illustrative composition within the focus of the present disclosure achieves improved cure times compared to these other exemplification examples. The results are shown below:
<td>Binder</td><td>Molding time to achieve total cure</td>
<td>Comparative Example 2- Binder one</td><td>240 second minimum</td>
<td>Comparative Example 3-Binder 2</td><td>300 second minimum</td>
<td>Example 5 - binder 4</td><td>Cured to 210 seconds</td>
Referring now to Fig. 3, characteristic temperature for
<img file="MX339649B_D0035.tif" />
binders 1, 2, and 4. It was observed qua ...., <3.1 ....... temperature profile is characteristic for each binder. It was not established that cure rate and cure time are not characteristic of the cure temperature profile. However, the cure temperature profile helps to understand and predict the cure rate and cure time. Specifically, Comparative Example 3 required the longest cure time; and, similarly, the cure time profile required the largest amount of time to maximize asymptomatically. Similarly, Example 5 required the least amount of time to maximize asymptomatically and demonstrate the shortest cure time.
Carbohydrate reagent: Effect of polyamine ratio on the cure cycle time. Mats were made
Wet Layers (WLM) with varying ratios of dextrose monohydrate (DMH) to hexamethylenediamine (HMDA). Weight ratios tested included 75/25, 85/15, and 92/8 respectively.
A 15% Dextrose-HMDA binder was applied to 5 WLM.
The following binder compositions were prepared:
Example 6
Example 7
Example 8
DMH / HMDA 75/25
DMH / HMDA 85/15
DMH / HMDA 92/8
Water 1677.45 g
DMH 246.78 g
HMDA 74.77 g
Silane 1.00 g
<img file="MX339649B_D0036.tif" />
1677.45g
279.68 g
44.86 g
1.00 g
The mats were prepared in pieces of 33.02x33.02 cm (13xl3), with a thickness of 0.95 cm (3/8). The pressure used to mold the mats is set to 204 ° C (400 ° F). Once the sample is molded it is approximately 1.58 cm (5/8) thick. A temperature profile was first determined at an interval of 15 minutes. The next sample was pressed for 4 minutes; this is the time it takes to cure a comparable phenol formaldehyde binder composition (results not shown). The experiments were repeated with varied cure times until the minimum time required to cure each composition was determined. The extent to which each binder had cured was determined based on its weight. The following results were determined:
Cure cycle time
Example 6 2:30 min.
Example 7 4 min.
Example 8 8 min.
As described above, the comparable phenol formaldehyde based product (eg Comparative Example 2) cures with a cycle time Jd ^ yj * jgi ·: Mexican INSTITUTE
FROM LA fROFUr. 'D
Furthermore, a comparable binder based on .carbohfd ^ tb example, Comparative Example 3) cures cüTr ~ urr 5 minute cycle. These results indicate that a binder within the scope of the present disclosure with a primary polyamine carbohydrate reagent of 85/15 or lower cures at a rate comparable or faster than the phenol formaldehyde-based product. Additional experiments showed that cure temperatures can be decreased in products that have a cure time to achieve equivalent cure times at low temperatures. The results obtained are in principle consistent with the applicant's expectations based on the equation
Arrhenius.
In addition to those examples described in detail, the following examples were made to ensure that the carbohydrate reagent and the polyamine can comprise a wide range of alternatives.
<td>Example</td><td>Polyamine</td><td>Reagent carbohydrate</td><td>Binder formed</td>
<td> 9</td><td>hexamethylenediamine</td><td>dextrose</td><td>Yes</td>
<td> 10</td><td>ethylenediamine</td><td>dextrose</td><td>Yes</td>
<td> 11</td><td>diethylenetriamine</td><td>dextrose</td><td>Yes</td>
<td> 12</td><td>hexamethylenediamine</td><td>Corn syrup high fructose</td><td>Yes</td>
<td> 13</td><td>hexamethylenediamine</td><td>saccharose</td><td>Yes</td>
<td> 14</td><td>octamethylenediamine</td><td>dextrose</td><td>Yes</td>
<img file="MX339649B_D0037.tif" />
Example 16: A suspension of 56.08 g of deionized water, 7.15 g of dextrose monohydrate, and 3.5 g of
1,12-diaminododecane was acidified with 11N HCI to pH 1.0, and heated to 70 ° C with stirring resulting in a clear, colorless solution. The solution forms a thermoset polymer, insoluble in water at 160 ° C. (Test condition: 2 g of binder solution are applied on a filter pad that is placed in a humidity balance. The filter pad is heated for 15 min at 160 ° C.) An extract from the cured filter pad with 100 g of deionized water is essentially colorless.
Example 17: A solution of 8.25 g of dextrose monohydrate, and 2.50 g 1,5-diamino-2-methylpentane (Dytek A,
Invista) dissolved in 56.08 g of deionized water forms a thermoset polymer insoluble in water at 160 ° C. (Test condition: 2 g of binder solution is applied on a filter pad that is placed on a moisture balance.
The filter pad is heated for 15 min at 160 ° C.) An extract from the cured filter pad with 100 g of deionized water is essentially colorless.
Example 18: A solution of 8.03 g 'í INSTITUTO MEXICANO. ·; (\ Dextrose, and 2.70 g of N- (3-aminopropyl) -l ·., 3-pgb ^^ g ^ g ^ dissolved in 56.08 g of water deionized fo rm ^ μη ρ o1í me rn thermostable insoluble in water, at 200 ° C. (Test condition: 2 g of binder solution is applied on a filter pad which is placed in a humidity balance.
The filter pad is heated for 15 min at 200 ° C.) An extract from the cured filter pad with 100 g of deionized water has a yellowish color.
Example 19: A solution of 3 g of dextrose (0.016 mol) and 0.5 g of hexamethylenediamine (0.004 mol) was prepared, which was dissolved in 9 mL of deionized water. This reaction mixture was heated at 100 ° C for 1 hour before 0.7 g of dithiothreitol (0.004 mol) was added to the mixture which was left on a filter pad, this filter pad was heated to 125 ° C. A brownish, water-insoluble polymer formed on the filter pad.
Example 20: A solution of 3 g dextrose (0.016 mol) and 0.5 g hexamethylenediamine (0.004 mol) was prepared, which was dissolved in 9 mL of deionized water. This reaction mixture was heated at 100 ° C for 1 hour before 0.52 g of butanedithiol (0.004 mol) was added to the mixture which was left on a filter pad, this filter pad was heated to 125 ° C. A brownish inorganic polymer formed on the filter pad.
<img file="MX339649B_D0038.tif" />
Procedure for analysis of a binder sample with gas pyrolysis. Approximately 10 g of a cured product that has the binder thereon is placed in a test tube, the tube of which is then heated to 1000 ° F (538 ° C) for 2.5 minutes at which time the dome space is sampled and analyzed by gas chromatography / mass spectrometry (GC / MS) under the following 10 conditions: Oven, 50 ° C for one minute - 10 ° C / minute at 300 ° C for 10 minutes; inlet, 280 ° C division; Column, HP-5 30mm x 0.32mm x 0.25um; flow column, 1.11 mL / minute Helium; Detector, MSD 280 ° C; injection volume, 1 mL; detector mode, scanner 34-700 amu; threshold, 50; and sampling rate,
22 sweeps / second. A computer search of the mass spectrum of a chromatographic peak in the sample is done against the Wiley collection of mass spectra. The best combination is reported. A quality index (closeness of the combination to the spectra of the collection) is generated in a range from 0 to 99. Only the identification of peaks with a quality index greater than or equal to 90 is reported.
datoj
<img file="MX339649B_D0039.tif" />
MEXICAN INSTITUTE. . FROM THE jr analysis:
The following table provides the representative one would expect of the gaseous compounds produced during the —ene · melanoidin based binder composition.
<td>Holding time (min)</td><td>ID attempt</td><td>% peak area</td>
<td> 1.15</td><td>2-cyclopenten-l-one</td><td> 10.67</td>
<td> 1.34</td><td>2,5-dimethyl-furan</td><td> 5.84</td>
<td> 3.54</td><td>Furan</td><td> 2.15</td>
<td> 3.60</td><td>3-methyl-2,5-furandione</td><td> 3.93</td>
<td> 4.07</td><td>Phenol</td><td> 0.38</td>
<td> 4.89</td><td>2,3-dimethyl-2- cyclopenten-l-one</td><td> 1.24</td>
<td> 5.11</td><td>2-methyl phenol</td><td> 1.19</td>
<td> 5.42</td><td>4-methyl phenol</td><td> 2.17</td>
<td> 6.46</td><td>2,4-dimethyl-phenol</td><td> 1.13</td>
<td> 10.57</td><td>dimethylphthalate</td><td> 0.97</td>
<td> 17.89</td><td>Octadecanoic acid</td><td> 1.00</td>
<td> 22.75</td><td>erucilamide</td><td> 9.72</td>
Below is a list of the species observed in gas chromatography mass spectrometry (Py GC-MS) pyrolysis of a binder sample prepared using hexamethylenediamine as the polyamine component. Pyrolysis was carried out at 200 ° C, 300 ° C, and 770 ° C. Fingerprints showed a very important peak corresponding to acetic acid on mass chromatography at both 200 ° C and 300 ° C, which was not seen in a sample made using dextrose and ammonium sulfate (see Comparative Example 3), in which the significant volatile was SO2, particularly at
<img file="MX339649B_D0040.tif" />
C, the observed peaks, in order of time d increase were assigned as follows: A: Co-elution C5H2, C<sub>5</sub>Hi<sub>2</sub>, acetone, possibly low pm acetic acid ester; B:
CsH<sub>8</sub> diene; C: C5H8 diene; D: probably a pentanol; AND:
C<sub>6</sub>H<sub>12</sub> - a methyl pentene; F: hexane; G: methylcyclopentane; H:
a cyclohexadiene; I: CgHio - probably a methylcyclopentane; J: benzene; K: acetic acid; L:
cyclohexene; M: probably nonanol; N: 2-methyl-3pentanone; 0: 2,5-dimethylfuran; Q: C7H10 + co-elute unassigned; Q: pyridine + co-elute unassigned; A: toluene; S:
possibly ten-year + co-elute unassigned; T: 2-ethyl-5methylfuran; U: a methyl pyridine; V: a methyl pyrrole; W:
a xylene; X: unassigned - with alcohol functionality; AND:
not assigned; Z: a xylene + co-elute unassigned; AA: unassigned; AB: a dimethyl pyrrole; AC: a dimethyl pyridine;
AD: a dimethyl pyridine; AE: unassigned; AF: unassigned;
AG: a pyrrole methyl ethyl + co-elute unassigned; AI: an unassigned but distinct mass spectrum (containing N), related pyrrole; AJ: an unassigned but with a different mass spectrum (containing N), possibly an acetamide;
AK: an unassigned but distinct mass spectrum (containing N), related pyrrole; AL: an unassigned but with a different mass spectrum (containing N), pyrrole
<img file="MX339649B_D0041.tif" />
related; AM: a mass spectrum without PM ¥ I<sup>p</sup>
INSTITUTO MEXICANO different (Containing N), related pyrrole.
mass spectrum seen from AI to AM peaks. Ven .. come — in.
data from preamps that do not have the polyamine component.
Procedure for evaluating dry and cured tensile strength. When evaluated for its dry and cured tensile strength, shell bone compositions containing glass beads prepared with a given binder provided an indication of the probable tensile strength and probable durability, respectively, of a product of fiberglass prepared with that particular binder. The predicted durability is based on the cured tensile strength of the shell bone: dry tensile strength ratio. Shell bones are prepared, cured, and tested as follows, for example, for a hexamethylenediamine-dextrose binder mixture.
A shell bone mold (Dietert Foundry Testing Equipment; Heated Shell Curing Accessory, Model 366, and Shell
Mold Accessory) is set to a desired temperature, usually 425 'F (797 ° C), and allowed to warm up for at least one hour. While the shell bone mold is heating, approximately 100 g of an aqueous binder (generally 15% solids binder) is prepared (for example as described in Example 7). Using a large glass beaker, 727.5 g glass beads (Quality'-BallptÍftij-fenpaet. IMPiSCR ..
Beads, Spec. AD, US Sieve 70-140, 106-212
INDUETIJÁt
Potters Industries, Inc.) are weighed by difference. The glass beads are poured into a clean, dry mixing bowl, the bowl of which was mounted on an electrical mixing rack.
Approximately 75 g of aqueous binder is poured onto the glass beads in the mixing bowl. The electric mixer is then turned on and the glass beads / binder mix is stirred for one minute. Using a large spatula, the sides of the whisk (mixer) are scraped to remove any of the lumps of binder, while also scraping the edges where the glass beads are at the bottom of the bowl. The mixer is then turned back on for an additional minute, and when the beater (mixer) is removed from the unit, followed by removal of the mixing bowl containing the glass beads / binder mixture. Using a large spatula, remove as much of the binder and as many glass beads attached to the beater (mixer) as possible, stir and stir in the glass beads / binder mix in the mixing bowl. The sides of the bowl are then scraped to mix in any excess binder that has accumulated on the sides. At this point, the binder mixture of
IMPI®
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY is considered as
<img file="MX339649B_D0042.tif" />
Contents19
45 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45
33 members in 14 offices
Priority claims9
| Document | Office | Kind | Date |
|---|---|---|---|
| 33245210 | United States of America | P | |
| 33245210 | United States of America | P | |
| 61332452 | United States of America | – | |
| 2011057364 | European Patent Office (EPO) | W | |
| 2011057364 | European Patent Office (EPO) | W | |
| 61332452 | – | – | – |
| PCTEP2011057364 | – | – | – |
| US20100332452P | – | – | – |
| WO2011EP57364 | – | – | – |
Members33
| Document | Office | Kind | |
|---|---|---|---|
| CA2797148A1 | Canada | A1 | |
| WO2011138459A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2011249760A1 | Australia | A1 | |
| US2013047888A1 | United States of America | A1 | |
| EP2566903A1 | European Patent Office (EPO) | A1 | |
| CN103025777A | China | A | |
| EA201291192A1 | Eurasian Patent Organization (EAPO) | A1 | |
| MX2012012635A | Mexico | A | |
| JP2013525586A | Japan | A | |
| KR20130092961A | Republic of Korea | A | |
| CL2012003124A1 | Chile | A1 | |
| AU2011249760B2 | Australia | B2 | |
| AU2015200758A1 | Australia | A1 | |
| JP2016000829A | Japan | A | |
| CN103025777B | China | B | |
| MX339649BThis record | Mexico | B | |
| BR112012028526A2 | Brazil | A2 | |
| JP5992903B2 | Japan | B2 | |
| US9493603B2 | United States of America | B2 | |
| US2017015694A1 | United States of America | A1 | |
| EA025774B1 | Eurasian Patent Organization (EAPO) | B1 | |
| MY160846A | Malaysia | A | |
| CA2797148C | Canada | C | |
| KR101835899B1 | Republic of Korea | B1 | |
| US2019352323A1 | United States of America | A1 | |
| BR112012028526B1 | Brazil | B1 | |
| US10913760B2 | United States of America | B2 | |
| PH12012502182A1 | Philippines | A1 | |
| EP2566903B1 | European Patent Office (EPO) | B1 | |
| US2021230201A1 | United States of America | A1 | |
| US2023203080A1 | United States of America | A1 | |
| US12054514B2 | United States of America | B2 | |
| US2024391943A1 | United States of America | A1 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 339649
- Publication, DOCDB
- 339649
- Publication, EPODOC
- MX339649
- Application
- 2012012635
- Application, DOCDB
- 2012012635
- Application, EPODOC
- MX2012012635
Titles
- Spanish
- AGLUTINANTES DE CARBOHIDRATO Y MATERIALES HECHOS CON LOS MISMOS.
Classification
- CPC, 9
- C07H5/06
- C08F251/00
- C08G12/00
- C08G14/00
- C03C25/25
- C08G16/00
- C08G83/00
- C08J5/04
- D21H19/12
- IPC, 3
- C08G12 00
- C08G14 00
- C08G16 00